text:
Lubbock shoppers back in stores looking for Black Friday deals
By Joshua Ramirez
Published: Nov. 25, 2022 at 10:13 PM CST
LUBBOCK, Texas (KCBD) - You did not have to travel far to see shoppers taking advantage of Black Friday deals.
Many Lubbock stores opened early to help customers check boxes off their Christmas lists, but the day after Thanksgiving has changed some in recent years.
One shopper, Julie Bynum, says she still misses the way Black Friday was before COVID.
"We miss the days when the mall was open overnight," Bynum said. "That was really awesome. We would just pull all nighters."
But one thing remains the same, with big appetites come big deals, and the biggest retail holiday of the year - Black Friday is returning to its post-pandemic popularity.
"My sister-in-law and I have been partners in crime doing Black Friday for over 12 years now," Bynum said. "We always hit all the stores, end up at the mall, and just have a great time."
With COVID-19 putting a damper on the retail holiday since 2020, Bynum says she's happy her family tradition is back to normal.
"As much as any turkey and dressing," Bynum said. "We get out our little note pads and make notes about what stores we're going to, what things we're gonna go for. We always have good luck, and we always spend more than we thought we would, but it's fun."
Bynum started her holiday shopping spree at 5 a.m., before sun up and says she is successfully checking names off her nice list ahead of Christmas Day.
"At least 20 gifts, lots of people, it's a really big family so it's fun to buy for them," Bynum said.
Bynum is staying tight-lipped about her purchases, though, preserving those special surprises for Christmas morning.
"What if they watch the TV and then they're gonna know what they got for Christmas," Bynum said.
Bynum says she made multiple trips home to unload, but she and her family won't be slowing down on this Black Friday.
"We're gonna go all day," Bynum said. "So 20 stores or more."
Copyright 2022 KCBD. All rights reserved.
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An opportunity to witness "fromacorn to seat" in the conversion of oak round timber (oak tree butts) into unique designed oak garden furniture through an informed guided tour and demonstrations. The tour will include round timber origins, grades and conversion into planks, seasoning, construction, demonstrations, waste products and uses. Additional woodland crafts will be displayed as part of the tour including charcoal making and chair bodging, plus a Steam engine with sawing platform.
Guided tours start at 10.30am and 2pm only. Refreshments available.
Meet at: Norbury Park Wood Products, Norbury Park Estate, Mickleham, RH5 6DN Venue signposted on the day from the main roads.


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Cory Gallant & The Red Dirt Posse @ Confederation Centre [POSTPONED]
Join Cory Gallant & The Red Dirt Posse for their Confederation Centre debut. Seating is limited. Tickets $10 each (non-refundable, includes all fees).
Location: 145 Richmond St, Charlottetown, PE C1A 1J1, Canada (Map)
Price: C$10
For more information about the Confederation Centre
PEI's Cory Gallant began 2021 with the honour of having his latest single "Easily Addicted" as the #1 song in the Canadian Indie Country Countdown's Top-100 of 2020, which is fan voted. The tune also was #18 on Indie Radio Airplay (across all genres) Top 100 of 2020 (as reported by Canadian Online Radio Charts).
His rich, soul-filled vocals helped gain him national exposure through CBC Searchlight, the ECMA's, and the Canadian Country Music Association. He has two Music PEI nominations this year, for FACTOR Song of the Year ("Easily Addicted") and Digital Achievement of the Year. Last year, Cory received Music PEI's Entertainer of the Year and New Artist of the Year awards. He also received an ECMA nomination for Country Recording of the Year.
The Island native's country roots run deep, being raised on the outlaw sounds of Waylon Jennings, George Jones, and Merle Haggard. He is still just as passionate about the genre to this day. While pursuing his dream to be a full-time musician, Cory supports his wife and three daughters as a first responder.

redpajama_set_name: RedPajamaCommonCrawl


Because talking about mental illness shouldn't be taboo.
Kids are more precious than gems. So it's our responsibility to do everything we can to make sure they're happy–well, except for when we ground them. But as much as we hate it, we can't always make our kids feel happy, or worse, prevent them from developing a mental illness. Which is why there's one thing kids need to do: learn about mental health…just in case mental health takes a turn for the worse and our ever-lasting hugs can't seem to make it better. And this isn't exclusive for kids who have mental illnesses; all kids need to not only know how to handle negative thoughts, but also how to be sensitive to others who may be struggling.
Kristen Legault-Donkers, an 18-year-old from St. Thomas, Ontario, is an inspiration to us all. She's written four children's books on mental health, which are based on her own experiences with depression and anxiety growing up. All in hopes of teaching children how to cope with mental illness. The books even come with an information page of local mental health resources for those struggling, so they're pretty great learning tools.
Each book (Zoey Has Very Glum Days, Zoey Has Worry Thoughts, Zack's Moods Are Like A Roller Coaster and Zack, The Very Busy Kid), explores a serious mental illness: depression, anxiety, bipolar disorder and ADHD.
Lagault-Donkers' website explains how each book accomplishes tasks like describing the symptoms of the illness, stressing how important medication and counselling are and suggests ways to talk about their feelings to their family and friends. Lagault-Donkers may be young, but she's about to change the lives of countless children and teens for the better.
There'll be a book launch for her children's mental health series this Saturday at 1 p.m. to 4 p.m. at Pinafore Park in St. Thomas, Ontario. You can also buy Lagault-Donkers' books here for $12.99/book.


Weddings are about many things. Friends, family, loved ones, laughter, tears, nostalgia, joy, and of course, fun!
Don't forget booze either. Only the good stuff of course! Prosecco. Champers. You know the drill.
When I photograph a wedding I capture all these things, and I find that every wedding is absolutely unique even if I've photographed at a venue many times before.
So what makes weddings unique? It's all about the people, innit? I always feel very honoured to photograph weddings, because I'm allowed into a couple's inner circle and become their friend for the day.
Here are some of my favorite photographs I've been lucky enough to capture as a wedding photographer (and a few from some cracking engagement sessions too). If you'd like to see more, please check out my featured weddings page, or contact me to arrange a chat about your wedding!


DECHEMA | EuroPACT 2017, 10-12.05.
EUROPACT 2017 is the fourth European Conference on Process Analytics and Control Technology.
The conference will cover new technologies in process analytics, the implementation of these technologies in various fields and the transformation of data into knowledge. The conference will be supported by an exhibition of instrumentation, applications and data evaluation tools.
EUROPACT 2017 provides a meeting and a discussion forum for scientists and users of process analytics from academia and industry. The conference programme will include plenary lectures and discussion during poster sessions.
The conference takes place 10-12 May 2017 in Potsdam (nearby Berlin), Germany.


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Hensley & Co., also known as Hensley Beverage Company, is an Anheuser-Busch beer wholesaler and distributor headquartered in the West Phoenix area of Phoenix, Arizona.  Its market territory covers nearly the entire state of Arizona.  As of 2007 it was the third-largest Anheuser-Busch distributor in the United States and one of the largest privately held companies in Arizona.

The company was founded in 1955 by Arizona businessman Jim Hensley and steadily grew based upon population growth in the region and a close arrangement with Anheuser-Busch.  Following Hensley's death in 2000, his daughter Cindy Hensley McCain became the controlling owner.  At the height of prominence of her husband, U.S. Senator and two-time presidential candidate John McCain, Hensley & Co. was arguably the best-known beer distributorship in America.  Previously focused on marketing to the Phoenix, Tempe, and Prescott Valley areas, its size and scope increased significantly with the 2016 acquisition of Tucson-based Golden Eagle Distributors.  Hensley Beverage Company maintains an active presence in the Phoenix area in terms of sponsorships and charitable giving.  Its representatives have held high positions in several city and state business groups and the company is active in political discussions that affect the industry.

History
The company was founded in January 1955 by Arizona businessman Jim Hensley  on a $10,000 loan. It originally had 12 workers, sold 73,000 cases of beer a year (a case typically being twenty-four 12-oz. bottles or cans), and had a 6 percent market share.  While it initially handled many brands of beer, Hensley accepted an offer later in 1955 to become Anheuser-Busch's sole distributor for Maricopa County in return for selling only that brand.  Under the names Hensley & Company Distributors and Hensley & Company Wholesale, the company saw decades of steady growth, aided by the Phoenix area becoming one of the fastest-growing regions of the country while the company still maintained exclusivity with Anheuser-Busch.  Jim Hensley's tireless sales efforts and the generous wages and benefits he gave employees were also key success factors. Hensley & Co. was the first Anheuser-Busch distributor to invest in refrigerated warehouses, which subsequently became standard in the industry.  By 1970, Hensley & Co. had a 20 percent market share; by 1980, that had grown to 50 percent, the business had become quite successful, and Jim Hensley was a multi-millionaire.

In 1981, Jim Hensley's new son-in-law John McCain, recently married to daughter Cindy Hensley McCain and retired from the United States Navy, was hired as Vice President of Public Relations.  McCain soon left to begin his Congressional career.  In 1993, the company consolidated operations under the name Hensley & Company.

Robert Delgado, who had been with the company since 1975, was named president in 1994—assuming day-to-day control of the business—and later was named CEO, while Jim Hensley remained chairman.  The company also acquired real estate throughout Arizona.  John McCain's son Andrew, from his first marriage, joined the firm around 1997; his MBA and banking experience would lead to his becoming the company's CFO and COO, and in 2017, President.

At the time of his death in 2000, Jim Hensley held most of the voting stock. Annual revenues were over $220 million on 20 million cases of beer sold.  Cindy Hensley McCain, who had been a vice president, became the controlling stockholder—she, her children, and Andrew McCain together control 68 percent of the company—and chair of the board.  As chair, she consults remotely with Delgado on major initiatives such as new products, new plants, employee welfare, or charitable giving.  She is considered by Anheuser-Busch to be an absentee owner, and Delgado is required to have complete control over business operations and investment decisions.  Anheuser-Busch inquired about buying the distributorship in the early 2000s, preferring not to have absentee owners, but she declined (all their U.S. beer distributorships are privately owned).

By 2007 Hensley employed 650 people, sold about 23 million cases of beer a year to over 5,000 retail accounts producing revenues of $340 million, and held 60 percent or more market share in its target area.  Beverage industry analysts estimated the company's value in 2008 at  more than $250 million.  Despite the late-2000s recession, which resulted in a rare decline in sales volume, revenues rose slightly to $350 million by 2009 and employment was still 650 in 2010.  It subsequently rose to 800 by 2015.  The company said it had record revenues in 2014 but did not disclose the amount.  The company's workforce was dominated by men in their twenties.  The company's facilities included its own printing shop.  It operated a fleet of some 750 trucks and other vehicles and conducts its own training program for commercial driver's licenses.

The company's Phoenix distribution plant occupies a number of acres, marked by a giant Budweiser sign.  In addition to beer, Hensley also distributes energy drinks, root beer, liquor, and wine, some of which are distributed from a warehouse in Tucson.  The move into wine was accelerated by the acquisition of Phoenix-based Quench Fine Wines Ltd. in 2010.  Via the holding company King Aviation, Hensley owns and operates Cessna Citation Excel aircraft.  Over half the beer sold in the Phoenix area is Anheuser-Busch, making it one of their better markets nationally.  Both companies benefit when major sports events are held in the area, such as Super Bowl XLIX.  The beer distribution business and its Phoenix market is very competitive; some Anheuser-Busch distributors eventually ended their exclusive arrangements with the beer maker, and for a while Hensley had no plans to do so.  However, in 2009 it did, in part related to Hensley's move into craft beers, an emerging force in the market.  Hensley worked with Four Peaks Brewery among others.   By 2015 Hensley sold some 850 drinks and brands from around the world and had around 8,000 retail customers in the Phoenix area.

