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Download Festival 2019 Sunday Review – The Last Reign
Jamie Giberti
Heads are sore, feet are weary but that matters not because there is one full day of Download 2019 left to go. The Donington masses collectively dust themselves down as they head towards Tool, Enter Shikari, Slayer's last ever UK show and much more, so let's get straight to it.
I Prevail (7), through no fault of their own land the awkward Sunday morning main stage slot and do their best to rouse a flagging Donington crowd. Opening with the ballsy Bow Down, the Michigan Rockers, early or not, mean business. Playing almost exclusively a set dominated by latest album Trauma the band packs as many punches as they can in their short set from the catchy chorus' of Deadweight to the furious, full out, wake-the-fuck-up anthem Gasoline all whilst Clean vocalist Brian Burkheiser spins one-legged on a broken foot! Vocalist Eric Vanlerberghe's get the crowd going at all costs mentality finally pays off when the band is rewarded with a sea of headbangers up front for Come And Get It. But it's still not enough. In the breakdown of the song, referring to himself as a greedy motherfucker, he calls for all the energy and for the crowd to show him why the band should come back to the UK again. The crowds respond with huge mosh pits, much to his delight. They end with the crowd firmly on their side for a storming rendition of DOA. CF
There is a certain awe and mystery surrounding American Rockers Starset (7.5) who are another of the bands making their Download Festival debuts in 2019. A concept band based on The Starset Society the band presented their space-infused cinematic rock with much conviction. Opening with the emotive Unbecoming into the oh so catchy Monster, Starset gave a masterclass of how to mix varying genres and bring it in the live arena dressed in what can only be described as post-apocalyptic attire. Frontman Dustin Bates lets his musical art speak for itself commanding the stage with ease without having to say a word, exuding the swagger of the big gun frontmen – the Cardinal Copia's, the Jared Letos and the Chester Bennington's of the rock/metal world. My Demon wraps up a brief but impactful set on Zippo. Starset is a band to watch over the next few years. Their sound is already massive, refined to perfection and they have the stage show to match. If they can build momentum this side of the pond, they certainly have the potential to knock on the doors of arenas within the next five years – you heard it here first. The only downside was watching this space-themed band perform in the daylight. CF
When Godsmack (8) last played Download they were midway up the 2nd stage, this time they are only a slot or 2 lower, but on the big boy main stage and still draw an impressive crowd. I am personally a fan, was looking forward to this and am always pleased by how many turn out for them, but often wonder whether it's genuine popularity or because Godsmack being in the UK is about common as Tool being anywhere. After an extended intro jam the boys launch into latest album title track When Legends Rise, following it up with the certified banger title track of the last album 1000hp and we are up and running.
Interestingly their previous set, which was a couple of tracks shorter featured cuts from every album released up to that point, but this set is much more about showcasing the new material – Something Different is the only other track performed from 1000hp and bar 2 songs from Awake, the rest of the set is all made up of new material. Apart from That Drum Battle. Once again, I find myself wondering why with such a short stage time any band would spend time doing anything other than playing actual songs, especially as it probably took the crew the same amount of time the band spent on stage to actually get all those drum mics onto both (massive) drumkits! That's not to say it isn't impressive and fun, but I always tell people who haven't seen the band live about the cool drum battle between Shannon (Larkin, actual drummer) and Sully (Erna, vocalist who used to be a drummer back in the day. Kind of like a metal Phil Collins), but anyone who saw it at Download has now seen it and has no real special reason to pay for a ticket for a show. It was still fun though, especially as 10 mins before stage time we actually saw the last of the rain for the weekend and as Sully works the crowd from the ego ramp the band sign off with their biggest hit over here I Stand Alone and everyone goes back to the bar happy. GL
If you were playing a game of metalcore bingo, you would have a full house by the end of Heart of a Coward's (6) first song. This isn't to say that the set is without merit, as they play with an impressive amount of energy and determination. Material from new album, The Disconnect, slots in well amongst more established tunes, and the set itself is well paced keeping the energy levels high throughout. The calls to 'open up this circle pit motherfuckers' may be as trite as you can get at Download, but despite hackneyed stage patter the band give it their all and provide a decent amount of entertainment. SS
Ahead of their set America's rising stars, State Champs (8), promise us big sing-songs and happy vibes ahead of their second trip to Download. And the East Coast contingent certainly doesn't disappoint in this regard delivering Pop-Punk anthem after Pop-Punk anthem. Their energy is simply infectious and you would be hard-pressed to find a band having so much fun all weekend. Period. Tracks from 2018's Living Proof shine brightly whether its set opener Criminal, Mine Is Gold or the strike of Lightning with its almighty chorus. It's all well fused in with fan-favourites from Around The World and debut The Finer Things though. Secrets and Elevated are thrown in there for good measure too in the champs afternoon Pop Punk Party. Put it this way, when your encore is a double-whammy of "big guns" in the form of All You Are Is History and Dead And Gone accompanied with a spinning bass player, you can't really go too far wrong. It's refreshing to see one of the genres newer faces giving the more established bands a very good run for their money. Proof that Pop Punk is very much alive and well in 2019 and has these Champs ready to contend for its throne. CF
Future festival headliners, Black Peaks (8.5), were pulling no punches. Opening with the colossal Single, Can't Sleep, proceedings are whipped into a frenzy from the off. Unfortunately for the first few songs, Will Gardener's voice seems a touch off the mark, but he is a man who even at a tenth of his powers remains one of the greatest vocalists at the entire festival. As the set hammers on, fire engulfs the front of the stage, adding an extra slab of gravitas to the wonder of Say You Will, and elevating things from phenomenal to positively incendiary. A truly momentous set and one that will remain talked about at the festival for years to come. SS
The sudden abundance of drinking horns in the audience and the massive viking helmet stage setup can mean only one thing – the metal world's favourite Vikings Amon Amarth (7) have arrived to do battle with Download. Quite literally in this case, as part of their set involved two warriors reenacting a battle while Johan Hegg and co thundered through The Pursuit Of Vikings. A set mainly drawn from the past two albums, Jomsviking and Beserker, was very well received, although the odd curve ball like opening with The Fate Of Vikings from 2004's Fate Of Norns was a wonderful bonus for the longtime fans. Whilst not quite on the earth shattering form that they are fully capable of at times, there's no such thing as a bad Amon Amarth performance, and the ever swelling metal masses in particular greatly enjoyed Shield Wall and the always excellent Guardians Of Asgard. Closing as it is written in law that they must with one of the greatest metal songs of the last fifteen years, Twilight Of The Thunder God, this performance should see Amon Amarth continue their steady ascent up the Download festival line up. Second stage headliners next time perhaps? JG
Evening is beginning to draw in as Anthrax (7) start their 2nd stage set by jamming along to a Cowboys From Hell intro tape and then opening proceedings properly with Caught in a Mosh, showing that they mean business today. Clearly feeling nostalgic about being back at Download ("but we all know it as Monsters of Rock!" Scott Ian) the all too brief set is mostly made of classic pre-John Bush era tunes such as Madhouse and I Am The Law. The set seems to almost dip a bit when they play In The End from Joey Belladonna's comeback album Worship Music, not coz it's a bad song, just everything else had been so "classic Anthrax". It's a real shame after all his years of service we never get to hear any of John's songs anymore, but I have no idea if that's a band decision or some other diva activity. They still kill the old way though and after the staple closer of Indians, the assembled throng is more than ready for Slayer to close the day in this particular corner of Donington. GL
Instrumental post metal is a hard sell at Donnington, but if anyone was going to do it bar booking Russian Circles, it was Toska (7). Their music is deftly performed and exploratory, expanding ad infinitum across the four or so songs they play for their set. The physical performance is surprisingly energetic given the genre within which Toska exist, and provides another layer of enjoyment to an already hearteningly well attended set. It's a no frills, no bells and whistles affair, just an immensely talented band playing vastly interesting music. SS
In a day that featured some of the greatest heavyweights of the rock and metal world, it comes as something of a surprise that Alcest (9) would pull such a deeply devoted, sizable crowd and play one of the best sets of the day. Neige, the frontman and progenitor of Blackgaze, stands with his thousand yard stare and seeming discomfort at being the focal point for a huge audience, but when the performance erupts he comes into his own as a proper rock star. Shimmering, glittering guitars juxtaposed with the dirt and bile of blackened music make for a dynamic and enrapturing set that goes pretty much unrivaled across the Sunday. SS
They may have less elaborate staging than their Viking metal brothers Amon Amarth but Lamb of God (8) did not come to fuck about, they came to lay waste to Donington Park and all those within it. Randy Blythe was on particularly cutting form, roaming the stage with something approaching murderous intent – but then when your opening consists of Omerta, Ruin and Walk With Me In Hell, that's one hell of a dose of enjoyable punishment for the huge throng of people watching. Making special reference to three special numbers, 512 was perhaps the highlight of the set (as it often can be), while those who have seen Lamb of God recently (such as on the Slayer tour) will have been pleased to see new additions to the set like Descending and Hourglass. Ending with the one-two uppercut combo of Laid To Rest and Redneck, Lamb Of God's most high profile position on the Download line up was fully justified, and they may well not be done climbing yet.
Recently reformed rock legends The Smashing Pumpkins (5) are making their eagerly awaited debut at Download Festival, and they have brought with them what appear to be enormous statues of giant illuminated Russian dolls. Opening with Zero we have high hopes for tonight's performance, unfortunately from then on it's all just a little bit flat. Not even a superb rendition of Bullet With The Butterfly Wings or a beautiful light show can breathe life in to this show. Barely cracking a smile, Billy Corgan looks like he would rather be anywhere else in the world than on the hallowed grounds of Donington Park as he stalks around the stage donned in black robes that put Ghost to shame.
In an attempt to do something special, we are given a cover of Black Sabbath classic Snowblind complete with a guest appearance from a heavily pregnant Amalie Brunn of Myrkur. Unfortunately, this feels so random that it just does not work. Why not duet on one of the classic tunes from The Smashing Pumpkins extensive back catalogue, rather than give us a fairly average cover? Omitting Today, 1979 and Tonight, Tonight is unforgivable, as is Corgan messing up the words to Ava Adore. By the end of the set we're left feeling totally disconnected from the band on the stage, which is a real shame given The Smashing Pumpkins are such a magnificent band on record. When you're that high on the bill you have a lot to live up to. Must try harder. LF
After their secret set at last year's Download, expectations were sky high for Fever 333 (6). The set is undeniably explosive, with Jason Butler in particular proving why he is such a revered frontman. The pedigree of the members speaks for itself and goes to explaining just why it is that people flock to see Fever 333 in their droves. However, how little of what happened on stage that was actually played live is downright shameful. The over reliance on backing tracks makes for a disjointed and inauthentic set, detracting from the power of the words and message that the band try their damn hardest to evoke. A drum solo in which the drummer does not remain at the kit, but the percussion keeps pounding, speaks volumes as to the lackadaisical attitude the band have to their musicianship. SS
Dream Theater's (9) first appearance at Download in a decade was eagerly anticipated, and the perfect warm up for the farewell to Slayer, despite the musical contrast. They were on absolutely scintillating form too. Dream Theater's live performances generally live and die by the form of James Labrie, but it was evident from the opening Untethered Angel that the mass of Dream Theater devotees gathered at Download had nothing to worry about – he was flying. The intro to As I Am had heads banging and fists flying, while you could see minds being blown by the looks on the faces of those present watching Barstool Warrior and in particular The Presence Of Enemies Pt 1. If minds were blown at this point, they were positively melted by The Dance Of Eternity, whetting appetites for the potential Scenes From A Memory 20th anniversary tour later in the year or next year (for more on that, stay tuned for our exclusive interview with Dream Theater's resident wizard Jordan Rudess very soon). Flipping from old to new to old with Lie, Blue Dot and then the epic conclusion of Pull Me Under, it has to be hoped it'll be a lot less than ten years before Dream Theater return to Donington next time. JG
Headlining the third stage and packing it to the rafters were Enter Shikari (8.5). Few bands are as hardworking and dedicated as the perennially underrated quartet, who deserve a far bigger slot than they are given. There is however no hint of contempt or envy in their performance or their greetings to the "carbon based lifeforms" making up the massive crowd. Using throbbing synthesisers to create their unique brand of post hardcore in a set that ups the ante on the heavy side of their sound makes for a tent shaking wild ride. The likes of Arguing with Thermometers and the blast beating Juggernauts make for a thrilling and dynamic performance, as pyro and confetti cannons burst out into the audience time and time again. Rou Reynolds is a wonderful frontman, bringing a genuine feeling of love and togetherness to the crowd, herding them through the genre blending journey their set takes you on. More than just a hit brilliant, Shikari are sure to become a staple of the festival, and deserving of far more exposure in the hallowed grounds. SS
Our review of Slayer's UK farewell performance ran just a couple of days after the festival. For those who haven't yet had the chance to read it, you can read our review of Slayer's last UK performance here.
Finally. After thirteen long, long years, the moment had come. Tool (9) graced the main stage of the hallowed home of rock and metal. From the opening 'Hey, Hey, Hey' whispered by Keenan into the microphone the set is a transcendently beautiful affair, with vivid technicolour lights and swirling psychedelic imagery adorning the back and side of the stage. It is a sight to behold and one that goes unparalleled by ninety nine percent of bands who have ever set foot on a stage. The quartet smash their way through a career spanning set in the truest sense, playing from as far back as the Opiate EP, all the way up to currently unreleased songs from their upcoming fifth studio album. It goes quite some way to explain the grandeur of Tool's music that in amongst huge hits and fan favourites, the new songs almost take precedence as the highlight of the set, in particular the latter of the two, Invincible.
As the sun sets into a distant shadow and night descends upon the arena everything begins to make all the more sense. The band are silhouetted against the aforementioned kaleidoscopic backdrop, shadows dancing off the light in a sweet symphony of sound and sight. The only real bugbear about the set is that it lacks a real moment of total wonder, there is no 'Oh my God' feeling, just one prolonged emotion of hushed reverence and quiet contentment. The performances themselves are pretty much spot on, though it is noticeable that Maynard James Keenan struggles to hit some of the high notes from his younger days, instead electing for a lower register harmony. This is a minor critique of course in what is a set that most bands could not dream of performing, and stands testament to the wonder of Tool. A perfect way to see out another mightily successful Download, and we can only hope they won't be away for so long next time.
If you've not yet had a chance to read the first two parts of our extensive Download Festival 2019 coverage, you can catch up on the links below:
Download Festival 2019 Friday Review
Download Festival 2019 Saturday Review
Words by Jamie Giberti (JG), Claire Frays (CF), Greg Latham (GL), Lisa Fox (LF) and Sam Savigny (SS). All photos by Jamie Giberti.
Download Festival 2019
Toska
Features and Live Editor for Rock Sins. Co-founder of Rage PR. Forever juggling the worlds of journalism, PR, web development, SEO and photography.
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Rainy evenings at the Disneyland Resort are magical, but they have an extra sense of sparkle in Cars Land, and particularly in Radiator Springs, where the neon provides added color and reflections on the slick pavement of the road. Here, the warm glow of the Cozy Cone Motel offers a bit of relief in the cold drizzle of the evening. With the glistening ground beyond, scenes like this are a pleasant respite in the winter.
I mean, Southern Californian winters aren't that cold, but the imagery can work, right?
A rainy evening on the main drag of Radiator Springs.


