Large Coupling Constant Research Articles

1.3 Å Crystal Structure of E. coli Peptidyl-Prolyl Isomerase B with Uniform Substitution of Valine by (2S,3S)-4-Fluorovaline Reveals Structure Conservation and Multiple Staggered Rotamers of CH2F Groups.

(2S,3S)-4-Fluorovaline (FVal) is an analogue of valine, where a single CH3 group is substituted by a CH2F group. In the absence of valine, E. coli valyl-tRNA synthetase uses FVal as a substitute, enabling the production of proteins uniformly labeled with FVal. Here, we describe the production and analysis of E. coli peptidyl-prolyl isomerase B where all 16 valine residues have been replaced by FVal synthesized with a 13C-labeled CH2F group. Although the melting temperature is lower by about 11 °C relative to the wild-type protein, the three-dimensional protein structure is almost completely conserved, as shown by X-ray crystallography. The CH2F groups invariably populate staggered rotamers. Most CH2F groups populate two different rotamers. The increased space requirement of fluorine versus hydrogen does not prohibit rotamers that position fluorine next to a backbone carbonyl carbon. 19F NMR spectra show a signal dispersion over 25 ppm. The most high-field shifted 19F resonances correlate with large 3JHF coupling constants, confirming the impact of the γ-gauche effect on the signal dispersion. The present work is the second experimental verification of the effect and extends its validity to fluorovaline. The abundance of valine in proteins and structural conservation with FVal renders this valine analogue attractive for probing proteins by 19F NMR spectroscopy.

On the conformal limit of a QED-inspired model

A conformal invariant QED-inspired model is solved for a general covariant linear gauge using the Dyson–Schwinger equations for the propagators assuming a pure vector like interaction. The leading corrections to the asymptotic solutions and the exponents, that characterize the corrections to each of the two fermion propagator functions, are computed as a function of the coupling and gauge fixing parameter ξ\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\xi $$\\end{document}. For the scalar component of the fermion propagator our findings generalizes for linear covariant gauges previous results found in the literature and reproduce the outcome of the perturbative analysis of quenched QED in the Landau gauge. Our solution for the exponent associated with vector component of the fermion propagator is new and, in the weak coupling regime, agrees with the estimation based on the perturbative analysis of quenched QED. Of the two critical exponents describing the conformal limit of the vector interaction, one of them is, in QED, associated with the regime where chiral symmetry is broken dynamically, which demands one mass scale, namely the Miransky scaling. A second mass scale has to be introduced at larger coupling constants and is associated with a change on the nature of the fermion wave function. This provides one example, that it is possible to find two interwoven cycles in Quantum Field Theory, albeit in a truncated framework, as it is known in the quantum few-body problem in the limit of a zero-range interaction.

Synthesis and Conformational Analysis of α,β‐Dichlorocarbonyl Compounds

α,β‐Dichlorocarbonyl compounds were synthesized by facile dichlorination of α,β‐unsaturated amides with TCIA‐PPh3 and the resultant amides were converted to ketones. Conformational analyses of the products were performed to confirm our previous hypothesis regarding vicinal dichlorinated carbonyl compounds. The compounds exhibited 1H NMR signals with large coupling constants (7‐11 Hz) for the 1,2‐anti‐configuration and small coupling constants (3‐4 Hz) for the 1,2‐syn‐configuration. The syn‐pentane interaction enabled rational conformational analysis of the α,β‐dichlorinated carbonyl compounds, although some interesting exceptions were observed. Consideration of these conformations is helpful in assigning relative configurations of α,β‐dihalogenated carbonyl compounds in general.

Capturing Metal Fluoride inside a Carbon Cage.