In 2016 Hensley acquired another family-owned Arizona firm, Golden Eagle Distributors, based in Tucson and founded  in 1974 by Bill Clements.  Cindy McCain said, "My father was very, very close with the founders of Golden Eagle. He always considered them good businessmen and women, and patriots to the state of Arizona. ... Arizona is a family and keeping that business in the family was important to me.  I didn't want to see someone from outside Arizona come in and do it."  The deal increased the number of Hensley employees to over 1,200, its fleet size to over 1,100, and for the first time gave Hensley distribution to virtually the entire state of Arizona.

During the COVID-19 pandemic in the United States, Hensley Beverage Company faced the challenges associated with kegs of beer in the distribution channel reaching their expiration date due to the bars and restaurants that normally sell beer on tap being shut down.

Political activities

Between 1982 and 2000, the company contributed $80,000 to John McCain's political campaigns; from 2001 to 2006, the company and its employees would contribute an additional $24,000.  In Congress, McCain recused himself on legislation involving alcohol issues.

In the late 1980s, Jim Hensley was active in legislative battles against neo-prohibitionist movements.  In 1992, a former Anheuser-Busch lobbyist accused Hensley & Co. of illegal "bundling" of contributions to state legislators.  Hensley denied the claim, which was later withdrawn by the lobbyist with no charges filed.

Hensley & Co. holds a seat on the board of the National Beer Wholesalers Association, and company spokesperson Douglas Yonko is the association's Arizona director. Company executives have contributed heavily to the association's funding.  Hensley executives have been active in successfully convincing the Alcohol and Tobacco Tax and Trade Bureau to not require alcohol content displays for beer labels.  In the early 2000s, Hensley sought unsuccessfully to keep liquor makers from entering the flavored malt beverage market, while it began distributing such beverages itself, including Anheuser-Busch's Tilt.  During the 2010s, Hensley supported proposed state legislation that, within the rigid three-tier framework of producers, distributors, and retailers,  would relax production caps on craft breweries with respect to how much beer they can make and "self-distribute", in the belief that such relief would help such breweries grow bigger and eventually need Hensley's distribution services.

Hensley & Co. has continued to be a strong presence in Arizona politics, opposing liquor tax increases in all circumstances, including those targeted for childhood education and children's hospitals.  Yonko has also been an officer of the Arizona Chamber of Commerce & Industry, which backed John McCain's successful bid for re-election in 2010.  In 2008, Andrew McCain was chairman of the Greater Phoenix Chamber of Commerce, where he focused the group's attention on the state's budget deficit, possible transportation initiatives, and immigration reform.

Like many businesses in the state, Hensley got caught up in the controversy surrounding the Arizona SB 1070 anti-illegal immigration law, with the group Somos America advocating a boycott of Hensley until the company denounced the law.  The company called the action "an obvious cheap political stunt motivated solely by self promotion" and said that "Hensley Beverage Company/Budweiser will continue to embrace and encourage the wonderful diversity of our state".  The boycott gained little attention.  Later that year, Hensley and Delgado joined the Partnership for a New American Economy, an effort started by Michael Bloomberg to push towards comprehensive immigration reform, and in early 2011 Delgado signed a letter from a number of Arizona CEOs directed at Arizona State Senator Russell Pearce requesting that the legislature back off any more anti-illegal immigration measures.

Community involvements
Hensley engages in various local sports sponsorships, including for Phoenix International Raceway.  Andrew McCain has served on the board of directors of the Fiesta Bowl and for 2014–15 was named chairman of the bowl.

Hensley is a major contributor to charity in the Phoenix metropolitan area, donating about $1 million per year to various causes and starting the Hensley Employee Foundation in 2001.  In addition, the company has helped promote safe ride businesses in an effort to avoid drunk driving incidents.  Another event is the Budweiser Shootout Golf Tournament, held in conjunction with the Arizona State University Hispanic Business Alumni since 1991, which has raised over $1 million for Latino student scholarships in the area.  Hensley & Co. has also been a supporter of the Phoenix gay community, sponsoring events by the Phoenix Lesbian and Gay Pride Committee, and Cindy McCain and her daughter Meghan McCain were outspoken proponents of the NOH8 Campaign.

References

Distribution companies of the United States
Companies based in Phoenix, Arizona
Food and drink companies established in 1955
Drink companies of the United States
Food and drink companies based in Arizona
1955 establishments in Arizona

redpajama_set_name: RedPajamaWikipedia


text:
Fort William, 2 And 11 Seaview Terrace
Recording Your Heritage Online
Flats (19th Century), Terrace (19th Century), Transport Workers House (19th Century)
Site Name Fort William, 2 And 11 Seaview Terrace
Classification Flats (19th Century), Terrace (19th Century), Transport Workers House (19th Century)
Site Number NN07SE 26
NGR NN 09964 73576
Council Highland
Parish Ardgour
Former Region Highland
Former District Lochaber
Former County Argyll
1-12 Seaview Terrace, 1890s. Former railway workers' houses, three blocks of four flats in a stepped terrace of polychrome brick, prettier than those at Mallaig, with gabletted porches to their front elevations and door canopies on decorative cast iron brackets to their rear. At the terrace's end, the rare survival of a communal laundry building with distinctive flue.
Taken from "Western Seaboard: An Illustrated Architectural Guide", by Mary Miers, 2008. Published by the Rutland Press http://www.rias.org.uk


text:
NEW – Standards & guidance
Providing evidence-based guidance and standards for the whole of the dental profession promotes high-quality practice and patient care.
We set the authoritative standards and guidance for general dental practice, inherited from FGDP. Digital copies are available below free of charge, together with the College's own guidance, for the benefit of all dental professionals and their patients.
We are also producing a series of webinars about our guidance and standards publications, in partnership with ProDental CPD, which are free to view live for all members of the dental professions. Visit our events page to find out what's coming soon.
Sign up to our monthly newsletter to be informed of new and updated publications, upcoming webinars and recent webinar recordings.
An introduction to research for primary dental care clinicians
An Introduction to Research for Primary Dental Care Clinicians introduces the principles of research methodology, discusses the relevance of research to primary dental care, and provides an overview of the different stages in a research project.
Antimicrobial prescribing in dentistry
Antimicrobial Prescribing in Dentistry gives clear, simple and practical guidance to dentists on when to prescribe antimicrobials, what to prescribe, for how long and at what dosage.
The Antimicrobial Prescribing Self-Audit Tool, co-published with the British Dental Association and endorsed by Public Health England, helps dental prescribers to complete a clinical audit of their antimicrobial prescribing and management of dental infections, and to compare audited practice against the guidance.
Further resources are available in the Dental Antimicrobial Stewardship Toolkit, which was developed by the FGDP(UK), the British Dental Association and the Dental Sub-Group of Public Health England's English surveillance programme for antimicrobial utilisation and resistance (ESPAUR).
Clinical examination and record-keeping
Clinical Examination and Record-Keeping is a complete reference guide to record-keeping and examination, including history-taking, consent, confidentiality, data protection and more.
Dementia-friendly dentistry
Dementia-Friendly Dentistry enables dental professionals to understand dementia and its implications for dental practice, and adapt their patient management and clinical decisions accordingly.
Guidance notes for dental practitioners on the safe use of X-ray equipment
Sets standards for the safe use of x-ray equipment within dental practice in line with the Ionising Radiation Regulations 2017 (IRR17) and Ionising Radiation (Medical Exposure) Regulations 2017 (IRMER17).
Implications of COVID-19 for the safe management of general dental practice
Our COVID-19 guidance supports dental professionals to take a risk-based, evidence-based approach to providing safe general dental care, and looking after team wellbeing, in the current circumstances.
Selection criteria for dental radiography
Selection Criteria for Dental Radiography is the leading guideline on indications for radiographic investigation, covering treatment planning and monitoring, ionising radiation regulations and best practice.
Standards in dentistry
Standards in Dentistry is a comprehensive collection of standards and guidelines for primary dental care.
Training standards in implant dentistry
Training Standards in Implant Dentistry summarises the training that should be undertaken to carry out implant dentistry safely, and the standards which should be met by training courses.
CGDent & FGDP(UK) update COVID-19 guidance synopsis
The Faculty of General Dental Practice UK and College of General Dentistry have published an updated synopsis of their guidance…
College of General Dentistry endorses FGDP(UK) and PHE revised guidance on radiation protection
The second edition of Guidance Notes for Dental Practitioners on the Safe use of X-ray Equipment sets standards of good…
Dental Fallow Time Calculator launched
A new free-to-use Fallow Time Calculator has been launched to enable dental professionals to determine, justify and record the fallow period necessary…
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Company Registration No. 2586636 | Registered Charity No. 1002769


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\section{Introduction}

Hole doping of $\rm La_{2-x}Sr_{x}CuO_{4}$ is described in the
Zhang-Rice singlet (ZRS)-upper Hubbard band (UHB) model for
$0<x\lesssim 0.2$ as ZRS states on in-plane oxygen atoms. These
holes are visible as a feature in X-ray absorption spectroscopy
(XAS) at the O K edge, called the mobile carrier peak (MCP). The MCP
gains intensity with doping at the expense of LHB (lower Hubbard
band) states and concurrent ``spectral weight transfer" from UHB
states. This model, expanding the Cu $d_{x^{2}-y^{2}}$ one-band
Mott-Hubbard model to the Cu $d_{x^{2}-y^{2}}$, O $p_x$, O $p_y$
three bands of the $\rm CuO_{2}$ planes, describes well the
variation, observed with XAS at the O K edge, of unoccupied density
of states in cuprates for relatively low doping ($x\lesssim
0.2$)~\cite{1991Eskes,1991Chen}.

However, the variation of the maximum critical temperature $\rm
T_{c,max}$ between different superconducting compounds cannot be
explained within the UHB-ZRS model and its in-plane orbitals only
and possible extensions of the model to out-of-plane orbitals have
been intensively investigated. Since there can be only one Fermi
surface for an isolated $\rm CuO_2$ plane, other indications of the
relevance of out-of-plane orbitals came from angle-resolved
photoemission (ARPES) measurements of square- and diamond-shaped
Fermi surfaces for $\rm La_{2}CuO_4$ (Ref. 3) and $\rm
Ca_{2}CuO_{2}Cl_{2}$ (Ref. 4). The most relevant out-of-plane
orbital that hybridizes with states in the $\rm CuO_{2}$ plane is
the apical oxygen $p_{z}$ orbital mixed with the Cu
$3d_{3z^{2}-r^{2}}$ (Refs. 5,6) or $4s$ (Ref. 7) orbital in the $\rm
CuO_{2}$ planes. The occupation of the apical oxygen orbitals
modifies the bond valence sums and was used to explain general
trends of $\rm T_{c,max}$.~\cite{1990deLeeuw, 1991Ohta} The effect
of apical oxygen $p_z$ energy level on parameters of an expanded
$t-J$ model has been considered for different
materials.~\cite{2009Yin} In contrast, the axial hybrid between the
O $p_z$ and Cu $4s$ orbitals, with $\rm Cu$
$d_{3z^{2}-r^{2}}$-states occupied, has been addressed in Ref. 7.
These calculations predicted that an empty apical oxygen $p_z$
orbital modifies the in-plane hole hopping parameter $t'$ between
sites along the orthorhombic axes, consistent with ARPES
measurements, with a suppressed $t'$ from the presence of unoccupied
apical oxygen orbitals correlating with a smaller $\rm
T_{c,max}$.~\cite{2009Yin, 2001Pavarini, 1996Raimondi}