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Lisa Arie has trained with horses for years, but her specialty is in training executives.The so-called "CEO whisperer" lives on 160 acres of Colorado plains, where since 2005, she and husband Jess have run an experiential learning center for CEOs, philanthropists, and entrepreneurs to unplug and discover how they can lead more mindful lives.
Vista Caballo, which roughly translates to "perspective of the horse" in Spanish, uses horses to guide the business elite through enlightenment. It's no ordinary corporate retreat.
"We can learn a lot from a species that thinks quite differently that we do," Arie says. "A horse is going to be honest with you. It's not safe for them if they lie to you. Their self-preservation is very important. They are prey animals — different from us — we are predators."
"If I can have a prey animal feel safe with me as a predator, it means I'm probably doing something pretty right as a leader," she says.
Over 800 people have taken advantage of Vista Caballo's offerings since 2006.
The signature program at Vista Caballo invites participants to stay three days and four nights. Arie talks to executives before their arrival about their expectations and goals, and she creates opportunities for "interspecies interaction" to help clients forge new ways of thinking. They might learn to approach a horse without spooking it, for example.


On 20 March 2028, it will be 200 years since Henrik Ibsen was born in Skien.
This is an occasion that Skien naturally intends to mark! We want to play a major role in commemorating Ibsen's 200th anniversary. At the time of writing, we have made an application to the National Library of Norway, which has overall responsibility for anniversaries of nationally important writers.
The Ibsen Library is one of our projects for the 200th anniversary.


Australia's Best Value Malbec. This wine shows vibrant primary fruit flavours of plums, red berries and spices. Finishing soft and round with velvety smooth tannins.
This wine shows vibrant primary fruit flavours of plums, red berries and spices. Finishing soft and round with velvety smooth tannins. Malbec is rarely seen as a varietal wine but here at Bleasdale and in Langhorne Creek it stands on its own two feet and performs well enough to earn its stripes.


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Miniature and durable spectrometer for wearable applications
5 December 2022 | News
Researchers have developed a wafer-thin chip-scale spectrometer that is suitable for wearable applications. The robust gallium nitride lab-on-a-chip device can also withstand harsh environments with severe radiation, such as space exploration, or those with high temperatures and can be adapted to do blood analysis by simply projecting light onto the skin. It measures 0.16 mm2.
"As a wearable device, we'll be able to put our device on a flexible substrate, such as sheets or fabric—or maybe on skin", said doctoral researcher Tuba Sarwar.
The prototype optical spectrometer created by Sarwar and other members of Prof. P.C. Ku's team was initially developed with a specific purpose: measuring an athlete's sweat in a device that could be worn as a skin patch. This application was determined by U-M's Exercise and Sport Science Initiative (ESSI). The device needn't last long; in fact, being disposable was a plus. Making such a device would require extreme miniaturisation of current devices available in the marketplace. It would also require creating a device that can work in real time under changing conditions.
Ku, Qu and their team took on the challenge of creating a device that could achieve ESSI's goal, and created a miniaturised, low power, integrated device that works in over the wavelength range of 400–645 nm. The team's spectrometer includes only 16 photodetectors, each responsive to a unique spectrum of the light. This low number of photodetectors was made possible by two key techniques. First, the team used strain engineering on gallium nitride (GaN)-based spectral encoders. Strain engineering is a technique used, for example, in semiconductor manufacturing in which the material is stressed or deformed. Done correctly, it can lead to new material properties that are better suited to specific applications. GaN semiconductors were selected as the foundational material because of their excellent optical properties across the visible spectrum.
The desired result of a dramatically reduced dependence on the angle of the light was accomplished, which eliminated the need for precise positioning of the spectrometer and the associated optics. It also allowed the photodetectors to reside alongside the spectral encoders on the same chip.
Second, the team incorporated machine learning into the device's operation in order to decode the signal emitted from the detector. Doctoral researcher Can Yaras used a simple non-negative least-squares (NNLS) algorithm to enable an efficient computational algorithm to recover the spectral information from the detectors' signal. In terms of performance, the device was highly accurate in determining the peak wavelengths (with a standard deviation of 0.97 %), but less accurate in measuring intensity ratio over different peak positions (with a standard deviation of 21.1 %, or 10.4 % after removing one outlier). The team expects that the reading of intensity ratios can be improved by increasing the number of photodetectors, and further developing the machine learning algorithm, such as by applying deep learning techniques. They are also working on several other enhancements to the prototype spectrometer.
"Our goal was not to build the best spectrometer in the world in terms of the resolution", said Ku, "but to focus on other aspects that are just as exciting if not more: the size, the thickness, the power consumption and the ease of operation."
In terms of future applications, Sarwar says that this miniature spectrometer could be built into a skin patch for health monitoring and diagnosis. The advantage it would have over existing devices is the fact that the excitation light source can also be easily integrated. The radiation hardness of the GaN semiconductors also makes the device potentially suitable for space exploration.
Read the original journal paper in Nano Letters
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redpajama_set_name: RedPajamaCommonCrawl


text:
\section{Introduction}

In \rev{hydrogen and proton transfer reactions} \cite{HYDROGEN_TRANSFER}, electronic polarization and anharmonicities of the potential energy surface (PES) cause a considerable coupling between different degrees of freedom in the system, leading to complex intra- and intermolecular vibrational energy transfer\cite{Warshel_1982_JPC}. In addition, due to the light mass of hydrogen, nuclear quantum effects (NQEs) such as tunneling and zero-point energy (ZPE) \rev{can} play a crucial role at remarkably high temperatures \cite{Tuckerman_Science_1997, Marx_1999_Nature, Klinman_AnnRevBio_2013, Meisner_Angew_2016, RossiMano2016},
and even heavy atoms (e.g., carbon or oxygen) can have an impact on \rev{hydrogen tunneling} \cite{Tuckerman_PRL_2001,Hinsen_JCP_1997}.
\rev{An accurate and quantitative description requires an all-atom, all-electron quantum simulation of these reactions, and makes theoretical approaches based on empirical potentials and/or a dimensionality reduction of the PES, as well as a classical treatment of nuclear dynamics inadequate.}