We report here a new type of metal fluoride cluster that can be stabilized inside fullerene via in situ fluorine encapsulation followed by exohedral trifluoromethylation, giving rise to rare-earth metal fluoride clusterfullerenes (FCFs) M2F@C80(CF3) (M = Gd and Y). The molecular structure of Gd2F@C80(CF3) was unambiguously determined by single-crystal X-ray analysis to show a μ2-fluoride-bridged Gd-F-Gd cluster with short Gd-F bonds of 2.132(7) and 2.179(7) Å. The 19F NMR spectrum of the diamagnetic Y2F@C80(CF3) confirms the existence of the endohedral F atom, which exhibits a triplet with a large 19F-89Y coupling constant of 74 Hz and a high temperature sensitivity of the 19F chemical shift of 0.057 ppm/K. Theoretical studies reveal the ionic Y-F bonding nature arising from the highest electronegativity of the F element and an electronic configuration of [Y2F]5+@[C80]5- with an open-shell carbon cage, which thus necessitates the stabilization of FCFs by exohedral trifluoromethylation.

Quantum Bipolaron Superconductivity from Quadratic Electron-Phonon Coupling.

When the electron-phonon coupling is quadratic in the phonon coordinates, electrons can pair to form bipolarons due to phonon zero-point fluctuations, a purely quantum effect. We study superconductivity originating from this pairing mechanism in a minimal model and reveal that, in the strong coupling regime, the critical temperature (T_{c}) is only mildly suppressed by the coupling strength, in stark contrast to the exponential suppression in linearly coupled systems, thus implying higher optimal T_{c} values. We demonstrate that large coupling constants of this flavor are achieved in known materials such as perovskites, and discuss strategies to realize such superconductivity using superlattices.

Single component long-lived dynamic room temperature phosphorescence with large-scale preparation and visible light excitation

A pure organic room temperature phosphorescence (PORTP) luminogen named as DCP was successfully prepared and showed long room temperature phosphorescence (RTP) and afterglow lifetimes (3 ms and 4 s in sequence). Meanwhile, DCP showed high fluorescence (0.14) and RTP (0.39) quantum yields in crystalline state, simultaneously presented visible light excitation and dynamic RTP. By host-guest doping and optimization, Urea/DCP doping system emitted blue RTP, with RTP and afterglow lifetimes of 341 ms of 5 s in turn. Crystal analysis and theoretical calculations indicated H stacking, large spin orbit coupling constant, and small energy gap between the lowest singlet and triplet states result in long RTP lifetime and high quantum yield for DCP. Based on long phosphorescence emission, an advanced anti-counterfeiting pattern was constructed. As far as we know, it is the first report that such small molecules containing 3, 5-dicyanopyridine show long-lived RTP in both crystalline state and doping system. In this paper, not only ultralong and blue PORTP materials with the advantage of large-scale preparation, but also single component dynamic RTP, and RTP of visible light excitation were achieved.

Coherent Interaction of a Few-Electron Quantum Dot with a Terahertz Optical Resonator.

We have investigated light-matter hybrid excitations in a quantum dot (QD) THz resonator coupled system. We fabricate a gate-defined QD near a THz split-ring resonator (SRR) by using a AlGaAs/GaAs two-dimensional electron system. By illuminating the system with THz radiation, the QD shows a current change whose spectrum exhibits coherent coupling between the electrons in the QD and the SRR as well as coupling between the two-dimensional electron system and the SRR. The latter coupling enters the ultrastrong coupling regime and the electron excitation in the QD also exhibits coherent coupling with the SRR with the remarkably large coupling constant, despite the fact that only a few electrons reside in the QD.

Host-guest interaction induced room-temperature phosphorescence enhancement of organic dyes: a computational study.

To achieve the effective regulation of organic room temperature phosphorescence (RTP) in supramolecular systems, the elucidation of host-guest interactions in RTP is of vital importance. Herein, we employed two organic dyes (PYCl and PYBr) and their four host-guest complexes with CB[6] and CB[7] and explored the mechanism of host-guest interaction induced RTP enhancement using quantum mechanics/molecular mechanics (QM/MM) approach. For the two organic dyes, we found that the better RTP performance of PYBr than PYCl is attributed to intersystem crossing (ISC) augmentation induced by the heavy atom effect. Binding to CB[6] through host-guest interactions can simultaneously accelerate the radiative decay process by increasing the transition dipole moment of T1 → S0 (μT1→S0), block the nonradiative decay process, and promote the ISC process, eventually leading to a remarkably boosted RTP. Upon complexation, the conversion of S1 from 1(n, π*) to 1(π, π*) is key to μT1→S0 enhancement; reduced reorganization energies reflect the suppression of the nonradiative decay process by restricting the rotation of rings A and B in organic dyes. In addition, the promoted ISC process is due to the activation of more ISC channels between S1 and high-lying triplet states with large spin-orbital coupling constants and small energy gap. The case of CB[7]-type complexes is much different, because of the extremely large cavity size of CB[7] for encapsulation. This work proposes the mechanism of host-guest interaction-induced RTP enhancement of organic dyes, thus laying a solid foundation for the rational design of advanced RTP materials based on supramolecular assemblies.