In addition, the depletion of the UHB states in bulk $\rm
La_{2-x}Sr_{x}CuO_{4}$ at $x\sim 0.2$,~\cite{1991Chen} shows that
the ZRS-UHB model also needs to be modified to describe the hole
doping for higher $x$. However, because of limits of bulk crystal
growth, doping dependence studies have been limited to doping near
$x=2$, realized in bulk $\rm Sr_{2}CuO_{4-\delta}$ with a very large
$\rm
T_c$,~\cite{2006Yang,1994Al-Mamouri,1999Choy,1994Shimakawa,1995Zhang,2007Yang,2009Geballe}
where the oxygen atoms are removed from the structure ($\delta >
0$), and for relatively low $x$, near the superconducting dome,
where there is evidence of a qualitative change with $x$ in the
doping process near $x_{optimal}$. Specifically, the effective Cu
ion magnetic moment in $\rm La_{2-x}Sr_{x}CuO_4$ and the magnetic
exchange between Cu spins are strongly reduced~\cite{1989Johnston}
at $x\sim 0.2$ and the $T$-independent Pauli paramagnetism is
replaced at $x\sim 0.22$ by $T$-dependent Curie paramagnetism with
increased doping.~\cite{2005Wakimoto}
Calculations~\cite{1991DiCastro, 1992Feiner} suggested that the
doping mechanism is different for $x
> x_{optimal}$, as the number of $a_{1}$-symmetry states, related to
the Cu $3d_{3z^{2}-r^{2}}$ orbital~\cite{2009Yin} and exceeding the
optimal doping $x_{optimal}$, correlated with $\rm T_{c,max}$. A
small but growing contribution from apical oxygen $p_z$ orbital
holes mixed with Cu $d_{3z^{2}-r^{2}}$ orbitals at MCP was inferred
from angle-resolved XAS measurements~\cite{1992Chen} and from the
variation of the Cu-apical oxygen distance with
doping~\cite{2005Bozin}, which also correlates with a variation in
$\rm T_{c}$.~\cite{2009Butko,2003Karimoto} Recently, a saturation of
the XAS MCP intensity with increasing doping near $x_{optimal}$ was
observed~\cite{2009Peets} and dynamical mean-field theory
calculations~\cite{2010Millis} concluded that either additional
orbitals become relevant in this doping range or that new model
parameters would be needed to account for multiple-hole
interactions. The additional orbital or band to consider in the $\rm
La_{2-x}Sr_{x}CuO_{4}$ hole doping process between $x \sim 0.2$ and
$x \sim 2$ is not known.

\begin{figure}
\centering\rotatebox{0}{\includegraphics[scale=0.65]{FIG1.eps}}
\caption{\label{fig:Figure1} (Color online) (a) Measurements before
and after ozone annealing (OA) show that all SL are superconducting.
The inset shows a sketch of one SL superperiod. The atomic planes
within the SCO and LCO layers are shown in Fig. 6(a). (b) Hard X-ray
reflectivity characterization ($E=8.05~\rm keV$). The sharp peak at
$2\theta \approx 14^{\circ}$ is the substrate (002) reflection peak,
with $\rm c_{LSAO}=12.64~\AA$.~\cite{2009Butko} Using this peak as a
reference marker, HXD measurements showed that the average ML
thickness was $\rm 6.64~\AA$, $\rm 6.63~\AA$ and $\rm 6.59~\AA$ for
SL-A, SL-B and SL-C, respectively. The difference is consistent with
the thicknesses of the SCO and LCO layers in each SL and the larger
$c$-axis parameter of SCO films $\rm
c_{SCO}=13.55~\AA$~\cite{2003Karimoto} compared to that of LCO films
$\rm c_{LCO}=13.3~\AA$. Superlattices with smaller LCO layer
thickness in a superperiod (not shown) had less good growth. The
inset shows the epitaxial growth, where $\rm
a_{LSAO}=3.76~\AA$.~\cite{2009Butko} (c) Characterization with soft
X-rays near the La edge ($E=832~\rm eV$). The dotted lines show the
evolution of the SL peaks with superperiod
thickness.~\cite{1942Hendricks} Inset shows L scans at MCP and SHP
energies (Sec. II D). The difference at L=3 between MCP and SHP
amplitudes is also visible in Fig. 4.}
\end{figure}

In this study, doping in the range $1 \lesssim x \lesssim 1.5$,
inaccessible with bulk crystal growth techniques, was obtained with
$\rm Sr_{2}CuO_{4-\delta}-La_{2}CuO_4$ (SCO-LCO) superlattice (SL)
growth. We observed that occupations of two distinct oxygen hole
states are gradually modified with doping. Using the interference of
the SL reflections with the surface reflection, we determined that
the two hole states are maximized in different layers. This suggests
that the states emptied preferentially in the SCO layers are the
additional states in the extension of the ZRS-UHB model to this
doping range.

\section{Experiments}

\subsection{Superlattice structure}

The superlattice samples were grown by molecular beam epitaxy on
$\rm LaSrAlO_4$ (LSAO) substrates at Brookhaven National Laboratory.
Three SL, called SL-A, SL-B and SL-C in the following, were chosen
after atomic force microscopy (AFM) and hard X-ray diffraction (HXD)
measurements. HXD measurements [Fig. 1(b)] were made using a Philips
X' Pert diffractometer. From a Nelson-Riley fitting, the number of
layers in one superperiod for SL-A and SL-C is $N=7.81\pm 0.1~\rm
ML$ and $N=9.27\pm 0.3~\rm ML$ respectively, where $\rm
1~ML~(``molecular ~layer")$ is the average d-spacing of one SL
``formula-unit" layer (half the unit cell), given by the (002)
reflection. The SL structure was further characterized with resonant
soft X-ray scattering (RSXS) measurements at beamline X1B at the
National Synchrotron Light Source. Reflectivity measurements near
the La edge [Fig. 1(c)] for $Q=(0,0,Q_{z})$, where $Q_{z}=2\pi
L/c_{SL}$ is the scattering momentum in units of SL superperiod
$c_{SL}$, show superperiods with an integer number of layers,
$N=8~\rm ML$ and $N=9~\rm ML$ for SL-A and SL-C respectively,
consistent with the HXD measurements. The slightly worse SL-B has
$N=7.8~\rm ML$. The thickness of the SCO layers within a SL
superperiod is $N_{SCO}\approx 2~\rm ML$ for all samples, but
somewhat larger for SL-A compared to SL-B or SL-C, because of larger
doping (Sec. II B). The number of repeats was 8, 7 and 8 for SL-A,
SL-B and SL-C, respectively. A sketch of one SL superperiod is shown
in Fig. 1(a) (inset).

The superconducting critical temperatures from AC susceptibility
measurements were 25 K for SL-A, 38/39.5 K for for SL-B and 14/36.5
K for SL-C, where the first and second values for SL-B and SL-C are
for measurements before and after ozone annealing at $\rm
350~^{\circ} C$ for $20$ min [Fig. 1(a)]. AFM images were taken on a
Dimension 3100 instrument. They showed a surface covered by islands
approximately 150 nm wide and 2 nm high for SL-B (data not shown);
SL-A or SL-C did not have these features. The AFM surface RMS
roughnesses $\sigma_{s}$ for SL-A, SL-B and SL-C were 0.61 nm, 0.76
nm, and 0.43 nm, respectively.

\begin{figure}
\centering\rotatebox{0}{\includegraphics[scale=0.55]{FIG2.eps}}
\caption{\label{fig:Figure3} (Color online) (a) Superlattice
fluorescence yields differ at the MCP and SHP energies only. The
relative intensities of the MCP peaks in fluorescence yield make it
clear that SL-A has more Sr than SL-B and SL-C. Since the LSAO
substrate SHP is smaller than that of either SL, sampling more
substrate FY in SL-A measurements (SL-A is thinner than SL-C) cannot
explain the higher SHP intensity. The inset shows for comparison FY
for bulk $\rm La_{2-x}Ba_{x}CuO_4$ (with $x=0.125$), $\rm
La_{2}CuO_{4+\delta}$ (with $\delta=0.12$) and $\rm
Na_{x}Ca_{2-x}CuO_{2}Cl_{2}$ (with $x=0.08$). (b) Angle-resolved
fluorescence yield on SL-A. The measurements have been aligned at
525 eV and 560 eV. Inset shows the measurement geometry. The
detector angle $2\theta$ was kept fixed at $110^{\circ}$.}
\end{figure}

The interface roughness can be characterized with HXD reflectivity.
The $L=1$ reflection width [Fig. 1(b)], dominated by the total SL
thickness and not sufficiently sensitive to small-scale roughness,
was approximately the same for all SL. However, the $L=2$ linewidth
was the same for SL-A and SL-C and $9~\%$ higher for SL-B. Also, the
$I(L=2)/I(L=1)$ ratio was the same for SL-A and SL-C and $23~\%$
smaller for SL-B. These observations suggest that SL-A or SL-C have
a smaller interface roughness than SL-B, consistent with the AFM and
superperiod measurements. In addition, although the surface
roughness $\sigma_{s}$ of SL-A is larger than that of SL-C, their
interface roughnesses $\sigma_{i}$ are similar. This will be used to
explain the difference in scattering at the O edge between SL-A and
SL-C (Sec. III B). For an estimate of the $\rm Sr$ doping range we
use a SL interface RMS roughness $\sigma_{i}\sim \rm 6~\AA$. The
maximum Sr doping is estimated with either a ``flat-top" or a
Poisson distribution as $x_{max} \sim 1.5$ and $x_{max} \sim 1$ for
a SL with 2 ML and 3 ML thick SCO layers, respectively, outside the
current possibilities of bulk crystal growth. Therefore, the middle
nominally SCO layer in a 3 ML thick SCO layer is approximately $\rm
La_{0.5}Sr_{1.5}CuO_{4}$ and the two nominally SCO layers in a 2 ML
thick SCO layer are approximately $\rm LaSrCuO_{4}$. The shorthand
notation ``SCO" and ``LCO" from the deposition sequence will
continue to be used for simplicity for the SL layers. Our
conclusions do not depend on the exact values of SCO and LCO layer
thickness or interface roughness.

\subsection{Oxygen edge fluorescence yield}

The first indication of hole doping at two distinct energies comes
from XAS measurements with fluorescence yield (FY) detection and
$\pi$-polarized incident light, made at beamline X1B at the National
Synchrotron Light Source. The sample and detector angles were
$\theta = 80^{\circ}$ and $2\theta=110^{\circ}$ respectively,
defined as shown in Fig. 2(b) (inset). SL measurements are shown in
Fig. 2(a). FY of bulk $\rm La_{2-x}Sr_{x}CuO_{4}$ (LSCO) has three
main low-energy features~\cite{1991Chen}: the MCP of the ZRS state,
the UHB feature and a peak called here the ``second hole peak"
(SHP). The highest peak at $\rm 536.1~eV$, sometimes associated with
orbitals mixed with La states~\cite{1991Kuiper}, is followed by
``continuum oscillations". There is no clearly discernible UHB peak
in SL FY. The UHB intensity in bulk LSCO is
negligible~\cite{1991Chen} for $x> 0.15$; therefore, the nominally
undoped LCO layers in the SL are instead thoroughly doped with MCP
holes (the occupation factor $\langle t_{l,LCO}^{MCP}\rangle
>0.15$), consistent with estimates based on roughness and hole
diffusion length~\cite{2009S}.

\begin{figure}
\centering\rotatebox{0}{\includegraphics[scale=0.75]{FIG3.eps}}
\caption{\label{fig:Figure4} (Color online) (a) Reflectivity at the
La edge for SL-A. The plots have been shifted vertically for
clarity. Inset: FY for SL-A and SL-C. The only clear difference in
FY is an increase in the overall height, consistent with a larger
number of La atoms in SL-C. The two lower curves are the LSAO
substrate FY and reflectivity at $\theta=60^{\circ}$, showing the
strong resonant increase in the substrate reflectivity. The
difference from measurements on SL is due to the absence of SL
scattering contrast $\delta f_{SL}$ (Sec. III A). (b) Line shapes at
the Cu edge. For intermediate conditions the scattering line shape
is flat: this is observed for SL-C at L=4 (not shown). The
two-dimensional profile has a saddle point for L=1: it is a peak
when scanning $L$ (inset) and a dip when scanning $E$. This is in
contrast to multiple-scattering effects in HXD that can be observed
for certain oxide SL, where a dip is present at integer $L$ instead
of a peak (data not shown). The lower curves compare the FY for SL-A
(full symbols) and SL-C (open circles).}
\end{figure}

The SL FY spectra in Fig. 2(a) have been aligned below and above the
edge. The alignment normalizes out the variation in the number of
oxygen atoms and therefore, the remaining differences between FY
spectra are due to electronic contrast from the difference in
valences of oxygen atoms. For SL-A and SL-C this occurs exclusively
at MCP and SHP energies. Therefore, the SHP peak is related to
doping of oxygen states, not to a structural defect, e. g. a vacancy
or interstitial oxygen. Further support for this interpretation
comes from FY measurements of bulk LSAO, where the SHP peak is
observed (Fig. 2); since LSAO has no vacancies or interstitial
atoms, SHP cannot be related to these defects. This is also
consistent with the observation that SL-A has a larger SHP intensity
than SL-C, while compounds without apical oxygen atoms, e. g. NCCOC,
have a smaller intensity at SHP [Fig. 2(a), inset]. These FY results
are a clear indication that the ZRS-UHB model extension in our
doping range beyond the MCP and UHB levels is related to SHP and not
to the vacancies of bulk SCO.