Porphycene, the first synthesized structural isomer of free-base porphyrin \cite{Vogel_AngChem_1986},
has emerged as a unique example of \rev{intramolecular double hydrogen transfer (DHT)} in a multidimensional anharmonic PES, where strong hydrogen bonds are formed in the molecular cavity \cite{Fita_PCCP_2017,Waluk_ChemRev_2017}.
\revi{The interest in this molecule has increased in the recent years, especially due to results obtained from scanning probe microscopy.
Those have shown how different external stimuli, such as light \cite{Bockmann_NanoLett_2016}, heat \cite{Kumagai_PRL_2013}, and force\cite{Ladenthin_NAT_2016} can control the DHT, establishing this molecule as a prototype for the manufacture of rapid optical molecular switches and logic gates. }

The presence of \revi{strong} hydrogen bonds results in a low reaction barrier and a high DHT
rate \rev{at room temperature} \rev{($k\approx10^{12}$ s$^{-1}$)} \cite{Fita_2009_CEJ} compared to other derivatives, e.g. porphine ($k\approx10^{4}$ s$^{-1}$) \cite{Braun_JACS_1994}.
The DHT reaction, which in this case connects the two degenerate {\it trans} tautomeric states (Fig. 1), can occur either through a stepwise or concerted mechanism.
In the former case, the hydrogen atoms are transferred sequentially \revi{through an} intermediate {\it cis} tautomeric state and \revi{the reaction pathway involves} a first-order saddle point (SP1 in Fig. \ref{fig:Porphycene}).
\revi{In the latter case, two hydrogen atoms are transferred in a correlated fashion without passing by a stable intermediate. This transfer can occur simultaneously through a second-order saddle point (SP2 in Fig. \ref{fig:Porphycene}), which is usually referred to as the synchronized mechanism\cite{Dewar_JACS_1984}}.
\rev{It is also well established that the tautomerization reaction in the porphycene molecule is a multidimensional process. The strong vibrational level dependence of the tunnelling splittings \cite{Mengesha_2013_JCP,Vdovin_2009_CPC} and the modification of the tautomerization rate upon deuteration of the peripheral hydrogens \cite{Mengesha_JPCB_2015} are two manifestation of the multidimensional nature of the tunneling process.}
\rev{At cryogenic temperatures in the gas-phase (or in a helium droplet), the vibrational ground state level exhibits a tunneling splitting of 4.4 cm$^{-1}$ \cite{Vdovin_2009_CPC,Mengesha_2013_JCP,Sepiol_1998_CPL},
showing that the {\it trans-trans} tautomerization takes place via coherent tunneling through the concerted mechanism  \cite{Smedarchina_JCP_2007,Smedarchina_JCP_2014}. Indeed, excellent agreement with the experimental values have been obtained considering only this pathway\cite{Zahra2014}.}
However, \revi{vibrational couplings to the environment or, at higher temperatures, couplings to the intramolecular vibrational modes} \rev{lead to decoherence of the wave-function such that the quantum state decays exponentially and the reaction dynamics can be described} as a rate process \cite{Ciacka_2016_JPCL}. In these cases, which are more relevant for biological or technological applications,
it is not straightforward to clarify which mechanism governs the DHT reaction, how temperature affects the reaction rates, and the character of the vibrational modes that play a role.

Vibrational spectroscopy is a powerful tool that can shed light on nuclear dynamics and the PES. \rev{The hydrogen-stretching} vibrational band in this system \rev{serves as a fingerprint of hydrogen bonding and can}
exhibit extremely complex spectral features, such as a  broadening and the emergence of satellite peaks.
In porphycene, the characterization of the N-H stretching mode ($\nu_{\text{N-H}}$) related to the  {\it trans-trans} tautomerization has been particularly controversial, because of its apparent absence in the experimental Raman and IR spectra, although theoretical calculations in the harmonic approximation predict a very intense band \cite{Gawinkowski_2012_PCCP}. The broadening of $\nu_{\text{N-H}}$ in porphycene resulting from the intermode coupling has been examined by a classical nuclear dynamics approach \cite{Gawinkowski_2012_PCCP}, but an agreement between simulations and experiment could not be fully achieved. This suggests that a strongly anharmonic PES, intermode couplings, and NQEs \rev{all} play a decisive role in the static and dynamic properties of the inner hydrogen atoms of porphycene.

\begin{figure}
    \centering
    \includegraphics[width=0.62\textwidth]{fig1.png}
    \caption{Characterization of the \textit{cis} and \textit{trans} isomers as well as a schematic 2D potential energy surface (PES) of the porphycene molecule. SP1 and SP2 stand for first order and second order saddle points and $r$ and $d$ are distances between atoms as marked in the figure. \revi{In the schematic 2D PES}, $\delta_1=r_1-r_2$ and $\delta_2=r_3-r_4$.}
    \label{fig:Porphycene}
\end{figure}

The situation outlined above has hampered the elucidation of the hydrogen-bonding structure and tautomerization dynamics in porphycene for a long time. \rev{\revi{Approximations to the} quantum dynamics have been \revi{reported} but they relied on a dimensionality-reduction of the system
\rev{and thus neglected vibrational coupling to several modes}
\cite{SmedarchinaKuhn2007,ShiblKuhn2007,Smedarchina_JCP_2014,McKenzie_JCP_2014}.
Classical molecular dynamics simulations have been performed which included the full dimensionality of the system, but neglected the quantum nature of nature of the nuclei \cite{Walewski_JPCA_2010,Gawinkowski_2012_PCCP}.
Imaginary-time path-integral simulations based on a semiempirical PES have been carried out to compute quantum statistical properties,
but did not use methodology that could give access to real-time dynamics of the system (e.g. rates or vibrational spectra)
\cite{Yoshikawa_CP_2012,Yoshikawa_CPL_2010}. To date, an atomistic full-dimensional \revi{study} of the quantum dynamics in this system has not been presented.}

Here we demonstrate that all-atom and all-electron quantum simulations of \rev{porphycene} can fully reveal the equilibrium and dynamical properties of this molecule in the gas-phase and explain a variety of experimental observations. \rev{Employing newly implemented and optimized ring-polymer instanton theory\cite{i-pi2} and the recently proposed ring polymer molecular dynamics coupled to colored noise thermostats\cite{Rossi_JCP_2018},}
we assess in detail the open questions regarding the hydrogen bonding geometry, the hydrogen transfer dynamics, and the nature of the $\nu_{\text{N-H}}$ band observed in the IR spectrum \rev{using a first-principles PES and without resorting to any dimensionality-reduction}.
We show that the hydrogen transfer mechanism in porphycene follows non-intuitive pathways at certain temperatures, which underlines the significance of NQEs and intramolecular vibrational coupling.

\section{Results and discussion}

We first analyze the equilibrium properties of the porphycene molecule obtained from density-functional theory (DFT-B3LYP+vdW) calculations and \textit{ab initio} path-integral molecular dynamics (PIMD) simulations (see Methods).
In Fig.\ \ref{fig:FreeEnergy}a we show the free energy profile projected on the two hydrogen transfer coordinates $\delta_1$ and $\delta_2$ defined in
Fig.\  \ref{fig:Porphycene} for the PIMD simulation at 290 K\@.
As expected, the {\it trans} isomer is the most energetically stable and the free energy barrier for hydrogen transfer is around  $2 k_\mathrm{B}T$, in agreement with previous studies where NQEs were also included \cite{Yoshikawa_CPL_2010, Yoshikawa_CP_2012}. For comparison, in the classical nuclei \textit{ab initio} molecular dynamics (MD) simulation at the same temperature, the hydrogen transfer reaction is a much rarer event with an effective barrier above $4 k_\mathrm{B}T$, as shown in the SI.

The stationary points of the free-energy surface can be assigned to the {\it cis}, {\it trans}, first order (SP1) and second order saddle point (SP2) states of the molecule.
\revi{While the exact boundary value ($b$) to distinguish different states is arbitrary due to the non-negligible density at all values connecting both states within the PIMD simulations, the {\it cis/trans} population ratio is robust for reasonable values $0.1<b<0.3$, as shown in Fig. S5 in SI.}
We calculate the {\it trans} population to be larger than the {\it cis} population by a factor 7. \rev{Note that these 2D free-energy surfaces are provided as a guide to understand this system. All our calculations are carried out in the full $3N$-dimensional space.}

The 1D PIMD free-energy projections along the $q_1$ and $q_2$ coordinates (defined along the lines $\delta_1=-\delta_2$ and $\delta_1=\delta_2$, respectively) \rev{are} shown in
Fig.\ \ref{fig:FreeEnergy}b at two temperatures, namely 290 K and 100 K\@.
These projections exhibit two interesting features. First, the effective energy difference between the wells, which within a first approximation would determine the {\it cis} and {\it trans} populations, does not change between 290 and 100 K. This means that in this temperature range only the lowest vibrational modes involving the N-H groups are populated and consequently the relative population is mostly governed by ZPE\@. The wells along $q_2$ ({\it cis}), however, are considerably softened towards the barrier when the temperature is reduced while the wells along $q_1$ ({\it trans}) are not. This effectively increases the probability of {\it cis} conformations at lower temperatures. Second, lowering the temperature has the surprising effect of decreasing the effective \rev{\textit{trans-trans}} free energy barrier by 10\% \rev{and the \textit{cis-cis} by 35\%.} This effect can be traced back to fluctuations in the cage dimensions. In Fig. \ref{fig:FreeEnergy}c we show the probability density of the N-N distances, $d_1$ and $d_3$, defined in Fig.\ \ref{fig:Porphycene}.
The quantum distribution at 290 K is broader and shifted to higher values in comparison to the one at 100 K\@. The cage expansion at higher temperatures leads to an increase in the effective potential energy barrier for the hydrogen transfer reaction and is directly translated to the free energy profile.
The smaller average N-N distances at lower temperatures correlates with an increased amount of $cis$-like conformations with respect to $trans$, and is consistent with the strengthening of the hydrogen bonds observed from previous calculations on a reduced PES and NMR experiments \cite{ShiblKuhn2007}.
\rev{In our PIMD simulations we also observe that the average absolute value of the dipole projected along the H-bonded N atoms is 0.5 Debye which is in contrast to the absent dipole moment of the {\it trans} minimum-energy isomer. At the same time, it is also lower than the corresponding dipole of the {\it cis} minimum-energy isomer (1.2 Debye). This observation is consistent with the observed N-N distance distribution shown in Fig. \ref{fig:FreeEnergy}c, which is centered closer to the N-N distance of the optimal {\it cis} isomer when considering quantum nuclei.}
In the classical-nuclei simulations, the \textit{cis}-like geometries are not visited at all, and the cage is much larger.

At this point, it is worth noting that a reduction of the effective free energy barrier along the chosen reaction coordinate does not necessarily result in an \emph{increase} on the hydrogen transfer rate. Within transition state theory
(TST), a probabilistic term that depends on the effective barrier height is multiplied by a dynamical correction factor (also called transmission coefficient). It has been shown that the dynamical factor can have a much stronger temperature dependence behaviour than the probabilistic one \cite{Craig_JCP_2005_2}. Consequently, rates and barrier heights are not always trivially correlated and the temperature dependence of the rate obtained based exclusively on free energy barriers should be \rev{treated with caution}.
In fact, for this system it is experimentally observed that the rates \emph{decrease} with decreasing temperatures \cite{Ciacka_2016_JPCL} and this is also what we find in our \rev{full-dimensional} calculations shown below.

\begin{figure}
    \centering
    \includegraphics[width=0.8\textwidth]{fig2.png}
    \caption{(a) Effective free energy profile of the porphycene molecule obtained from PIMD simulations at 290K, projected on the $\delta_1$ and $\delta_2$ coordinates.  The contour lines start at 0.75 $k_\mathrm{B}T$ and are separated by 1 $k_\mathrm{B}T$. The x and o symbols mark the position of the \textit{trans} and \textit{cis} conformers, respectively, when optimized at the potential energy surface. \rev{We define ``{\it cis}-like" conformations as the ones lying in the vicinity of ($\delta_1,\delta_2$) equal to (+0.4,+0.4) or (-0.4,-0.4)}
    (b) Effective free energy projections along  $q_1$ ($\delta_1 = -\delta_2$) (solid lines) and $q_2$  ($\delta_1 = \delta_2$) (dashed lines) directions. Red and blue lines correspond to PIMD simulations at 290K and 100K respectively.  (c) Nitrogen-nitrogen distance probability density obtained from PIMD simulations at 100K (blue), PIMD simulations at 290K (red) and MD simulation at 290K (orange). Vertical lines indicate the minimum energy geometry values for the {\it trans} isomer (solid) and  {\it cis} isomer (dashed).}
    \label{fig:FreeEnergy}
\end{figure}

We now examine the quantum dynamical aspects of the hydrogen transfer reactions, which we \revi{approximate} with ring-polymer instanton theory \cite{Miller_JCP_1975,Jor_perspective_2018} and thermostatted ring-polymer molecular dynamics \cite{Rossi_JCP_2014}. We \rev{located} two instanton pathways, namely, the one related to the {\it trans-trans} concerted pathway and the one related to the {\it trans-cis(-trans)} stepwise pathway.
\rev{Each instanton is a uniquely-defined path which best describes a tunneling mechanism in porphycene.}
With these pathways, we can compute the thermal rate as $k= 2k_\text{step}+k_\text{conc}$ \cite{SmedarchinaKuhn2007},
where $k_\text{step}$ and $k_\text{conc}$ are the rate constants corresponding to the concerted and stepwise mechanisms, respectively. The factor 2 takes into account the two possible \textit{cis} intermediates. The ratios $R_s=2k_\text{step}/k$ and $R_c=k_\text{conc}/k$ show the relative contribution of each pathway to the total observed double-hydrogen transfer rate.
\rev{The fact that we find two stable instanton pathways means that there are at least two independent pathways for the DHT. Even though we cannot guarantee that all possible DHT tunneling pathways are being considered, the symmetry of porphycene indicates that these should be the dominating (or the only) ones.}
Our best estimate for the DHT rates are presented in Table \ref{tab:rates}. These values are in good agreement with the experimental values measured in solution.
\rev{Direct comparison between our gas-phase calculation and these results in certain condensed-phase environments is supported by the observation of negligible solvent dependency in experiments \cite{Ciacka_2015_JPCB,Gil_JACS_2010}.}
\revi{In other types of environment such as surfaces \cite{Koch_JACS_2017,Kumagai_JCP_2018} or polymer matrices \cite{Piatkowski_2018_JPCL}, the rate depends more strongly on the environment. Larger porphycene derivatives show rate dependency in both isotropic\cite{Gil_JACS_2010} and non-isotropic environments \cite{Piwonski_JPCL_2013}.}

The tunneling enhancement factor, also reported in Table \ref{tab:rates}, is defined
as $\kappa_{\text{tun}}=k_\text{inst}/k_{\text{TST}}$, where $k \equiv k_{\text{inst}}$ is the rate obtained with the instanton method and $k_{\text{TST}}$ is the rate obtained with the Eyring \revi{transition state theory} (TST)\@.
\rev{As expected,} tunnelling effects thus increase the rates by almost 2 and 3 orders of magnitude at 150 K and 100 K, respectively.
More interestingly, at $T$=150 K the concerted and stepwise mechanisms have a comparable contribution to the total rate, while at $T$=100 K the concerted path accounts for 95\% of the rate. Note that if we neglect NQEs, the scenario is completely different and at both temperatures the stepwise \revi{mechanism} fully dominates.

\begin{table}
\centering
	\begin{tabular}{|c|c|c|c|c|c|c|}
	\hline
	& $T$ (K)& $k$  $(10^{11} \mathrm{s}^{-1})$ & $k_{\text{exp}}$ $(10^{11} \mathrm{s}^{-1})$ & $R_c$ & $\kappa_{\text{tun}}$ & KIE\\
	\hline
    HH & 150 & 2.190 & 1.62$\pm$0.04  & 0.63 & 70 &  \\
    HH & 100 & 0.630 & 1.09$\pm$0.08  & 0.95 & 1135 &  \\

    DD & 100 & 0.0025 & 0.03$\pm$0.02 & 0.59 & 471   & 250\\
    \hline
	\end{tabular}
	\caption{Our calculated hydrogen transfer rates $k$, compared to experimental $k_{\text{exp}}$ data from Ref. \cite{Ciacka_2016_JPCL}, as well as the tunneling enhancement factor $\kappa_{\text{tun}}$, the contribution from the concerted path to the rate $R_c=k_\text{conc}/k$, and the calculated kinetic isotopic effect KIE=$k^{\text{HH}}/k^{\text{DD}}$}\label{tab:rates}
\end{table}

This result can be understood in terms of the mechanisms predicted by the instanton pathways.
In Fig.\ \ref{fig:Mechanism}a and b we show the minimum energy path (MEP) for the concerted {\it trans-trans} path and the stepwise {\it trans-cis} path, respectively, at 150 and 100 K\@ (\revi{black solid curves}).
The concerted path has a higher barrier than the stepwise one.  Analyzing the tunneling paths themselves, we note that the stepwise path requires that the initial \textit{trans} geometry \rev{is thermally excited to} an energy comparable to the intermediate \textit{cis} geometry, which is around 100 meV higher than the minimum, in order for tunneling to take place. From that point, the tunnelling path follows quite closely the MEP and has essentially no temperature dependence between 100 and 150 K\@. In contrast, \rev{the concerted path enables tunneling at an energy close to the bottom of the well. The energy at which the system tunnels in this mechanism is temperature dependent
and is defined by instanton theory to give the optimal balance of the probability of barrier penetration and the probability of thermal excitation}.\cite{Jor_perspective_2018}.
At 100 K the tunnelling path starts at 25 meV above the minimum and reaches points above 350 meV\@. At 150 K, since more thermal energy is available, the path starts at 64 meV but does not reach such high values, keeping closer to the MEP.

\begin{figure}
    \includegraphics[width=\textwidth]{fig3.png}
    \caption{(a) Potential energies of different instanton imaginary-time slices along the \textit{trans-trans} path at 100 K (open blue circles) and 150 K (filled red circles). The black energy profile marks the ground state potential energy surface and the dashed lines mark the minimum energy \revi{of the intanton slices}. (b) Same as in a for the \textit{trans-cis} path. (c) Decomposition of the instanton turning point displacement of the \textit{trans-trans} path into the mimimum energy \textit{trans} geometry normal modes. The inset shows the breathing mode at 197 cm$^{-1}$  (2A$_g$) with largest contribution. (d) Competition of different transfer mechanisms at different temperatures: C denotes the concerted mechanism and S the stepwise mechanism.
    $R_c$ is the contribution from the concerted path to the rate as defined in the caption of Table \ref{tab:rates}.
    }
    \label{fig:Mechanism}
\end{figure}

At low temperature, only the concerted mechanism is possible since there is not enough thermal energy available to reach the high energy conformation at which the stepwise path takes place. The concerted mechanism presents a larger effective path length because two particles need to tunnel and consequently the microcanonical tunnelling probability is always smaller than for the stepwise case (See SI). For this reason, increasing the available thermal energy strongly favors the stepwise mechanism. Indeed, above the crossover temperature of this system \cite{Gillan1987}, $T_\mathrm{c}=\hbar\omega^{*}/2\pi k_\mathrm{B}\approx 300$ K, where
\rev{in most cases the contribution to the rate from classical hopping over the barrier becomes more important than tunneling, the stepwise mechanism is dominant. Previous evidence of the stepwise mechanism at 300 K from classical-nuclei molecular dynamics simulations reported in Ref. \citen{Walewski_JPCA_2010} benefit from this fact, but those simulations would not be able to predict the intricate balance between the two mechanisms at lower temperatures.} Our calculated DHT mechanisms at different temperatures are \rev{summarized} schematically in Fig.\ \ref{fig:Mechanism}d.