The SHP energy is relatively insensitive to the type of oxygen
neighbors. For instance, it is not influenced by the Cu $d$ states
since $\rm Al^{3+}$ in LSAO has no $d$ states or by replacing La
with Sr. The FY increase from SL-C to SL-A is at the same energy
(SHP) as the energy of a peak of the undoped LCO compound, which
suggests that the SHP state, partly empty in undoped LCO, is
gradually emptied further, rather then removed, with additional hole
doping in SL-A compared to SL-C; that is, doping also makes holes at
SHP. Therefore, the total numbers of MCP and SHP holes in one
superperiod are related by the charge conservation equation as
$\sum_{l}\langle t_{l}^{MCP}\rangle+\sum_{l} \langle
t_{l}^{SHP}\rangle=2N_{\rm SCO}$, where $l$ sums over one
superperiod, $N_{\rm SCO}$ is the number of SCO layers and $2N_{\rm
SCO}$ is the total number of doped holes in one superperiod (each
$\rm Sr_{2}CuO_{4-\delta}$ layer dopes 2 holes when $\delta \approx
0$).

Knowledge of the SCO oxygen vacancy site would suggest the site of
SHP; however, the question of the vacancy site is not
settled.~\cite{2009Geballe} The absence of this feature in the
cuprate NCCOC, which does not have the apical oxygen (Fig. 2),
suggests that SHP is an apical oxygen state. It is possible that SHP
is absent in NCCOC for other reasons than the absence of the apical
oxygen. For instance, in an alternative view of angle-resolved FY
measurements on bulk LNO~\cite{1991Kuiper,1998Kuiper}, SHP are
considered in-plane oxygen states mixed with Ni, and polarized
in-plane. However, the SHP energy is not influenced by the Cu $d$
states or replacing La with Sr, which suggests various
hybridizations are not essential. The incipient out-of-plane doping
for low $x$ (Refs. 2, 22) supports the view that doping is not
confined to the $\rm CuO_{2}$ planes for high $x$. Indeed, more
detailed early calculations of the $\rm La_{2-x}Sr_{x}CuO_4$
system~\cite{1988Guo} suggested that the shift with doping in the
relative alignment of the in-plane [O(1)] oxygen and apical [O(2)]
oxygen ionization potentials will eventually lead to the
preferential emptying of the apical oxygen orbitals at larger $x$.
If SHP is an apical state, the Cu ions would be surrounded by holes
on all six neighboring oxygen atoms. This transition to a gradual
emptying of apical oxygen orbitals, balancing the valences of all
six oxygen atoms near a Cu site (this hole distribution is seen in
undoped $\rm La_{2}NiO_{4}$~\cite{1991Kuiper}) is a sensible
intermediate step toward the process of vacancy creation in SCO.
This kind of change with doping in the site of the doped holes has
been seen in other cuprates, for instance in $\rm
YBa_{2}Cu_{3}O_{6+\delta}$, where the holes stay in chains in Cu and
O orbitals up to $\delta \sim 0.25$, only then doping the oxygen
states in the $\rm CuO_{2}$ planes.~\cite{2006Liang,2011Hawthorn}

To address the question of the orientation of the state behind SHP,
angle-resolved FY measurements have been made. A quantitative
analysis of the angular dependence of FY requires measurements on
bulk crystals cut at a series of angles with respect to the
crystallographic planes, to account for footprint and
self-absorption effects~\cite{1993Eisebitt}. Superlattice samples
cannot be grown at arbitrary angles. However, the SL footprint
effects are almost identical for MCP and SHP energies because of the
very similar scattering geometry. Self-absorption effects would have
to be very strong for the observed suppression of intensity at SHP.
That SL self-absorption effects are relatively small is supported by
the very small difference in the momentum linewidth between MCP and
SHP [Fig. 1(c), inset], which shows that the entire SL is probed at
both energies. In addition, the O edge step height is approximately
the same before the alignment in Fig. 2(b), which also suggests that
self-absorption effects are relatively small at the O edge.

The MCP and SHP intensities follow a similar angular dependence
[Fig. 2(b)]. We assume that the SHP state can be associated with a
single orbital (if localized) or a collection of orbitals of the
same type (if delocalized, as for the ZRS state, corresponding to
MCP), in which case the SHP state would correspond to a band of a
specific symmetry. The similar variation with angle of MCP and SHP
intensity in angle-resolved FY measurements [Fig. 2(b)] suggests
that the state corresponding to the SHP energy is oriented as the
in-plane ZRS. Also, the MCP and SHP scattering amplitudes remain
similar over a wide angular range (Fig. 4), which would be difficult
to explain if they were polarized in different directions.
Therefore, our data provide evidence that SHP is a state at the
apical oxygen site polarized in the $a-b$ plane. There are three
relevant apical oxygen orbitals: $p_z$ pointing to the Cu in the
neighboring $\rm CuO_{2}$ plane, $p_{x,y}$ pointing to Sr or La in
the same LaO plane and $p_z$ pointing to the Sr or La in the
neighboring LaO plane. The only possibility consistent with this
interpretation is the orbital pointing to the La atoms in the same
LaO plane.

\subsection{Fluorescence yield and scattering at the La and Cu edges}

RSXS can measure
bulk~\cite{2002Abbamonte,2004Abbamonte,2005Abbamonte} and
SL~\cite{2007S,2009S,S-LNOLCO} charge order. SL scattering
measurements were made with $\pi$-polarized light at beamline X1B in
an UHV diffractometer. Before the more complex SL reflectivity at
the O edge, we present the measurements at the La and Cu edges,
which will be used to illustrate the model of Sec. III A.

FY measurements at the La $\rm M_5$ edge for SL-A and SL-C are shown
in Fig. 3(a). The scattering contrast between the SL layers from
$L=1$ to $L=7$, $\delta f^{(\rm La)}_{SL}=(f_{SCO}-f_{LCO})\bigg
|_{\rm La~edge}$, is given mainly by the difference between the
number of La atoms in the LCO and SCO layers, $\langle
t_{l,LCO}^{La} \rangle$ and $\langle t_{l,SCO}^{La} \rangle$.
Consistent with this observation, there is a large non-resonant tail
in scattering at the La edge for SL peaks, which was used to
characterize the SL structure [Fig. 1(c)]. The line shape in Fig.
3(a) is approximately the same for different $L$ because of the
relatively small contribution from the surface reflectivity compared
to the SL reflection (Sec. III A).

FY measurements at the Cu edge [Fig. 3(b)] are very similar for SL-A
and SL-C; the scattering contrast at this edge is given by a small
difference in the Cu valence, $\delta f^{(\rm
Cu)}_{SL}=(f_{SCO}-f_{LCO})\bigg |_{\rm Cu~edge}$, the difference in
the dispersion corrections at the Cu edge between the SCO and LCO
layers. Even for the SL higher doping levels, holes do not appear to
empty unusual Cu states, unlike the case of
YBCO.~\cite{2011Hawthorn} Small SL imperfections shift the peaks
from integer values. The line shape changes with $L$ from a dip on
resonance (low $L$) to a peak (high $L$). This change is not due to
absorption (the calculated absorption depth is much larger than the
SL thickness), refraction (from two-dimensional profiles, data not
shown) or multiple-scattering at low $L$ (similar effects are seen
at high $L$ in manganite SL, data not shown).

\begin{figure}
\centering\rotatebox{0}{\includegraphics[scale=0.7]{FIG4.eps}}
\caption{\label{fig:Figure5} (Color online) Line shapes at constant
$L$ for different SL peaks (solid line), compared to substrate
reflectivity (dotted line) at the O edge, for SL-A (a-c) and SL-C
(d-g). Results on SL-B (not shown) were similar to those for SL-A,
supporting the observation that small structural irregularities do
not affect our conclusions. The scans have been normalized to unity
below the edge. SL-A and SL-C have different scattering line shapes
at high $L$ because of different SL roughness and structure (Sec.
III B). Measurements on the substrate, approximating the surface
reflectivity $S_0$ (Sec. III A), show that the surface reflectivity
resonant contribution gets negligible at higher $L$, where the
substrate reflectivity becomes more featureless. Vertical dashed
lines are guides to the eye.}
\end{figure}

\subsection{Scattering at the O edge}

RSXS measurements at the O edge (Figs. 4 and 5) probe the spatial
distribution of holes in the SL. Consistent with FY measurements
(Sec. II B), the absence of a scattering peak at UHB shows that the
UHB states have been uniformly removed in all layers. The scattering
contrast in Fig. 4 occurs mostly at the two energies (MCP and SHP),
where SL-A and SL-C differed in the FY (Fig. 2). Because scattering
peaks at SL reflections (Fig. 5), the charge density is modulated at
MCP and SHP energies between SCO and LCO layers of the SL.

Sharpening of the features is observed at higher $L$ (Fig. 4). The
MCP and SHP peaks are well-separated (the additional splitting of
the MCP in SL-C will be discussed in Sec. III B). It is difficult to
explain this clear separation with a difference in the energy of the
same MCP hole state in the LCO and SCO layers, given the inherent
interface roughness of the structure. This is strong evidence for
considering SHP a qualitatively distinct hole state.

The low L line shapes for SL-A, SL-B (not shown) and SL-C are more
similar than the high L line shapes because of the reduced
importance of roughness (Sec. III B). At low L, the energy profiles
show increased intensity between MCP and SHP [Figs. 4 and 5(a)],
unlike the La $\rm M_5$ and $\rm M_4$ edges (Fig. 3). Although the O
edge line shapes are more complex, they can be qualitatively
analyzed with the same model as for the La and Cu edges (Sec. III
A). The difference in the MCP and SHP line shapes at low $L$ is due
to different interference conditions with the surface reflection
(Sec. III B).

Vacancies are present~\cite{2009Geballe} in bulk SCO as well as at
certain interfaces, even when the bulk materials do not contain
vacancies.~\cite{2006Nakagawa} If there were vacancies in the SCO
layers or at interfaces, these would give a peak in scattering at
all O edge energies. However, we do not observe large features above
the SHP energy that would indicate a structural difference (either
vacancies or oxygen atoms at interstitial sites), between the LCO
and SCO layers (Fig. 5). Since the samples were annealed in ozone,
the SCO layer thickness is relatively small, and there is little SL
scattering at the O edge other than at MCP and SHP (Fig. 5), we will
neglect vacancies in the following analysis, that is $\delta \approx
0$. The number of oxygen atoms is approximately the same throughout
the SL, while their valence is different in the SCO and LCO layers,
giving the scattering contrast. Therefore, SL scattering at the MCP
and SHP energies probes the difference between SCO and LCO layers
form factors $\delta f^{(\rm MCP, SHP)}_{SL}=(f_{SCO}-f_{LCO})\bigg
| _{\omega=\rm MCP, SHP}$, measuring the change in the dispersion
corrections with doping.