The competition of both mechanisms below $T_\mathrm{c}$ is compatible with some previous 2D-model studies \cite{Smedarchina_JCP_2007}. However, it goes against the common experimental
interpretation that this reaction happens exclusively through the concerted path at any (low) temperature \cite{Mengesha_JPCB_2015,Gil_JACS_2007}. In particular, the lack of {\it cis} conformers observed in
fluorescence anisotropy studies is treated as an indirect evidence for the concerted mechanism \cite{Ciacka_2015_JPCB,Fita_2009_CEJ}. We propose that this is not a conclusive observation. The
energy difference between the two isomers results in a very small {\it cis} population and due to the low barrier height for the {\it cis-trans} reaction, any transient {\it cis} isomer will have a very short lifetime. Therefore,
anisotropy measurements performed so far cannot rigorously confirm the mechanism in this particular scenario. Another possible experimental strategy to discern the DHT mechanism is to monitor kinetic isotope effects (KIE) upon substitution of two (DD) internal hydrogens by deuterium \cite{Braun_JACS_1994}.
However, due to the lack of well defined $\nu_{\text{HH}}$ and $\nu_{\text{DD}}$ bands, it has been difficult to interpret and quantify the isotopic purity of any sample.
\revi{The KIE is easily accessible from out calculations and}
we report in Table \ref{tab:rates} the DHT rate and the KIE for the DD \rev{isotopologue} of porphycene at 100 K.
KIEs from instanton theory benefit from error cancellations \cite{hexamerprism} that make them typically more reliable than direct rate calculations.
Nonetheless, our calculated KIE is 7 times higher than what was reported from experiments \cite{Ciacka_2016_JPCL}. \revi{This discrepancy would be consistent with an error of the theoretical barrier width with respect to experiment, especially for the stepwise mechanism. Indeed, we are correcting the B3LYP+vdW barrier height with data from CCSD(T), but we cannot correct the barrier width with the available data. Since the {\it trans-trans} pathway is symmetric and the {\it trans-cis} (stepwise) pathway is not, correcting only the barrier should work better for the former. The deuterium rate at 100 K involves a large fraction of the stepwise-mechanism contribution and thus is prone to a larger error.}
\rev{From our simulations, we find that} the DHT mechanism itself changes upon isotopic substitution, with deuteration strongly favoring the stepwise path as reflected by $R_c$.
This situation is different for porphyrin, where there is no competition between the different pathways already for HH, such that it was possible to confirm the dominance of the stepwise mechanism from experiments \cite{Braun_JACS_1994}.

Our full dimensional description allows us to go one step further and understand mode-coupling in this DHT in more detail. \rev{We employ the normal-mode decomposition proposed in Ref.\ \citen{Zahra2014} to analyze mode-specific contributions to tunneling splittings in porphycene. We take} the \textit{trans} isomer normal modes to
decompose the displacement between the geometry from where the tunneling takes place (the instanton turning point) of the concerted path and the global minimum.
Our decomposition, shown in Fig. \ref{fig:Mechanism}c, shows that more than \rev{87\%} of the displacement is given by the breathing mode of the molecular cage at around 200 cm$^{-1}$ (\revi{24 meV}). The coupling of the \rev{concerted} DHT to this low-energy mode implies a temperature-dependence for this reaction rate at low-temperatures that can look like an Arrhenius behavior, despite the massive contribution from tunneling.
\rev{Therefore, we show that the concerted mechanism is related to the} temperature dependence of the rate at low temperatures measured in Refs. \citen{Ciacka_2016_JPCL} and \citen{Gil_JACS_2007}, which is consistent with a barrier of 22 meV and the previous suggestion that this vibrational mode contributes to the DHT\@.
\rev{A novel insight that we gain from our simulations is that we can unambiguously explain the origin of the activation barrier for the second thermally activated channel reported in Ref.\ \citen{Ciacka_2016_JPCL}. From Fig.\ \ref{fig:Mechanism}b, it is apparent that for the stepwise tunneling path to be activated, the {\it cis} conformer minimum-energy needs to be reached. Detailed balance thus imposes an effective activation energy for this mechanism equal to the {\it trans} to {\it cis} energy difference. Our best estimate for this value is 107 meV (CCSD(T) with MP2 ZPE corrections), which matches the experimentally inferred activation barrier of 108 $\pm$ 9 meV.}

The signature of anharmonic intermode coupling and quantum contributions in the DHT is directly reflected in the vibrational fingerprints that appear in an IR spectrum. We compare in Fig.\ \ref{fig:IR-B3LYP} the IR spectra obtained with the quantum harmonic approximation (QH), the (anharmonic) time-correlation formalism with classical-nuclei dynamics (CL) at 290 K, and the same formalism with \revi{the approximation to} quantum-nuclei dynamics \revi{from TRPMD} (QA) at the same temperature (see Methods). We also present the experimental IR spectrum reported \revi{in Ref. \citen{Gawinkowski_2012_PCCP}. Below 1700 cm$^{-1}$ this spectrum was measured for porphycene in a CS$_2$ solution and above 1700 cm$^{-1}$ for porphycene in a KBr matrix.}

\begin{figure}
    \centering
    \includegraphics[width=0.9\columnwidth]{fig4.png}
    \caption{Porphycene IR spectra obtained through the (a) harmonic approximation, (b) Fourier transform of the dipole autocorrelation function from DFT-B3LYP+vdW trajectories with classical nuclei at 290 K, (c) Fourier transform of the dipole autocorrelation function from DFT-B3LYP+vdW trajectories with quantum nuclei at 290 K from TRPMD. (d) Experimental spectra as reported in Ref. 27. \revi{Below 1700 cm$^{-1}$ this spectrum was measured for porphycene in a CS$_2$ solution and above 1700 cm$^{-1}$ for porphycene in a KBr matrix.}
    The harmonic spectrum was artificially broadened with Gaussian functions for better visualization \revi{and all the theoretical spectra have a constant red shift of 40 cm$^{-1}$}. Dotted lines serve as guides to the eye.

    (e) Representative snapshots of the trajectory with quantum nuclei where all the replicas are superimposed. (f) Zoom of the Fourier transform of the \revi{TRPMD IR spectrum} in the N-H stretching mode region (orange) together with the adiabatic model (red dashed line) described in the text. }
    \label{fig:IR-B3LYP}
\end{figure}

Our calculated QH and CL spectra are in good agreement to the theoretical simulations previously presented in Ref. \cite{Gawinkowski_2012_PCCP}.
As discussed there, (classical-nuclei) anharmonicities play an important role for  $\nu_{\text{N-H}}$ at around 2900 cm$^{-1}$ (easily assignable from normal mode analysis) and coupling to low-frequency vibrations considerably broaden the peak.
However, the band is still present and shows a different shape than the experimentally measured spectrum at 290 K from Ref. \citen{Gawinkowski_2012_PCCP}.
With the inclusion of NQEs, this peak is red-shifted by 300 cm$^{-1}$ and broadened, producing a very weak signal, remarkably similar to the experimental line shape. We only observe a constant shift of \revi{$\approx$40 cm$^{-1}$} between our simulations and experiment, which likely originates from the B3LYP+vdW PES. We corroborated the NH-stretch character of this peak by comparing spectra from hydrogenated and deuterated molecules (see SI, Figure S9). The overtone peaks just below 2000 cm$^{-1}$ that were also observed in Ref. \citen{Gawinkowski_2012_PCCP} are present in our CL and QA simulations, albeit with a much lower intensity than the experimental bands. \revi{This discrepancy in intensities could stem from the fact that both CL and QA spectra cannot capture quantum coherence. It could also stem from a particular enhancement of these bands due to the KBr matrix present in the experiment or to the laser power profile. In order to resolve this issue, comparison to gas-phase experimental spectra at lower temperatures would be desirable, but such data is not available. Overall, the present} results show that NQEs are essential to explain quantitatively the softening of the $\nu_{\text{N-H}}$ band and resolve its apparent absence in the experimental spectrum \cite{Gawinkowski_2012_PCCP, Malsch_JPCA_1997}.

One can relate this lineshape also to the N-N distance distributions shown in Fig.\ \ref{fig:FreeEnergy}c. The shorter N-N distances in the path-integral simulations point to a strengthening of the H-bonds, which is related to the mode-softening (red-shift). Characterizing the strength of mode couplings and the fine-structure of this band, however, requires a deeper analysis, especially due to the fact that, as shown in Fig.\ \ref{fig:IR-B3LYP}e, the hydrogens are delocalized over the several energy wells.

We follow the approach suggested in Ref.\ \citen{Blaise_ACP_2008}, that provides a way of calculating IR lineshapes for coupled low and high-frequency vibrational modes, that we detail in the SI. We used the adiabatic model including direct damping (relaxation of the high-frequency mode) and indirect damping (relaxation of the low-frequency mode which is coupled to the high-frequency one). The most relevant parameters of the model are the high ($\Omega$) and low ($\omega$) frequency values, as well as the strength of the coupling between them ($\alpha$). As shown in Fig.\ \ref{fig:IR-B3LYP}f, the agreement of the model with the TRPMD IR-spectrum is good, especially for the fine-structure of the mode. \revi{Since this model disregards hydrogen transfer, and since the DHT occurs in very long time-scales compared to the N-H vibration, we safely conclude that DHT does not contribute to the lineshape of this peak, similar to recent reports regarding the formic-acid dimer \cite{Qu_JCP_2018}}. The parameters for the curve shown in Fig.\ \ref{fig:IR-B3LYP}f are reported in the SI. We can obtain good agreement for $2680<\omega<2750$ cm$^{-1}$ and $100<\Omega<115$  cm$^{-1}$, with corresponding $\alpha$ ranging from 0.70 to 0.85. The exact value of $\Omega$ most likely reflects an effective value that averages the coupling to several low-frequency cage-vibration modes. The coupling parameter $\alpha$ is more than one order of magnitude larger than a simple evaluation in the strong anharmonic coupling theory \cite{Blaise_BOOK} based on harmonic modes, reflecting the enhancement of coupling due to anharmonic NQE. Notably, the $\omega$ values are very illuminating. They lie between the \textit{trans} (2907 cm$^{-1}$) and \textit{cis} (2680 cm$^{-1}$) harmonic frequency values. \revi{This shows the importance of visiting {\it cis}-like structures, which is only possible due to tunnelling and ZPE contributions.}

\section{Conclusions}

In this paper we have presented a combination of techniques joining high level density-functional theory simulations and \rev{state of the art} path-integral based approximations to nuclear quantum dynamics that provides a deep physical understanding of hydrogen transfer reactions. We validated the predictive power of our approach through comparison with experimental data.

In particular, we have shown that in an accurate potential energy surface, NQEs involved in hydrogen transfer events can {\it qualitatively} change dynamical properties \rev{of the porphycene molecule. Our calculated \rev{full-dimensional} ring-polymer instanton rate of DHT is in good agreement with experiment at different temperatures}. From our simulations, we are able to \rev{quantitatively obtain the} relative contribution from the stepwise and the concerted DHT mechanisms at any temperature. \rev{We conclude that both tunneling pathways have a} similar contribution \rev{to the rate} at 150 K\@ and that \rev{only below 100 K the concerted pathway becomes dominant. We corroborate that the skeletal low-frequency vibration that couples to the DHT coordinate leads to an Arrhenius-like temperature dependence for the rate, even when the DHT is dominated by tunneling. Additionally, we show that the contribution of the stepwise pathway down to low temperatures explains the second thermally activated reaction channel reported in experiments.}

\revi{From the path-integral simulations}, we have shown how NQEs can strengthen N-H$\cdots$N bonds, modify the N-N distances, and shift peaks up to 300 cm$^{-1}$. The coupling and delocalization of the hydrogens within the cage explains the apparent absence of the N-H stretch band in the IR spectrum of this molecule, which had long puzzled researchers. \rev{The IR spectrum calculated from thermostatted ring-polymer molecular dynamics yields an exquisite agreement with the experimental lineshape of $\nu_{\text{N-H}}$, even for the fine-structure of the peak. We could reproduce this lineshape with a simple model of coupled quantum harmonic oscillators, which allowed us to confirm that the coupling of this mode to low frequency vibrations is enhanced when NQEs are included.}

\rev{A shortcoming of increasing the complexity is that a detailed quantitative understanding of vibrational mode-coupling can be compromised. \revi{Techniques like vibrational configuration interaction can, nevertheless, provide quantitative numbers even for rather complex molecules \cite{Chen_FarDis_2018}. Techniques based on dynamics, however, do not give direct access to coupling coefficients without the application of other models \cite{Geral_2011_JCTC}}. The \revi{adiabatic} model we employed in this work could give a qualitative explanation of the coupling and fine-structure of the NH-stretching mode in the IR spectrum. Mode-specific experimental and theoretical techniques, like time-resolved 2D-spectroscopy, would be necessary for a quantitative characterization of mode coupling at finite temperatures in high dimensional systems. Nevertheless, the approaches presented here pave the way to
address important problems in biology, related to  enzymatic reactions through low-barrier H-bonds \cite{Cleland1998}, unusual fingerprints of N-H$\cdots$N bonds in proteins \cite{Adhikary2014}, as well as to model functional materials that take advantage of hydrogen transfer events \cite{Ueda_JACS_2014, Sunairi_JPCC_2018,Horiuchi_Nat_2010}.}

\section{Methods \label{sec:methods}}

We performed CCSD(T) calculations extrapolated to the infinite basis-set limit to obtain benchmarks for the energetics of local minima and saddle points of porphycene (see more details in SI). We then compared less expensive exchange-correlation (xc) functionals within density-functional theory (DFT) to these benchmarks, and concluded that the B3LYP functional \cite{B3LYP4} including pairwise van der Waals corrections (vdW) \cite{TS} presented the best agreement with our reference for both energetic and geometrical properties. We thus chose this functional to perform all further electronic-structure calculations in this work. The Orca package \cite{ORCA} was used to perform CCSD(T) simulations and the FHI-aims \cite{FHI-AIMS} package for DFT simulations.

The nuclear degrees of freedom were sampled according to the B3LYP+vdW PES with MD and PIMD through the i-PI program \cite{i-pi,i-pi2} in connection with FHI-aims. The PIMD simulations  were performed coupled to the colored noise PIGLET thermostat \cite{PIGLET}. We were therefore able to use 6 and 12 beads for 290 K and 100 K simulations, respectively.

Thermal rates were calculated with instanton rate theory \cite{Miller_JCP_1975,Jor_perspective_2018}.
The instanton path represents \revi{an approximation to} the optimal tunneling pathway at a given temperature and can be determined for the full high-dimensional problem. We used the ring-polymer approach \cite{Andersson2009Hmethane,Richardson_JCP_2009,Jor_review_2018,Rommel_JCTC_2011} where the path is discretized and represented by $P$ beads in a harmonic ring polymer \cite{Chandler_JCP_1981}, through our recent implementation in the i-PI code \cite{i-pi2}.
We include all the 108 porphycene degrees of freedom in the path optimization. We have achieved convergence with 192 replicas at both 100 and 150 K (see SI). \rev{This corresponds to a simulation involving, effectively, 7296 atoms with first-principles and on-the-fly force evaluations.} We included a correction factor to the instanton action detailed in the SI, that linearly scales the action to match the CCSD(T) reference barrier, similar to Ref.\ \citen{Meisner:2018}.

Restarting an instanton calculation with higher number of replicas can be computationally expensive due to the necessity of
calculating all Hessians for the new amount of replicas. In order to overcome this bottleneck, we have derived and implemented in i-PI a ring-polymer expansion of the Hessian, given by $\mathcal{H}^{(k)}_{jm} = \sum_{s=1}^{P}  H^{(s)}_{jm} T(P',P)_{ks}$, where $P<P'$ and $H^{(s)}_{jm}$ is the $j m$ matrix element of the Hessian corresponding to the \textit{s-th} original replica and $\mathcal{H}^{(k)}_{jm}$ is the $j m$ matrix element of the Hessian corresponding to the \textit{k-th} expanded replica. The $P' \times P $ matrix $T(P',P)$ is the same transformation matrix used in other contraction/expansion approaches and given in Ref.\citen{Markland_2008_JCP}. \rev{We provide the derivation of this expression in the SI}. This procedure completely removes the necessity of calculating \textit{any} new Hessians during the optimization, after their calculation for the first ring-polymer geometry with a small number of beads (replicas).

The IR spectra were computed from the Fourier transform of the dipole autocorrelation function.
The classical correlation function was computed from 4 different 10 ps NVE trajectories and \revi{an approximation to the} quantum correlation function was computed using thermostatted ring polymer molecular dynamics \cite{Rossi_JCP_2014} coupled to generalized Langevin equation (TRPMD+GLE) thermostats, \revi{as described in Ref.\citen{Rossi_JCP_2018}}. In this case, we ran 7 different 10 ps trajectories using 16 beads (see convergence tests in the SI) and computed the dipole for all beads. In all cases, the starting configurations were taken from uncorrelated thermalized structures and we used a 0.5 fs time step for the integration of the equations of motion.

\begin{acknowledgement}
MR and YL acknowledge financial support from the Max Planck Society.
JOR's research is financially supported by the Swiss National Science Foundation (Project No.\ 175696).
\end{acknowledgement}

redpajama_set_name: RedPajamaArXiv


One 1904-O $1 Morgan Silver Dollar Coin PCGS MS64. PCGS Graded.
One 1854 Type 2 $1 Indian Princess Head Gold Dollar Coin NGC AU50. NGC Certified.
One 1723 Colonial 1/2 Penny Wood's Hibernia Coinage ANACS VG8 Details. ANACS Certified.
One 1884-CC $1 Morgan Silver Dollar Coin ANACS MS60. ANACS Certified.
One 1826 Capped Bust Half Dollar Coin NGC AU Details. NGC Certified.
One 1997-W $10 American Gold Eagle Proof Coin PCGS PR69DCAM. PCGS Graded.
One 1988A $1 Federal Reserve Note Misalignment ERROR.
One Lot of (2) 1983Mo Mexico Silver Libertad Coins.
One 1881-S $1 Morgan Silver Dollar Coin NGC MS64. NGC Certified.
One 1927 $2 1/2 Indian Head Quarter Eagle Gold Coin PCGS Genuine. PCGS Graded.
One 1953 Roosevelt Dime Proof Coin NGC PF67. NGC Certified.


text:
Internet Security: MT Show
Apr 5, 2016 1:00 pm
Adam K. Levin has an AB in Political Science from Stanford University and a JD from the University of Michigan, School of Law. He is a consumer advocate with more than 30 years experience in personal finance, privacy, real estate and government service. An expert in personal finance, credit, identity management, fraud and privacy. Author of "Swiped: How to Protect Yourself in a World Full of Scammers, Phishers, and Identity Thieves." Levin is the chairman and founder of Credit.com and former director of the New Jersey Division of Consumer Affairs. Today he talks about the importance of internet security and how we can protect ourselves.
Nepal Recovery
Bishnu Adhikari, is an in-country director in Nepal for Choice Humanitarian USA. The Center for Humanitarian Outreach and Inter-Cultural Exchange', is a strategic non-governmental agency (NGO) currently working all over the world to end extreme poverty and improve quality of life through a bottom-up, self-developing village-centered approach. Adhikari has two master degrees in Civil Engineering and Environmental Policy. He works with remote villages in the Himalayan Mountains to build roads, schools and water systems. Since the April magnitude-7.8 earthquake struck Nepal, where more than 9,000 people and injured more than 23,000 his work and our help is needed more than ever.
Vocal Fry
Dr. Mark Liberman is an American linguist. He has a dual appointment at the University of Pennsylvania, as Trustee Professor of Phonetics in the Department of Linguistics, and as a professor in the Department of Computer and Information Sciences. He is Faculty Master at Ware College House, Director of Linguistic Data Consortium and Christopher H. Browne Distinguished Professor of Linguistics. His recent publications include: "Development of Pitch Contrast in Korean Prosody: A Corpus Study" and "Vocal Fry: 'Creeping in' or 'still here'?" Dr. Liberman talks about the phenomenon of "Vocal Fry" and why it is used.


introduction to mining machinery industry modern mining technology,like that of all industry,languished during the dark ages.
· mining equipment, technology and service providers – where is the industry going?
shipyard equipment; stage technology; sugar industry; testing technology; transport technology; home > industries > machinery applications and engineering > mining .
efficiency and reliability are key requirements to operate within the mining industry. ge is committed to providing equipment with leading edge design in efficiency, as well as proven and reliable technology for this segment.
western australia's dynamic mining industry, which operates in some of the world's harshest and most remote conditions, relies heavily on the mining equipment, technology and services (mets) sector.