\section{Discussion}

\subsection{Scattering model}

To analyze the line shapes at the O edge, we develop a model for the
interference between the surface and a SL reflection. The X-ray
scattering intensity is $I=A|S|^2$ , with the structure factor given
by:
\begin{eqnarray}
S(\omega, Q)=\sum_{l,n}{f_{n}(\omega, Q) t^{n}_{l} e^{iQz_{l}}}
\end{eqnarray}
\noindent where $\omega$ is the incident X-ray energy, $Q=(0,0,2\pi
L/c_{SL})$ is the scattering momentum in the reflectivity geometry,
and $t_{l}^{n}$ is the occupation factor in atomic plane $l$ of
element and valence $n$.~\cite{S-LNOLCO} The form factor $f(\omega,
Q)$ for soft X-ray momenta is $f(\omega,
Q)=f^{0}(Q)+f'(\omega)+if''(\omega) \approx
f^{0}(0)+f'(\omega)+if''(\omega)$. For only one source of scatterers
($n=1$), the variables $\omega$ and $Q$ in the structure factor
$S(\omega, Q)$ are separable, that is $S(\omega, Q)=g(\omega)h(Q)$.
This implies identical line shapes (up to an overall scaling factor)
for the same edge at all $L$. This is not observed at the Cu edge or
for the MCP state [Figs. 3(a) and 4]. Therefore, at least two
scattering sources, interfering in the total structure factor
$S(\omega, L)$, need to be considered. ``Stray light" only
contributes an overall background level. To interfere, the
contributions to $S(\omega, L)$ must be coherent and of the same
energy.

With the above approximation for $f(\omega, Q)$, the structure
factor for more than one type of scatterer (the condition of a SL)
becomes:
\begin{eqnarray}
S^{ij}(\omega, L)=\sum_{n}f_{n}^{ij}(\omega) \sum_{l}\langle
t^{n}_{l}\rangle e^{2\pi iLz_{l}/c_{SL}}
\end{eqnarray}
\noindent where $\rho^{n}(L)=\sum_{l}\langle t^{n}_{l}\rangle
e^{2\pi iLz_{l}/c_{SL}}$ is the Fourier transform of the
distribution $\{ \langle t^{n}_{l}\rangle \}$ of in-plane averages
of the occupation factors for layer $l$ and element and valence $n$.
Considering only two elements, $n=\rm A$ and $n=\rm B$ as an
example, and $\langle t^{\rm A}_{l}\rangle+\langle t^{\rm
B}_{l}\rangle=1$ for all $l$, we obtain a total structure factor
$S^{ij}(\omega, L)=S_{0}^{ij}+S_{SL}^{ij}$ made of two terms:
\begin{eqnarray}
S_{0}^{ij}=\bigg( f_{\rm A}^{ij}\frac{N_{\rm A}}{N}+f_{\rm
B}^{ij}\frac{N_{\rm B}}{N} \bigg
)\rho_{0,SL}=f_{0,SL}^{ij}\rho_{0,SL}
\end{eqnarray}
\noindent and
\begin{eqnarray}
S_{SL}^{ij}=(f_{\rm B}^{ij}-f_{\rm A}^{ij})\bigg [ \rho^{\rm
(B)}_{SL}\frac{N_{\rm A}}{N}-\rho^{\rm (A)}_{SL}\frac{N_{\rm B}}{N}
\bigg ] =\delta f_{SL}^{ij} \rho_{SL}
\end{eqnarray}
\noindent where $N_{\rm A}$, $N_{\rm B}$, $N=N_{\rm A}+N_{\rm B}$
are the number of ML in one A layer, one B layer and one
superperiod, $f_{0,SL}^{ij}$ is the average of the SL layers form
factors, $\delta f_{SL}^{ij}=f_{\rm B}^{ij}-f_{\rm A}^{ij}$ is the
contrast between the form factors of the SL layers, and the
substrate contribution has been neglected.

\begin{figure}
\centering\rotatebox{0}{\includegraphics[scale=0.7]{FIG5.eps}}
\caption{\label{fig:Figure6} (Color online) Two-dimensional plots in
variables energy $E$ and momentum $L$ for two selected SL peaks. (a)
Scattering two-dimensional resonance profile (logarithmic scale) for
SL-C near L=2 at the O edge shows the mirror symmetry of the MCP and
SHP scattering line shapes. Same results were obtained for SL-A and
SL-B. (b) Scattering two-dimensional resonance profile (logarithmic
scale) for SL-C near L=4 at the O edge shows that the MCP and SHP
holes are qualitatively different.}
\end{figure}

A complex oxide SL has more than two constitutive elements. We
neglect for soft X-ray momenta the small difference in $z_{l}$
between the $\rm SrO/LaO$ and $\rm CuO_{2}$ planes, or equivalently
between oxygen sites O(1) (in-plane) and O(2) (apical), within 1 ML.
In this case, $f_{0}$ becomes the average total form factor and Eqs.
3-4 can be applied by replacing $\rho^{\rm (A,B)}_{SL}$ with
$\rho^{\rm (LCO,SCO)}_{SL}$, $N_{\rm A,B}$ with $N_{\rm LCO,SCO}$,
and $f_{\rm A,B}$ with $f_{\rm LCO,SCO}$, the total form factors of
1 ML.

The indices $i$ and $j$ are dotted with the light polarization
vectors $\widehat{\epsilon}_{final}$ and
$\widehat{\epsilon}_{initial}$ as
$f=\widehat{\epsilon}^{*}_{i,final}f^{ij}\widehat{\epsilon}_{j,initial}$.
Only the in-plane $f^{xx}$ remains at the Cu edge, at MCP, as well
as at SHP from the similar angular dependence of FY (Sec. II B). In
this case, the angular dependence given by the double product
simplifies to $S \propto
\widehat{\epsilon}^{*}_{i,final}f^{ij}\widehat{\epsilon}_{j,initial}
\propto f^{xx}\rm sin^{2}(\theta)$, with an additional factor [$\rm
sin^{2}(\theta)$] that can be absorbed into the arbitrary units.

The momentum dependence of $S_{0}$ and $S_{SL}$ in Eqs. 3-4 is
contained in the functions $\rho_{0,SL}$, $\rho^{\rm (LCO)}_{SL}$
and $\rho^{\rm (SCO)}_{SL}$. For a SCO-LCO superlattice with no
roughness, they are ($r$ is the number of repeats):
\begin{eqnarray}
\rho_{0,SL}=\sum_{l, All} e^{2 \pi iLz_{l}/c_{SL}}=\frac{1-e^{2\pi i
Lr}}{1-e^{2 \pi iL/N}} \\
\rho^{\rm (LCO)}_{SL}=\sum_{l, LCO} e^{2\pi iLz_{l}/c_{SL}}
\end{eqnarray}
\noindent and
\begin{eqnarray}
\rho^{\rm (SCO)}_{SL}=\sum_{l, SCO} e^{2\pi
iLz_{l}/c_{SL}}=\rho_{0,SL}-\rho^{\rm (LCO)}_{SL}
\end{eqnarray}
\noindent Except near $L=mN$, where $m$ is an integer, the functions
$\rho^{\rm (LCO)}_{SL}$ and $\rho^{\rm (SCO)}_{SL}$ are related as
$\rho^{\rm (LCO)}_{SL} \approx -\rho^{\rm (SCO)}_{SL}$. Therefore,
they are out-of-phase:
\begin{eqnarray}
\rm {Arg}[\rho^{\rm (LCO)}_{SL}(L)]=\pi+\rm{Arg}[\rho^{\rm
(SCO)}_{SL}(L)]
\end{eqnarray}
\noindent where $\rm Arg[\rho_{SL}^{(LCO)}(L)]=\pi L \rm
(N_{LCO}-1)/N$.

The $S_{0}$ term in Eq. 3 gives the reflection from the
discontinuity in the index of refraction $n$, or equivalently in the
average form factor $f_{0,SL}$, at the sample surface. For a SCO-LCO
SL, $f_{0,SL}=\frac{N_{\rm LCO}}{N}(2f_{\rm La})+\frac{N_{\rm
SCO}}{N}(2f_{\rm Sr})+f_{\rm Cu}+ 4f_{\rm O}$, which can be
calculated from tabulated~\cite{1993Henke} values. $f_{0,SL}$ is
made mostly of non-resonant terms at the Cu and O edges (but not at
the La edge~\cite{INPREP}) and, because of this, does not depend
strongly on energy or polarization. Considering the substrate
extends the sum in Eq. 2 to an infinite number of layers, with the
function $\rho_{0,SL}$ replaced by $\rho_{0}(L)=1/(1-e^{2 \pi
iL/N})$ and $f_{0,SL}$ replaced by $f_{0}=(1-\tau) f_{0,SL}+\tau
f_{0,LSAO}$, where $f_{0,LSAO}$ is the substrate contribution and
$\tau (\theta, 2\theta, \omega)$ is a weighting factor which depends
on the scattering geometry ($\theta, 2\theta$) and energy ($\omega$)
through a variable absorption depth.

\begin{figure}
\centering\rotatebox{0}{\includegraphics[scale=0.65]{FIG6.eps}}
\caption{\label{fig:Figure6} (Color online) (a) Sketch of the two
components in the structure factor $S$: the surface $S_{0}$, from
the discontinuity between the vacuum and the surface, and $S_{SL}$,
from the modulation $\delta f_{SL}$ between SCO and LCO layers. The
circles show the location of the MCP and SHP holes doped in the LCO
and SCO layers, if the SHP is scattering from a hole on an orbital
at the apical O(2) sites (Sec. II B). A few examples of atomic
planes in the SCO and LCO layers are indicated. (b) Calculations of
$|\rho_{SL,8}(L)|$ and $|\rho_{SL,1}(L)|$ for a $\rm [2\times
SCO+7\times LCO]$ SL with no roughness and 8 and 1 repeats, compared
to the surface $|\rho_{0}(L)|$.}
\end{figure}

The $S_{SL}$ term is the reflection from the SL modulation. The
modulation of the La and Sr numbers in the SL also gives modulations
of the form factors at the Cu ($\delta f^{(\rm Cu)}_{SL}$) and O
($\delta f^{(\rm MCP,SHP)}_{SL}$) edges. Therefore, the interference
at different edges will be analyzed in terms of two main components:
a SL reflection $S_{SL}$ and a surface reflection $S_{0}$ [Fig.
6(a)]. Fig. 6(b) shows the functions $|\rho_{0}(L)|$ and
$|\rho_{SL}(L)|$ for a $\rm 8\times [2\times SCO+7\times LCO]$
structure. The $L$ dependence of $|\rho_{0}|$ and $|\rho_{SL}|$ is
very different; while $|\rho_{0}|$ has peaks at $L = m N$, where $m$
is an integer, $|\rho_{SL}|$ follows a momentum dependence with
pronounced peaks at integer $L \neq m N$. $|\rho_{SL}|$ is therefore
much higher than $|\rho_{0}|$ at these $L$ values:
$|\rho_{SL}|>>|\rho_{0}|$. It would appear that the surface
reflection can be neglected near SL reflections. However, $|f_{0}|$
is considerably larger than $|\delta f_{SL}(\omega)|$ at certain
edges, with the SL and surface structure factors comparable in
magnitude $|S_{SL}| \sim |S_{0}|$.

Including both terms, the intensity of X-ray scattering can be
written as:
\begin{eqnarray}
I=A |\rho_{SL}|^2 \Bigg |\delta
f_{SL}+\frac{f_{0}\rho_{0}}{\rho_{SL}}\Bigg|^2 =A' \big|\delta
f_{SL}(\omega)+z_{L}\big|^2
\end{eqnarray}
with $|\rho_{SL}|^2$ (independent of $\omega$) absorbed into the
arbitrary units. It is not possible at present to calculate from
first principles the energy-dependent form factor $\delta
f_{SL}(\omega)$ for a correlated oxide SL. However, FY measurements
(Fig. 2) show that the energies of MCP and SHP do not depend on the
environment of the oxygen atom, which suggests a simplified model.
Therefore, the line shapes at different edges will be modeled with a
harmonic oscillator functional dependence. The function used for the
imaginary part of the form factor is $\delta
f_{SL}''(\omega)=\frac{\alpha E}{(E-E_{0})^2+\Gamma^2}$. This is
Kramers-Kronig transformed to obtain the real part $\delta
f_{SL}'(\omega)$ [Fig. 7(a)]. Fig. 7(b) shows $|\delta
f_{SL}+z_{L}|$ for different $z_{L}$.

The interference between the surface $S_{0}$ and superlattice
$S_{SL}$ terms can qualitatively describe the scattering line shapes
at all edges. At the La edge, $|\delta f^{\rm (La)}_{SL}|$ is
comparable to $|f_{0}|$, $|S_{SL}|>>|S_{0}|$ and little change of
the resonance line shapes with $L$ is expected. Indeed, there is
little change with $L$ at the La edge [Fig. 3(a)], except at low L.
Measurements on the substrate at the La edge [Fig. 3(a)] indicate a
strong resonance in $f_{0,LSAO}$, and therefore $f_{0}$, which is
responsible for the variation in the line shape at low $L$.
Refraction effects shift the peaks and complicate the interpretation
of the measurements at low $L$; because of this, the measurements at
the La edge will be discussed in detail separately.~\cite{INPREP}
The scattering line shape at the $\rm M_5$ and $\rm M_4$ edges has
the same shape because it originates in states on the same La atoms;
this is in contrast to the scattering at the O edge at low $L$,
where the line shape at the MCP and SHP resonances is different
(Sec. III B).

At the Cu edge, $\rm \delta f^{\rm (Cu)}_{SL}$ is the change in the
dispersion corrections with doping and, because of the small
modulation in the Cu valence, $|\delta f^{\rm (Cu)}_{SL}| <<
|f_{0}|$ and $|S_{SL}|<<|S_{0}|$. Strong interference effects are
expected and observed [Fig. 3(b)]. The scattering shows a strong
surface contribution to reflectivity. The non-resonant ($f_{0,SL}$
and $f_{0,LSAO}$) form factors have large imaginary parts $f_{0}''$
because of the neighboring La edge and the line shapes resemble
those of panels (2) and (8) in Fig. 7(b).

The O edge scattering, with $|S_{SL}|\sim |S_{0}|$, is an
intermediate case. $\rm \delta f^{\rm (MCP,SHP)}_{SL}$ is relatively
large and $f_{0}''$ is smaller than at the Cu edge, with the line
shapes in a different region of Fig. 7(b): for low $L$ the MCP and
SHP are of the type (4) and (6), for high $L$ of the type (5) and
(2). Scattering line shapes are the most variable, with large
complex changes with $L$. The scattering at the O edge is analyzed
in more detail in the next section.

\begin{figure}
\centering\rotatebox{0}{\includegraphics[scale=0.5]{FIG7.eps}}
\caption{\label{fig:Figure6} (Color online) (a) Functions $\delta
f''_{SL}$ and $\delta f'_{SL}$ obtained by Kramers-Kronig transform.
The parameters were $\alpha=2.5 \times 10^{-3}$ (top) and
$\alpha=-2.5 \times 10^{-3}$ (bottom), $E_{0}=528.5~\rm eV$ and
$\Gamma=1~\rm eV$. (b) Line shapes $|\delta f_{SL} + z_{L}|$
calculated for different interference conditions, arranged in the
$(z_{L}',z_{L}'')$ plane according to the $z_L$ term used, show the
variety of behaviors at the Cu edge [panels (2) and (8)], La edge
[panel (4)] and O edge [panels (4) and (6)].}
\end{figure}

\subsection{Locus of MCP and SHP scatterers}

Interference between the surface and the SL reflections determines
the line shape. This can be used to find the locus of the MCP and
SHP scatterers within the SL structure.

As pointed out, the functions $\delta f_{SL}^{(\rm MCP,SHP)}$ cannot
be calculated. However, the change with doping in the dispersion
corrections at MCP and SHP energies can be estimated by looking at
the difference in FY ($\delta f''_{FY}=f''_{SL-A}-f''_{SL-C}$)
between \emph{two} differently-doped \emph{SL}, which gives the
scattering contrast between SL \emph{layers} ($\delta
f''_{SL}=f''_{SCO}-f''_{LCO}$) in \emph{one} SL (either SL-A or
SL-C). Specifically, when comparing SL-A with SL-C, FY intensity
increases concurrently at MCP and SHP [Fig. 2(a)]. Therefore, for
both MCP and SHP energies, the difference in the dispersion
corrections in the SCO and LCO layers is positive:
\begin{eqnarray}
\delta f''_{SL} ({\rm MCP,SHP}) \propto \delta f''_{FY} ({\rm
MCP,SHP}) > 0
\end{eqnarray}
\noindent The Kramers-Kronig transform of a $\delta f''_{SL}>0$ peak
gives the shape shown in Fig. 7(a) (top panel) for $|\delta f_{SL}|
= |\delta f_{SL}'+i \delta f_{SL}''|$.

However, measurements show line shapes for the MCP and SHP states
with a mirror symmetry at $L=1$ and $L=2$ (Figs. 4 and 5). It is
necessary therefore to consider the contribution to scattering of
$z_{L}$, the other factor in Eq. 9. Measured line shapes for MCP [of
type (3)-(6)-(9), right side] and SHP [of type (1)-(4)-(7), left
side] are on opposite sides of the complex $(z'_{L},z''_{L})$ plane
in Fig. 7(b). Therefore, $z^{\rm (MCP,SHP)}_L$ for MCP and SHP have
opposite phases.

Considering the factors combined in $z^{\rm (MCP,SHP)}_{L}$, since
$\rho_{0}$ is the same at MCP and SHP, and $f_0$ cannot change sign
over the $\rm \sim 4~eV$ between the MCP to SHP energies, as
evidenced by the weak energy dependence of the substrate reflection
(Fig. 4) and the large non-resonant component of $f_{0}$, the
difference between $z^{\rm (MCP,SHP)}_{L}$ must be in $\rho^{\rm
(MCP,SHP)}_{SL}(L)$, the Fourier transforms of the distributions $\{
\langle t^{\rm (MCP)}_{l}\rangle \}$ and $\{ \langle t^{\rm
(SHP)}_{l}\rangle \}$ of the occupation factors at the two energies.
Because $z_{L}$ and $\rho_{SL}$ are inversely proportional,
$\rho_{SL}$ also has opposite phases at the MCP and SHP energies:
\begin{eqnarray}
\rm{Arg}[\rho^{\rm (MCP)}_{SL}(L)]=\pi+\rm{Arg}[\rho^{\rm
(SHP)}_{SL}(L)]
\end{eqnarray}
\noindent Therefore, the distributions $\rho^{\rm
(MCP,SHP)}_{SL}(L)$ are out-of-phase, with the spatial distributions
of the MCP and SHP holes (Eq. 11) related in the same way as the
spatial distributions of the LCO and SCO layers in the SL (Eq. 8).
Then, it is necessary that the MCP and SHP hole distributions peak
in different layers.

This conclusion, using measurements at low $L$, where roughness
effects are less important, is independent of the thickness of LCO
and SCO layers in one superperiod or roughness amplitude. Roughness
effects become more important at higher $L$, where the MCP and SHP
line shapes resemble line shapes closer to the origin of the complex
plane in Fig. 7(b). We consider the $L$ dependence of the intensity
in Eq. 9, contained in the $z_{L}$ phase and amplitude. The $z_L$
phases for the MCP and SHP holes follow those of the LCO and SCO
layers, which are linear functions of $L$: $\rm
{Arg}[z^{(LCO)}_{L}]=Arg[f_{0}]+\pi L N_{SCO}/N$ and $\rm
{Arg}[z^{(SCO)}_{L}]={Arg}[z^{LCO}_{L}] +\pi$. The other
contributing factor to the change in the line shape with $L$, is the
variation in the $z_{L}$ amplitude. For Gaussian roughness, the
ratio $|\rho_{0}/\rho_{SL}|$ in $|z_{L}|$ depends on the surface
$\sigma_{s}$ and the interface $\sigma_{i}$ roughness as
$|\rho_{0}/\rho_{SL}|=|\rho_{0}/\rho_{SL}|_{\rm ideal}R(Q_{z})$,
where $R(Q_{z})=e^{-(\sigma^{2}_{s}-\sigma^{2}_{i})Q^{2}_{z}/2}$ and
$Q_{z}=2\pi L/c_{SL}$. The factor $R(Q_{z})$ becomes increasingly
important at higher $L$. Therefore, the linear increase of the
$z_{L}$ phase with $L$ and the reduction in the amplitude of
$|z_{L}|=|z_{L}|_{\rm ideal}R(Q_{z})$ at higher $L$ for
$\sigma_{s}>\sigma_{i}$ combine to make the vector $z_L$ spiral
inward in the ($z_{L}'$, $z_{L}''$) plane of Fig. 7(b) with
increasing $L$, systematically sampling different line shapes at the
same edge.

Fig. 4(c) for SL-A, with the first peak in the split MCP almost
absent, shows the interference line shape in a slightly different
location in the plane of Fig. 7(b) than the location corresponding
to the line shape in Fig. 4(g) for SL-C, where both peaks are
visible at MCP. This divergence between measurements for SL-A and
SL-C with increasing $L$ (Fig. 4) can now be explained by
considering the different roughness of SL-A and SL-C. SL-A has a
larger surface $\sigma_{s}$ than SL-C (Sec. II A) but similar
interface roughness $\sigma_{i}$. Therefore, $R(Q)$ is smaller for
SL-A, which makes the end of the $z_{L}$ vectors for SL-A and SL-C
follow slightly different trajectories with increasing $L$ in the
plane of Fig. 7(b).

The interference between $S_{SL}$ and $S_{0}$, resembling
multi-wavelength anomalous diffraction in molecular crystallography,
allows determining the superlattice MCP and SHP hole distributions
on a relatively large scale. To confirm the FY measurements of Sec.
II B and the site of the SHP state within 1 ML, a fit with the
interference model of Sec. III A would be necessary for higher wave
vectors ($L>2$), giving better spatial resolution. In future work,
fitting the evolution of measured interference line shapes (Figs. 4
and 5) with $L$ would also allow obtaining $\delta f^{\rm
(MCP,SHP)}_{SL}$, $\sigma_{s}$ and the energy-dependent $\sigma_{i}$
(on which the $z_L$ amplitude depends), and $N_{\rm SCO}$ or $N_{\rm
LCO}$ (on which the $z_L$ phase depends).

The MCP and SHP hole distributions, maximized in different layers,
are consistent with the observation that the MCP holes are
mobile~\cite{2009S} and that remotely doping a new distinct type of
holes (SHP) in the LCO layers from the Sr in the SCO layers is an
unlikely strong long-range process. In contrast, the SHP holes
remain centered on the SCO layers. The relatively smaller number of
MCP holes in the SCO layers is consistent with the saturation of FY
in Ref. 25 and observations in Ref. 32, where the apical hole site
is favored at high doping. The distributions of MCP and SHP holes
are illustrated in Fig. 6(a).

\section{Conclusion}

Using X-ray absorption and resonant soft X-ray scattering, we found
that doping in SCO-LCO superlattices empties two distinct oxygen
hole states. The location of sub-surface scatterers within the
superlattice was determined using the interference with the surface
reflection, with the distributions of the two hole states maximized
in different layers.

X-ray absorption measurements suggest that the hole state at the
higher energy is on apical oxygen atoms and polarized in the $a-b$
plane. Since the creation of a vacancy removes two holes, this would
suggest that the vacancies in bulk SCO are at the apical sites as
well.