Ear Protection - Ear Muffs - Industrial strength Noise Reducing Ear Muffs.
Thunder series earmuffs are designed with all-day comfort in mind. Thunder headband earmuffs feature a unique dual headband for better positioning and breathability, and a non-deforming outer headband that minimizes pressure on the head. Plus, its dielectric construction withstands use and abuse, while protecting workers in electrical environments. The Thunder series features patented Air Flow Control� technology for optimal attenuation across all frequencies and also snap-in ear cushions for easy maintenance. Dielectric construction suitable for all workplaces, especially electrical environments Uniform headband pressure for all head sizes, providing better comfort for long-term wear Non-deforming outer headband withstands rough treatment in the toughest workplaces Quick-Click height adjustment remains fixed during wear Snap-in ear cushions make replacement quick and easy. Agriculture & Farming Building Construction Forestry General Contracting Heavy Construction Landscaping Lumber/Wood Products Metal Fabrication Military and Law Enforcement Petrochemical Sporting Steel Transportation Mining Utility/Waste Management This item cannot be shipped to APO/FPO addresses.
Howard Leight QM24+� Economical Earmuff, Ultra lightweight design and multiple-position headband allows wearer to select position over-the-head, behind-the-head or under-the-chin. Alternative to cap-mounted earmuffs � wear with hard hats, face shields, respirators and other PPE. Dielectric construction suitable for electrical environments. 25 NRR.
Radnor� Low Pressure Foam Disposable Earplugs are preshaped and tapered for easy insertion. Winged end for quick removal. Non-allergenic foam. Bright orange color eases compliance checks. Ideal for people with smaller ear canals Low-pressure polyurethane foam expands gently for comfortable, long-term wear Contoured T-shape for easy handling and fit Smooth, soil-resistant skin prevents dirt build-up Agriculture & Farming Automotive Aviation Building Construction Forestry Furniture Manufacturing General Contracting Heavy Construction Landscaping Lumber/Wood Products Manufacturing Metal Fabrication Military and Law Enforcement Mining Petrochemical Pulp & Paper Sporting Steel Transportation Equipment Utility/Waste Management This item cannot be shipped to APO/FPO addresses.
Softies� are made of extra-soft, extra-light foam and tapered design seal gently and snugly without pressure, while the outer surface is smooth, so it doesn't irritate the ear canal. NRR 33, making them the highest independently tested NRR available. Radiant orange color for easy compliance checks. 100% PVC-Free. Corded earplugs prevent earplug loss. 100% PVC-Free. Radiant orange color for easy compliance checks. Extra soft, low-pressure foam for comfort and fit. Tapered shape for easy insertion and removal Shaped to fit even very small ear canals Non-irritating smooth surface Highest independently tested NRR 33 Independently tested to ANSI S3.19-1974. This item cannot be shipped to APO/FPO addresses.
Optimized for exceptional in-ear comfort, AirSoft's new four-flange design creates a better seal in the ear canal, delivering optimal protection and increased comfort for long-term wear. Internal fins create an interlocking, noise-blocking barrier within the air pocket, providing dependable attenuation for all wearers upon proper insertion. At the same time, AirSoft's firm stem and tapered shape facilitate easy insertion and removal, and allow the earplug to sit comfortably in the ear canal. Advanced air pocket design features internal noise-blocking fins. Four-flange profile creates better seal in the ear canal. Less pressure in the ear canal eliminates that plugged up� feeling Rounded flanges, tapered shape fits better in the ear cana.l Firm stem facilitates easy insertion and removal. Outstanding noise-blocking protection � highest attenuation in multiple-use Agriculture & Farming Airport Ground Crews Building Construction Food & Beverage Processing Forestry General Contractor Landscaping Lumber/Wood Products Metal Fabrication Pulp & Paper Warehousing Printing Utility/Waste Management Petrochemical Assembly/Light Manufacturing Aviation Reusable durable storage case This item cannot be shipped to APO/FPO addresses.
Comfort meets performance as Swerve� incorporates a cutting-edge band design with the effectiveness of E-A-R foam earplugs. Lightweight and durable plastic flexes and rebounds easily for frequent on-and-off wearing. Two tip choices for wearer preferences. Sold with two tip choices - higher attenuating E-A-RFlex 28 pod and the soft Comfort Pod Neckband adjusts for optimal fit- band slides forward and back for custom neck and ear positioning. Ergonomic design helps to minimize interference- Neckband shape helps eliminate contact with collars and headgear. Also reduces band sound transmission. Noise Reduction Rating (NRR)*: 28 dB with the Flex 28 pod, or 19 dB with the Comfort Pod The NRR may overestimate the hearing protection provided during typical use. 3M recommends reducing the NRR by 50% for estimating the amount of noise reduction provided. CSA Class AL (Flex 28), CSA Class BL (Comfort Pod) This item cannot be shipped to APO/FPO addresses.
Meteors� unique curved design provides exceptional comfort. The contours follow the shape of the ear canal which means less pressure at the smallest diameter of the earplug. Meteors� innovative undercut design affords a secure fit, all day long. Plus, they have the highest independently tested NRR 33 available, a bright green color for easy compliance checks, and are PVC-Free 100% PVC-Free. Highest independently tested NRR 33 The contours follow the shape of the ear canal which means less pressure at the smallest diameter of the earplug. Meteors� innovative undercut design affords a secure fit, all day long Meteors are independently tested to ANSI S3.19-1974 by Michael & Associates, Inc., State College, PA. The bright green color is a trademark of Moldex-Metric, Inc. and also provides easy compliance checks. Independently tested to ANSI S3.19-1974. This item cannot be shipped to APO/FPO addresses.
Classic cylindrical shape provides the high-grade protection that you've come to expect. Slow-recovery, gradual post-insertion expansion ensures the creation of an effective sound barrier. Top-quality, moisture-resistant, dermatologically safe foam minimizes the potential for irritation. Corded/Cordless: Cordless; Shape: Cylinder; Material(s): PVC Foam; Noise Reduction Rate (NRR): 29 dB.
Eye-catching random color patterns on top of the highly successful Softies� design put SparkPlugs� first in line. Extra-soft foam provides a comfortable no-pressure fit. Form-fitting, tapered bullet ensures excellent attenuation. PVC-free. Corded/Cordless: Cordless; Shape: Bullet; Material(s): Foam; Noise Reduction Rate (NRR): 33 dB.
Replacement Pods for E-A-Rflex 28 Hearing Protector E-A-Rform� foam reacts to body temperature, warms, conforms, and becomes softer with wear time Non-irritating, dermatologically safe plugs NRR 28dB NRR 28dB This item cannot be shipped to APO/FPO addresses.
3M� E-A-R� Classic� earplugs were the first foam earplugs ever and are the most popular in the world. Today, they are still the leading seller across the world because of their outstanding advantages including: Excellent protection with an NRR 29dB; Easy to use cylindrical shape; Soft, low pressure for all day comfort; Non-allergenic, moisture resistant and non-flammable; Yellow for high visibility. E-A-R� Classic� earplugs are proven performers. Their proven size has been tested to be the right size to fit the widest range of ear canals while the cylinderical shape has been shown to protect better than tapered plugs. E-A-R� is the only manufacturer to make its own foam, so it can regularly test for optimum and consistant performance. No wonder they've been the most requested hearing protector in the world for over 30 years. Most popular earplug in the world. Laboratory tested NRR 29dB. The E-A-R� yellow color is your assurance of proven protection. Moisture resistant dermatological safe foam is not irritating. Slow recovery PVC foam provides comfort with low pressure. Flame retardant - critical for storage considerations. Meets ANSI S3.19-1974 Standards This item cannot be shipped to APO/FPO addresses.
The X3P3E utilizes a newly designed spacer to help improve attenuation without the need for amuch larger cup or double cup design. The lightweight earmuff is designed for protection against high-level industrial noise and other loud sounds. A universal mounting attachment fits most hard hats. Earcup pivot points that tilt for optimum comfort and efficiency. Replaceable ear cushions and foam liners (Hygiene kit HYX3). Stainless steel band construction resists bending and warping to offer consistent pressure over prolonged wearing periods Noise Reduction Rating (NRR) 25 dB. CSA Class AL.
Radnor� Reusable Earplugs feature a triple flange design that seals the ear canal completely to provide greater hearing protection. Its special design also allows users to have long-wearing comfort for all day use. Since they are reusable, they can be washed for extended use, saving you money. A triple flange design that provides exceptional hearing protection, long-wearing comfort and reusability They can be washed for weeks of use Intense orange plugs and cord make them highly visible Assembly/Light Manufacturing Automotive Aviation Building Construction Food & Beverage Processing General Contractor Landscaping Lumber/Wood Products Metal Fabrication Pulp & Paper Printing Utility/Waste Management Warehousing Agriculture & Farming Forestry Manufacturing Military and Law Enforcement Petrochemical This item cannot be shipped to APO/FPO addresses.
E-A-R� exclusive patented orange Fitting Ring. Most popular earplug in the world Moisture resistant dermatological safe foam is not irritating. Slow recovery PVC foam provides comfort with low pressure. Laboratory tested NRR 33dB. Meets ANSI S3.19-1974 Standards This item cannot be shipped to APO/FPO addresses.
Meteors� ear plugs now come in a new, small size to fit smaller ear canals. The same exceptional comfort that comes from the unique curved design of Meteors� is now available for women and other workers with smaller ear canals. The contours follow the shape of the ear canal which means less pressure at the smallest diameter of the earplug. Meteors� innovative undercut design affords a secure fit all day long and are PVC-Free. The large base helps provide proper insertion, fit and removal. And now the same high-level comfort and fit is available to women and other workers with smaller ear canals with the new Meteors�, Small. 100% PVC-Free. Soft, slow recovery foam and contoured shape molds easily to the ear canal for all day comfort. The contours follow the shape of the ear canal which means less pressure at the smallest diameter of the earplug. Meteors� innovative undercut design affords a secure fit, all day long Meteors� are independently tested to ANSI S3.19-1974 The bright green color is a trademark of Moldex-Metric, Inc. and also provides easy compliance checks. Independently tested NRR 28 for Meteors� small This item cannot be shipped to APO/FPO addresses.
3M� E-A-R� Classic Soft� earplugs are made of a patented, thermal-reactive foam used by the NASA space program. The material feels smoother than ordinary foam, and starts out firm to allow for easy insertion. Then, the plugs warm with the body temperature. They actually soften and shape to the ear canal. This "custom," low pressure seal helps provide an excellent NRR of 31 dB. Better yet, the plugs get even softer and more comfortable with extended wear. Not Just A New Plug, A Whole New Foam. E-A-R� Classic Soft� earplugs will change the way people �feel� about foam earplugs � because they feel entirely different. Made of a patented new foam, these plugs have a smaller cell structure and feel smoother "to the touch" than other foam. But that's just the beginning, the foam plugs actually react to the wearer's body temperature. Thermal-Reactive: Soft Gets Even Softer. The new plugs start out firm enough to make roll-down and insertion easy. As the foam warms to the body temperature, it becomes even softer and shapes to the individual's ear canal. This �shaping� allows the plugs to form an excellent seal against noise (NRR 31 dB) and, as time goes on, the foam continues to soften for added comfort. Most popular earplug in the world. Laboratory tested NRR 31dB. The E-A-R� yellow color is your assurance of proven protection. Thermal Reative Foam� gets softer with wear. Meets ANSI S3.19-1974 Standards This item cannot be shipped to APO/FPO addresses.
3M� E-A-R Push-Ins� combine the easy use and benefits of a reusable earplug with the cost and comfort advantages of a disposable earplug. It's all made possible with the innovative, simple-to-use design and the ultra-soft performance of a tip made of patented E-A-Rform foam, a derivative of the foam developed for NASA for use in their space shuttle seats. SofTouch� Push-Ins� have the highest NRR of any Push-In product in an easy fitting narrow to wide design. It's also the most comfortable Push-In style product. No rolling or touching plug portion during insertion; eliminates fear of ear contamination EARform foam tip is shaped and sized to mold comfortably to fit virtually every size earcanal Stem allows for better hygiene The E-A-R� yellow color is your assurance of proven protection. Simple to use design and ultra soft performance. Workers don't have to take the time to roll-down the foam tip. Quicker and easier to use. Laboratory tested NRR 31dB. Meets ANSI S3.19-1974 Standards This item cannot be shipped to APO/FPO addresses.