The increase in the density of the unoccupied states at SHP has to
come from an occupied state. Photoemission experiments to determine
if a change with doping occurs in the density of states of occupied
states that mirrors the change with doping seen at SHP in this study
would be interesting.

Calculations showed that making in-plane axial orbitals more
localized, by gradually spatially removing the apical oxygen atoms,
increases $\rm T_c$,~\cite{2001Pavarini} and that, conversely,
unoccupied apical oxygen $p_z$ orbitals lower $\rm T_c$. If similar
ideas are applied to the SHP state, the doping of SHP holes might be
responsible for the decrease of $T_c$ and the hole pair breaking at
$x>x_{optimal}$~\cite{1995Emery}, and their partial removal, with
the appearance of vacancies in SCO near $x=2$, for the high $T_{c}$
of bulk SCO.

\section{Acknowledgments}

We thank A. Gozar for useful discussions. This work was supported by
the Department of Energy: RSXS measurements by grant
DE-FG02-06ER46285, superlattice growth by MA-509-MACA, NSLS
facilities by DE-AC02-98CH10886, and MRL facilities by
DE-FG02-07ER46453 and DE-FG02-07ER46471. A. R. was also supported by
MOE AcRF Tier-2 grant (MOE2010-T2-2-121) and NRF CRP.

redpajama_set_name: RedPajamaArXiv


text:
World figure skating champions make Olympic season debuts this week
By Nick ZaccardiSep 18, 2017, 12:13 PM EDT
Nobody can accuse the last two male figure skating world champions of ducking the competition.
Yuzuru Hanyu and Javier Fernández, training partners who combined to win every global title since 2014, open their Olympic seasons by competing against each other this week.
The Japanese megastar and the Spanish trailblazer headline the Autumn Classic, a lower-level event in Quebec starting Thursday.
The men's short program is Friday (8:15 p.m. ET) and the free skate Saturday (8 ET). A live stream is here.
Showdowns like this are usually reserved for, at the earliest, the Grand Prix series in late October and November.
Hanyu and Fernández are very familiar with each other, having shared a coach in Canadian Brian Orser, the 1988 Olympic silver medalist, since 2012. They train in Toronto.
In that time, Hanyu became the first Japanese man to win an Olympic title (and the second teen from any nation to do it). He followed it up with world titles later in 2014 and this year.
Fernández achieved unfathomable success for a Spanish skater — world titles in 2015 and 2016, overtaking Hanyu in the free skate both times.
In PyeongChang, Hanyu can become the first man to repeat as Olympic champion since Dick Button in 1952. Fernández can become the third Spaniard to earn a Winter Olympic medal of any color in any sport, and the first since 1992.
But first they face off in Quebec.
Hanyu is the decided favorite after winning last season's world title by breaking his own free skate record score. He moved up from fifth after the short program, while Fernández dropped from first after the short to fourth.
However, Hanyu has proven beatable early in the season, losing his first two international events in 2014, then one of his first two in 2015 and 2016.
More pressure is on Fernández, who missed the podium at the two biggest events last season — worlds and the Grand Prix Final. He is 26 years old. Aside from Hanyu, every medalist at worlds and the Grand Prix Final was a teen.
Another world champion makes an international season debut this week — Russian Yevgenia Medvedeva.
She skates at the lower-level Nepela Trophy in Slovakia on Thursday and Saturday. The 17-year-old is on the longest major winning streak in singles skating in 30 years, having not lost since November 2015.
The Nepela field includes the only woman to beat Medvedeva in a senior competition — countrywoman Yelena Radionova. But Radionova faded to fifth at last year's Russian Championships and is in a battle just to make the Olympic team.
Medvedeva might better be judged against two women who aren't in Slovakia but won B-level events last week.
Alina Zagitova, 15 and the 2017 World junior champion, won her senior international debut in Italy with 218.46 points. That score would have won silver at last season's senior worlds.
Marin Honda, 16 and the 2016 World junior champion, won her senior international debut in Salt Lake City with 198.42 points.
VIDEO: Nathan Chen makes more history at season opener


Seventeen South African wines have been included in respected UK wine writer Matthew Jukes The Wine List 2007, The Top 250 Wines of the Year and Leopard's Leap The Lookour White 2006 was right there among them.
South Africa, Jukes writes, 'wins new places thanks to an ever-improving attitude and the ageing of their finest vineyards.'"
This is great news for us and follows other accolades that our wines have been receiving lately. In a nutshell, Leopard's Leap is being recognized as an exceptional wine that is surprisingly affordable. Or as we like to say, affordable luxury.


My sweet dog, Dusty, turned 13 years old this week and to celebrate, I made one of his favorite things—homemade treats. Don't get me wrong, he won't discriminate against the store-bought kind but there is just something about these oven-baked "cookies" that gets him super excited. I've been making the same recipe for years but have tweaked it a bit here and there.
The absolute best part about making these treats (besides how happy they make your best friend) is that you probably have most of the ingredients in your pantry right now. I have used applesauce in the past but because I didn't have any on hand, I substituted with canned pumpkin, found deep in the cupboard. You can also feel good about the fact that this recipe is much healthier than most dog treats available for sale at pet stores. But beware...the treats smell so good while baking, you may be tempted to eat them yourself! Try this easy recipe if you're tired of spending a fortune on dog treats but still want to spoil your pup.
Preheat oven to 350°. Add all ingredients in a bowl and mix thoroughly until dough forms.
Spread dough in a round cake pan and bake for 1 hour. Cool before serving. Keep in covered container for up to a week.
Roll out dough on floured surface with rolling pin and punch out bone shape with cookie cutter. Place on baking sheet covered with wax paper or foil. Bake 30 minutes, then flip cookie over and bake for another 30 minutes until crunchy and hard. Cool before serving. Keep in covered container for up to a week.


The Clean Eating August 2014 Book of the Month is Eating on the Wild Side: The Missing Link to Optimum Health by Jo Robinson. I give this book FIVE strawberries- an absolutely fascinating book.
Robinson examines the varieties of foods to determine which foods and which varieties are the healthiest. She also looks at the healthiest methods for preparation and when certain food need to be prepared in order to obtain the most nutrients.
In Eating on the Wild Side, You'll learn that sweet potatoes aren't in the potato (nightshade) family but in the morning glory family, that drinking a glass of beet juice before a run will help you run longer (due to the naturally occurring nitrates), that the outer leaves on lettuces are the most healthy because they make the most chlorophyll, and that broccoli loses most of it's phytonutrients within 24-hours of harvest – so grow your own or shop at the farmer's market and look for it on ice.
There's about million more gems like these in the book, so take a look for yourself and learn how to eat on the wild side.
Well, this post is later than I had planned, but better late than never! Summer is in full swing here in Northern California and it has been quite warm. School is out, the days are long, sunny, and beautiful, and the bounty of produce options leaves me like that heart googly eyed emoji.
nectarine season. And that summer squash will be coming to a zoodler near you! Here is the Spiralizer that I use to turn my zucchini into "noodles": Tri-Blade Vegetable Spiral Slicer, Strongest-Heaviest, Best Veggie Pasta Spaghetti Maker for Low Carb/Paleo/Gluten-Free Meals .
Happy June! Enjoy the bounty from the farmer's market!! Or join a CSA!
Jennifer Tyler Lee suggests serving strawberry sauce on pancakes instead of syrup. I LOVE that idea. I also had sliced strawberries in a turkey sandwich with arugula (think: turkey and cranberry sauce) at an amazing place called Centrally Grown in Cambria, CA.
Wild berries and heirloom varieties have more nutritional value and more phytonutrients.
picked ripe. This also means that if your strawberry has traveled some distance to arrive to you, they are being picked when only three-quarters ripe.
Most supermarket berries are large, firm, white-fleshed, and hollow. This variety has been chosen because of their ability to travel well and last longer. There are many other varieties with other flavor profiles, softer textures, pink flesh, and juicy. I HIGHLY encourage you to go the farmers market and taste them all.
Jo Robinson, of Eating on the Wild Side, suggests that consumers up their standards for produce, especially for berries, so that the stores will have to supply higher quality produce (ripe, not moldy, flavorful, etc.).
Organic berries offer more of an anti-cancer effect than conventional berries.
The antioxidant activity of berries increases when left out at room temperature. The antioxidants contained in strawberries include: ellagic acid, anthocyanin, catechin, quercetin, and kaempferol.
They help to fight against inflammation, cancer, and heart disease.
Good source of vitamin C, folate, and manganese. They are also rich in vitamin K, potassium, and magnesium.
From The 52 New Foods Challenge: A Family Cooking Adventure for Each Week of the Year, with 150 Recipes by Jennifer Tyler Lee, Encyclopedia of Healing Foods by Michael Murray, Joseph Pizzorno, and Lara Pizzorno, Eating on the Wild Side: The Missing Link to Optimum Health by Jo Robinson, and Superfoods: The Healthiest Foods on the Planet by Tonia Reinhard.
Place coconut milk, chia seeds, and strawberries in food processor and pulse until it becomes a smooth consistency.
Add the vanilla and honey. Pulse until just incorporated.
Place into small jars and store in refrigerator for 1-2 hours or overnight. Chia seeds become gelatinous and will thicken the pudding as it sits. It can also be eaten right away.
There are many other options for chia seed pudding. Try experimenting with other seasonal fruits like peaches, raspberries, pears, blueberries, and even pumpkin. Also consider adding nuts, other seeds, and spices. The possibilities are endless!
Coconut Milk comes from the coconut and is found in tropical regions in Asia, Latin America, and the Pacific Islands. Coconuts contain healthful medium chain fatty acids such as lauric acid and capric acid, which are antiviral and antibacterial. These medium chain fatty acids are easily absorbed by the body and help to increase the metabolism. They also protect against heart disease and promote weight loss. In addition to fatty acids, coconuts also contain healthy carbohydrates and some protein. Coconuts are a good source of manganese, molybdenum, copper, zinc, and selenium. When choosing a coconut milk, avoid the low fat options because the beneficial medium chain fatty acids have been removed.
Chia seeds are those same seeds that are used in the popular Chia pets. They come from the plant Salvia Hispanica that grows in the deserts of Mexico. They help to reduce food cravings, reduce blood pressure, control blood sugar, and they are easier to digest than flax. Chia seeds should be soaked in water before using, creating a chia gel, which helps to hydrate the body. Chia seeds are rich in Omega-6 and Omega-3 fatty acids. They are also a good source of antioxidants, potassium, calcium, iron, dietary fiber, and they have some protein too!
Strawberries are the most popular berries in the world and are native to many parts of the world. Strawberries are rich sources of vitamins C, K, B6, and B1, silicon, fiber, flavonoids, manganese, pantothenic acid, iodine, folic acid, and biotin. Their flavonoid content helps to protect against inflammation, cancer, and heart disease. When storing berries, do not wash them until you plan on eating them because berries start to breakdown when they are moist. Strawberries are consistently on the Environmental Working Group's Dirty Dozen list, so it is very important to buy organic strawberries.
Honey is one of the four items that bees produce. Honey is rich in riboflavin, iron, manganese, and vitamin B6. It is also rich in antioxidants and it is an antiseptic. Local honeys are also said to help with seasonal allergies.
DISCLAIMER: I am NOT a Registered Dietician or Medical Doctor. As such, I do NOT provide medical nutrition services, or diagnose and treat disease. Rather, I educate people on the benefits of a healthy lifestyle to improve their quality of life. I advise people with existing medical problems to consult with medical doctors. I shared evidence-based health information, whether to class participants, wellness counseling client sessions, or on this website.
Bauman, E. & Friedlander, J. (2014). Foundations of Nutrition. Penngrove, CA: Bauman College.
Murray, M., Pizzorno, J., & Pizzorno, L. (2005). The Encyclopedia of Healing Foods. New York, NY: Atria Books.


text:
Eastern Redbud (Cercis canadensis) [SIR-sis kan-ah-DEN-sis]
Other Names Judas Tree, Love Tree, Cercis canadensis-Standard, CERCIS , RED BUD EASTERN { CLUMP FORM }
The showy rose-purple flowers of this small tree are one of the first signs of spring, opening a couple of weeks before its leaves come. Leaves start with a purplish color before maturing to dark green. In the wild, eastern redbud is typically an understory tree. There are a number of cultivars, including Cercis canadensis 'Alba' (white flowers), Cercis canadensis 'Lavendar Twist' (weeping form), Cercis canadensis 'Forest Pansy' (purple leaves), Cercis canadensis 'Hearts of Gold' (yellow leaves).
Named Cultivars Cercis canadensis 'Ace of Hearts', Cercis canadensis 'Alley Cat', Cercis canadensis 'Appalachian Red', Cercis canadensis 'Cascading Hearts', Cercis canadensis 'Columbus Strain', Cercis canadensis 'Covey', Cercis canadensis 'Forest Pansy', Cercis canadensis 'Greswan' BURGUNDY HEARTS, Cercis canadensis 'Hearts of Gold', Cercis canadensis 'JN7' SUMMER'S TOWER, Cercis canadensis 'Little Woody', Cercis canadensis 'MN Strain', Cercis canadensis 'Morton', Cercis canadensis 'Northern Strain', Cercis canadensis 'Pauline Lily', Cercis canadensis 'Pink Heartbreaker', Cercis canadensis 'Pink Pom Poms', Cercis canadensis 'Ruby Falls', Cercis canadensis 'Silver Cloud', Cercis canadensis 'Tennessee Pink', Cercis canadensis 'The Rising Sun', Cercis canadensis 'Vanilla Twist', Cercis canadensis 'White Water', Cercis canadensis f. alba, Cercis canadensis var. texensis
I am a... Deciduous Perennial Tree
Where to Find It There are three redbuds between the east and central paths relatively close to the south end of the woods. They're easiest to see in early spring, when their pink/purple flowers stand out.
How to Recognize It Redbuds are unmistakable in early spring, as the purple buds emerge directly on the branches and open into pink flowers. The leaves are distinctively heart-shaped, turning yellow in fall. As an understory forest tree, the branch structure is often graceful and spreading, while in full sun in our yards they can be so dense as to be impenetrable. The smaller branches typically twist somewhat one way then the other.
Why to Like Before coming to the garden, Eastern Redbud were understory trees. As in our yards, Redbuds provide an early season burst of color. Many animals and birds eat the seeds, especially in winter when they frequently remain on the tree. The flowers are important component of the production of honey.
Mature Size 20 - 30 feet tall. 20 - 30 feet wide.
Sun Exposure Part Shade - Full Sun
Moisture Tolerance Medium : Prefers average to moist conditions, and shouldn't be allowed to dry out.
Zones 4a - 9b
Tags Fall Color, Showy Flowers, Thornless, Accent, Attractive to Butterflies, Deciduous, Deer-Resistant; Clay Soil; Black Walnut, Asian Garden, Border, Butterfly Garden, Cottage Garden, Flowering Tree, Rain Garden, Shade Tree, Street Tree, Urban, Well-Drained Soil, Ornamental Tree, Illinois Native Accent Trees, Bareroot Trees, Fast Growing Trees, Flowering Trees, Ornamental Trees, Small Yard Trees
Bloom Period Early Spring (First Bloom: 191 GDD, Full Bloom: 245 GDD)
Flower Color Rose-Purple
Foliage Color Purplish Green
Animals That Use It
Nectar:
Seeds:
Eastern Redbud, Cercis canadensis (University of Wisconsin-Extension)
A very detailed introduction to the Eastern Redbud [e,d]
More Photos: Google Image Search & Flickr


text:
Anthony Holborne (nacido en 1545 - Londres, 29 de noviembre de 1602) fue un intérprete de laúd y compositor inglés.

El compositor era el hermano de William Holborne y se casó con Elisabeth Marten el 14 de junio de 1584. En la portada de sus dos libros, afirma estar al servicio de la reina Isabel.

Como casi todos los músicos isabelinos, fue laudista, pero sobre todo un personaje versátil del ambiente musical de su tiempo. Intérprete de cistro, y también cantante, se distinguió asimismo como uno de los más autorizados y refinados compositores ingleses del siglo XVI.

Sus composiciones se conservan en dos antologías: The Chittham Schoole, de 1597, con 32 piezas para cistro con tablatura francesa y Pauans, Galliards, Almains and other short Aeirs, de 1599, con pavanas, gallardas y algunas composiciones de títulos sugestivos. La producción de Holborne también incluía reelaboraciones de motivos populares y de aires tradicionales.

Bibliografía
 Edita SARPE, Gran Enciclopedia de la Música Clásica, vol. II, pág. 594. (ISBN 84-7291-226-4)

Músicos de Londres
Fallecidos en Londres


text:
Instagram caught a lot of flak for its rebranding last week, but it's only the most recent in a string of companies that have gone through brand makeovers. Uber, Airbnb, and Yahoo each debuted new brand identities in the last couple years that were widely lampooned.
The biggest rebranding cautionary tales remain Tropicana in 2009, which backtracked after sales dropped by 20%, and Gap in 2010, which reverted to its old logo after just 6 days of criticism.
What cracks me up the most about rebranding efforts is the self-indulgent way that brand teams can articulate what went into them. They often put together overly intellectual and ridiculously complex justifications for even minor elements of a brand redesign. They get swept away by their own hyperbole.
My favorite example of a brand "waxing poetic" to introduce a new identity is Uber and their "Bits and Atoms" manifesto.
"For Uber, the bit represents our technology. It's complex, precise, and advanced. But when it's expressed, it's effortless and refined…
"And if you think the bit is a big deal, consider the atom. Born 13.8 billion years ago, the atom is responsible for everything. From the BLT … to moms everywhere … to New York City. And for us, the atom signifies our rapidly improving cities, the goods we move from place to place, and most important, the people we serve…
"Until a few short years ago, atoms and bits existed in entirely different worlds. But then, something happened.
"What if we brought these two worlds together?
"What would that look like?"
Apparently, what it it looks like is this.
Uber CEO Travis Kalanick described the logotype as "at once more grounded and elevated." Whatever that means.
Rebranding efforts sometimes read like "The Emperor's New Clothes." The brand team rhapsodizes about all that went into it, without seeming to realize when it misses the basics.
I'd love to hear your thoughts on what to keep in mind when considering a rebranding exercise.
Here's another cartoon I drew on rebranding a couple years ago.
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John Dodds says
First question to be answered. Have we changed sufficiently for a rebranding to be justified or are we just re-logoing?
BC says
If you have to explain a logo, it's a fail.
If you feel the need to explain a logo, it's a bigger fail.
So, probably best to not explain it at all.
Nike's "swoosh" gets meaning from promoting the brand. Googling reveals a connection to Greek mythology, which is all well and fine if you choose to dig for it. But lots and lots of $ have successfully connected the mark to the brand without most of us ever knowing the backstory — including me until I just looked it up…
Changing a brand mark is just begging for differences of opinion. In the end, any change to a brand's visual i.d. is going to bring out supporters and detractors — it's a subjective thing. Interestingly, I didn't really care at all about Instagram's logo until they changed it.
And for the record, I didn't get it.
Which was fine until they felt compelled to react to reactions.
Which loops back to the first 2 sentences in this post… 😉
Once again, Tom, you've hit it the nail on the head. I do believe clients — and their agencies — get swept away by their own hyperbole. I have worked for Gannett Co. for many years and was dumbfounded when USA Today unveiled their new logo: a plain blue circle. I would love to have been in that room as the agency was selling that one. I also shutter to think what Gannett paid to have it created. Personally, I think it says nothing or does anything for the brand.
Luka says
The logo arouses strong feelings and means so much to so many people … and yet, at the end of the day, it's often better to have a recognisable if boring and imperfect logo, than a revamped and completely different logo (e.g. Uber, EY).
Instagram's new logo is, in my opinion, a step back. However, it stays recognisably in the same visual space and metaphor, and it might be a case of "there's no such thing as bad publicity."
The Better Breads Baker says
Agree with you! Re-doing a logo without Re-thinking Brand Shift/Perception is an unnecessary exercise!
Susan Goewey says
Uber's "before" wins by a mile! In Consumer Behavior class (UVA, 1980) or it might've been in Marketing class (where I had this fabulous text by Leonard Barry called Marketing Mistakes.)
I remember being taught that company executives/boards get tired of their ad campaigns/logos/slogans long, long, long before consumers do. And changing them too soon and/or too often is a huge, but common, marketing mistake.
I think that is still true. Consumers want comfort not change. A great jingle is a great jingle. A good logo is comforting. A new logo is confusing. That's why it's so important to get it right the first time and then just stick with it.
PS Tom if you're still giving away a free print to a commentor…this is NOT a picture I'd like to win or see hanging on my wall… Not even (especially even) my bathroom wall! I hope you understand 🙂
Allen Roberts says
Straight to the heart of bullshit central!
As usual.
Well done Tom.
Really interesting…was reminded of a "creative presentation" where the presenter was waxing eloquent about the "dot" over the "i" in the brand logo, and how that was supposed to mean something.
And in these meetings, you actually sit there going, "am i the only one who does not get it?"
LOL! It's an era where truly i matters more than I
Tina Li says
We have a China player Didi Taxi that did the same thing last year. For two weeks I could not find it on my mobile and I thought that I accidentally deleted from my phone. This kind of rebranding is a completely waste of time and effort! It is damaging the brand ! Only small group of users complain about it. Majority of other people completely ignored or missed the brand among the many other choices and turn to alternative offer in the market.
This gets to one of my biggest pet peeves in the marketing industry – the use of the term "rebrand". We can't "repersonality" ourselves and it's no different for companies. Sure, a logo is part of a brand but it's not the whole. Much like the wolf in sheep's clothing cartoon, and as we who read Tom know, a brand is slow to develop, change and adjust. A logo won't magically alter that perception, despite what I feel many companies believe, thus my frustration with rebrand. Great cartoon, as always!
Michaela says
This is a great cartoon, which inspired me to write a blogpost about a rebranding exercise I was involved with at Blockbuster Online, which was a good example of how this should be done. You can read the blogpost here: http://www.relevantinsights.com/how-to-avoid-rebranding-mistakes
RSF says
"…missed the basics" that sums it up with most brand refreshes.
I had trouble locating the Uber app on my phone for days because I could not recognise the app logo.
Was I happy? NO!!!
Besides, what EVER was wrong with the 'U' …
What does the power-on symbol imply?
Soooo many questions…so much gibberish
Michael Zimmerman says
Artists and art critics sometimes refer to it as "the intentional fallacy." Simply put, "if you have to explain it, it isn't." The artist's intent is irrelevant, except to himself. Art must stand on its own. That said, I fully concur with Doug's comment that we can't re-personality ourselves without a great deal of effort and time. Rebranding is a process involving the entire organization – just like marketing.
Daniel Nobre says
Not wanting to be the Devil's Advocate here (most branding presentations are indeed full of crap intended to make a brand's conceptual background more abstract and intelectual than it is needed) but I do need to say that although people tend to not be receptive to change and although branding agencies bullsh*t a lot that doesn't mean change is outright bad. Most of the problem comes from having a 60s Mad Men approach, based on the old school concepts of the 'creative' genious that leads a team to a glorious sign off that pays the bills for years to come. This is only good for the agency but bad for the client and it's customers. Not because branding is not needed, but because they want to make it sound revolutionary and explosive to clients since they are only worried about sign off. But the truth is a) branding is an area that can rely on data, just like almost everything else and b) it should have a plan for gradual implementation due to 'user adoption cycles' for gradually transforming the old logo into a logo that fits the current strategy and finally c) change it ONLY if there is a real need i.e. to reflect a change in the company – it needs to be consistent and a multichannel experience since just changing your branding means anything if not coupled with consistent improvements in other sides of the company.
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