Submitted by anya.rao on Wed, 08/22/2018 - 2:37pm.
Insta Graphic Systems, located in Cerritos, California and Graphics One, located in Sunnyvale, California have inked a distribution agreement encompassing the distribution of Insta's leading line of heat presses. This agreement covers certain vertical market segments where Graphics One is heavily involved, including the toner textile transfer business segment.
"We are pleased to enter into this agreement with Graphics One whose focus on solution selling fits well with our overall strategy. Additionally, Graphics One's focus of only working through graphics dealers involved in the transfer and dye-sub markets dovetails with our efforts to further penetrate this market. We are pleased to have Graphics One partner with us in this effort," stated Janet Wells, President of Insta. "Graphics One will be bundling our heat presses with a variety of printers which include the OKI Textile Transfer line, the new GO SubliMate printers and with a variety of other printers focused on unique industrial applications."
Amir Ajanee, Managing Partner of AD International, the owner of Graphics One indicated, "we have long wanted to partner with a heat press manufacturer located in the U.S. who offers high-quality heat presses. Many people do not know that Insta has been involved in the toner transfer market longer than any other heat press manufacturer in the market. In fact, the leading transfer papers were all developed using Insta Graphics heat presses. We are really pleased to enter into this distribution agreement with one of the leaders of our industry."
Insta's leading heat presses are available immediately via Graphics One's extensive dye sub and heat transfer sales channel.


Thank you for visiting the Saint James Parish website! Saint James has been serving Catholic believers and our local community for over 100 years. Our Parish family strives to bring the Gospel of Christ into our daily lives at home, at school and at work.
Please click the link below to make your donation today!
Sunday, June 2, 2019 - Save the Date!
WeShare, now provides an easy way to plan out your Mass Intentions, Fuel & Maintenance, Weekly Offertory or second collection donations for the whole year!
To start today, click on the below Donate icon and View Collections or All Second Collections. Simply choose the amount you wish to contribute to each collection or second collection, enter a payment source, and submit your second collection donations for the entire year at one time. Make sure to check the "Recurs Annually" box if you wish to continue contributing year after year.
Please contact the parish office if you have questions or need help setting up your Collections or Second Collection donations. Thank you for your continued support to our parish!
Parish Office is closed on all Holy Days.


text:
Q: What's wrong with this stored procedure (nested SELECT)? This is throwing a syntax error on the first SELECT - why?
CREATE DEFINER=`root`@`localhost` PROCEDURE `get_cand_by_pos_skill`(IN id INT)
BEGIN
SELECT *  FROM candidates
WHERE cid = ANY(SELECT candid FROM positionskills p, candidate_skills s WHERE p.positionid = id and s.skillid = p.skill);
END

A: *

*You need to define the Delimiter to something else (eg: $$) other than ;. At the end redefine back to ;

*Please do not use comma based Implicit joins. These are obsolete and error-prone. Please switch to modern JOIN .. ON based syntax.

*Switch to IN instead of = ANY:

Try the following instead:
DELIMITER $$
CREATE DEFINER=`root`@`localhost` PROCEDURE `get_cand_by_pos_skill`(IN id INT)
BEGIN

SELECT *
FROM candidates
WHERE cid IN (SELECT candid
              FROM positionskills p
              JOIN candidate_skills s ON s.skillid = p.skill
              WHERE p.positionid = id);

END $$
DELIMITER ;

redpajama_set_name: RedPajamaStackExchange


text:
Alert October 23, 2019
Trump Administration Lifts Sanctions on Turkey
On October 23, 2019, the Trump Administration moved to lift sanctions against Turkey it imposed on October 14, 2019, in response to Turkey's invasion of northern Syria. The Treasury Department's Office of Foreign Assets Control (OFAC) removed sanctions on all five sanctioned entities (three Turkish government officials and the Turkish Ministries of National Defence and Energy and National Resources). Congress could impose new sanctions on Turkey going forward, so stay tuned.
*Note: this is an update to an alert that was originally published on October 16, 2019, which appears below.
Trump Administration Imposes Sanctions on Turkey in Response to Syrian Invasion
In the wake of Turkey's invasion of northern Syria, the Trump Administration issued an Executive Order (EO) on October 14, 2019, authorizing sanctions on Turkish government officials and government ministries. Additionally, President Trump said that he would halt ongoing trade talks with Turkey and that the United States would re-impose 50% tariffs on imports of Turkish steel.
The sanctions announced on Monday target three Turkish government officials: the Ministers of Defence, Energy and Natural Resources, and the Interior. The Treasury Department's Office of Foreign Assets Control (OFAC) also designated Turkey's Ministry of National Defence and its Ministry of Energy and Natural Resources as Specially Designated Nationals (SDNs). The new sanctions block all property and interests in property of these individuals and entities that are in, or come within, the United States or the possession or control of a United States person, essentially cutting these individuals and entities off from the U.S. market and dealings with U.S. companies. The prohibitions also extend to transactions with entities in which the newly-sanctioned individuals and entities hold a direct or indirect ownership interest of 50% or more.
In conjunction with the new SDN designations, OFAC issued general licenses—or broad authorizations—permitting certain otherwise prohibited transactions by U.S. government employees, grantees, or contractors as well as the United Nations, including its Programmes and Funds, and its Specialized Agencies and Related Organizations. OFAC also issued a general license allowing U.S. persons to wind down operations, contracts, and other agreements with the Ministry of National Defence or the Ministry of Energy and Natural Resources, which is effective until November 13, 2019.
The new EO is drafted broadly such that it can be used to impose additional sanctions on Turkey, other persons providing goods or services to SDNs or engaging in destabilizing activities in Syria, and foreign financial institutions that engage in a significant financial transaction involving an SDN. Additionally, Congressional leadership, after criticizing the efficacy of the Trump Administration's new sanctions, has indicated that it plans to introduce legislation providing for a more extensive package of sanctions on Turkey, including the potential of cutting off U.S. military support to the NATO partner.
Wiley Rein continues to closely monitor the developing situation in northern Syria and the Trump Administration's response. Should you have any questions about the new sanctions on Turkey, or the potential for further sanctions, please do not hesitate to contact one of the attorneys listed on this alert.
Jack R. Shane
jshane@wiley.law
Lori E. Scheetz
lscheetz@wiley.law
Economic Sanctions/OFAC


If it moves, we plan for it.
by air, rail, truck or on water.
The recommendations, data and public input from short range projects advance us toward meeting the goals outlined in our 25-year Long Range Transportation Plan.
The MIC's short range planning projects are conducted over the course of six to 24 months and focus on specific locations, modes of travel, or both.
Improving truck-based freight movement throughout Duluth, MN and Superior, WI This study will examine current truck routes and the factors that influence truck movements to, through and around the Duluth-Superior area to determine the most efficient, safest and least disruptive truck routes.


Thunder Tactical Shooters is a nonprofit organization of private individuals that hosts defensive pistol competitions for the enjoyment of IDPA members in Southeast, Texas. Whether you just purchased your first handgun or you've owned one for years (but never competed) you are welcome to join us!
We can send you a text when range conditions are a cause for cancellation. To sign up, please send an email to Thundertacticalshooters@gmail.com.
Match results for those IDPA matches shot at TTS will be posted at the Match Signup page (referenced above). Scores for matches that are NOT standard IDPA formats (PASS, Hybrid, etc.) are not able to be posted at the Match Signup. You will find those results on PractiScore. Visit the link and search using the term TTS.
We have instituted a new REFUND Policy for cases where the range is not open or a shooter cannot attend a scheduled event. To view a summary of the policy CLICK HERE.
Make plans to join Thunder Tactical Shooters on Wednesday or Thursday (or both) for one of our weekly practice matches. This is your chance to practice the basic skills required to safely and accurately shoot your defensive handgun. It's also a big bunch of fun!
Practice matches involve breaking into 8-10 person "squads" and shooting each of five separate stages/scenarios. Each stage/scenario cusually requires 12-24 rounds and will often include your need to reload, shoot at targets while moving, shooting around barricades or barrels, or other skills that challenge the shooter.
New (or first-time) shooters MUST arrive by 6 pm for a New Shooter's Orientation. TTS staff will review stage designs, the range commands, safety topics, and other issues that you'll confront in the weekly match.
The weekly match is one reason that "practical shooting" is the MOST FUN you can have shooting at paper targets at any gun range! Don't miss out! Register at the MATCH SIGNUP graphic at the top of this page.
Thunder Tactical Shooters is planning our monthly match for May. Put it on your calendar now so that you don't double-schedule any other events.
The May match directors are Jennifer Kroll and Danny Thompason who are planning to bring us USPSA pistol match. This match is scheduled to have 5 stages plus one classifier. Estimated round count is "about 170.".
Thunder Tactical Shooters fees for this match are $10 per shooter. NOTE: Thunder Gun Range fees are a separate fee to be paid to Jessie when you arrive at the range.
Make plans to join us and register using the MATCH SIGNUP link at the top of this page.
(Friday The 10th) starting at 4pm!
Help with setup - Shoot for Free!


text:
package com.dbflow5.models.java;

import com.dbflow5.TestDatabase;
import com.dbflow5.annotation.Column;
import com.dbflow5.annotation.ModelView;
import com.dbflow5.annotation.ModelViewQuery;
import com.dbflow5.database.DatabaseWrapper;
import com.dbflow5.models.Author_Table;
import com.dbflow5.query.SQLite;
import com.dbflow5.sql.Query;

@ModelView(database = TestDatabase.class)
public class JavaModelView {

    @ModelViewQuery
    public static Query getQuery() {
        return SQLite.select(Author_Table.first_name.as("firstName"), Author_Table.id.as("id"));
    }

    @Column
    String id;

    @Column
    Integer firstName;

}

redpajama_set_name: RedPajamaGithub


text:
Kia Kokalitcheva Mar 23, 2017
Twitter is weighing whether to build a paid version of TweetDeck
Richard Drew / AP
Twitter is considering whether to build premium software geared toward power users of its service.
The company already owns TweetDeck, a program geared toward those who juggle multiple Twitter accounts and spend a lot of time on the social media service. A paid version could offer extra features and bypass advertising.
Andrew Tavani, managing editor of Women in the World, first spotted a message from Twitter about the potential service.
Still pondering: It appears the idea is still in the early stages and Twitter hasn't decided if it'll build this. "We're conducting a survey to assess the interest in a new, more enhanced version of TweetDeck," a Twitter spokesperson told Axios, adding that Twitter is "exploring several ways to make TweetDeck even more valuable for professionals."
Why it matters: Twitter acquired TweetDeck in 2011 from developer Iain Dodsworth, but hasn't done much with it since as far as expanding features and capabilities. This could be a welcome option for users for whom Twitter is a critical part of doing their job.