Triplet-triplet energy transfer between host and guest induced strong phosphorescence in the organic doped system

Recently, purely organic room-temperature phosphorescence (RTP) from guest-host-doped systems has grown exponentially due to their high modulation flexibility. Benzophenone has been found as a preferred host matrix thanks to its low melting point, minimal biological toxicity, remarkable stability, and cost-effectiveness. However, the precise role of benzophenone remains elusive and has been debated within the scientific community concerning mechanistic elucidations. Here, five indole derivatives were designed and synthesized as guest molecules while retaining benzophenone as the host to construct doped materials exhibiting outstanding RTP properties. Our experimental findings unequivocally establish that the host benzophenone initially absorbs excitation energy, subsequently intersystem crossing into triplet exciton, facilitating the exciton transfer to guest molecule through the triplet energy transfer and culminating in guest RTP emission. Mechanistic investigation corroborates the superiority of benzophenone in possessing a large spin-orbit coupling constant and quantitatively triplet energy transfer. Collectively, this work provides compelling evidence deciphering energy transfer between host and guest entities for the manifestation of phosphorescence performance in benzophenone-hosted doped materials.

Entanglement area law violation from field-curvature coupling

We investigate the ground state entanglement entropy of a massive scalar field nonminimally coupled to spacetime curvature, assuming a static, spherically symmetric background. We first discretize the field Hamiltonian by introducing a lattice of spherical shells and imposing a cutoff in the radial direction. We then study the ground state of the field and quantify deviations from area law due to nonminimal coupling, focusing in particular on Schwarzschild-de Sitter and Hayward spacetimes, also discussing de Sitter spacetime as a limiting case. We show that large positive coupling constants can significantly alter the entropy scaling with respect to the boundary area, in case of coordinate-dependent spacetime curvature. Our outcomes are interpreted in view of black hole entropy production and early universe scenarios.

Modulating excited state properties of thermally activated delayed fluorescence molecules by hybrid long-range and short-range charge transfer strategy

Balancing the rapid radiative decay process and the fast reverse intersystem crossing (RISC) process of thermally activated delayed fluorescence (TADF) molecule remains a great challenge and efficient molecular design strategies are highly desired. Herein, from a theoretical perspective, excited state properties of three reported TADF molecules (1TICz, 1BOICz and 2BOICz) are investigated based on density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations coupled with the thermal vibration correlation function (TVCF) method. Results indicate that, by introducing the multi-resonance (MR) acceptor, 1BOICz possesses hybrid long-range and short-range charge transfer features, balanced small energy gap (ΔEST) and large oscillator strength (f) is obtained. Furthermore, by incorporating double equivalent MR acceptors in 2BOICz, largely enhanced f with slightly changed ΔEST is achieved, inner mechanism for remarkable photophysical property is illustrated. Keep this strategy, seven new TADF molecules (2pDBA-bICz-1, 2pDBA-bICz-2, 2OSBA-bICz, 2DQAO-bICz, 2QAO-bICz, 2SQAO-bICz and 2OQAO-bICz) are theoretically designed, detailed physical parameters are analyzed and excited state energy consumption process is studied. Strong electrophilicity on acceptor is determined and the strength of nucleophilic sites on the bridge-phenyl of 2DQAO-bICz, 2QAO-bICz, 2SQAO-bICz and 2OQAO-bICz is increased, this promotes the short-range charge transfer property. In addition, the excitation processes for all studied molecules are dominated by long-range charge transfer from donor to acceptors, and supplemented by the short-range charge transfer on the bridge-phenyl with MR effect. Compromise energy gap and oscillator strength as well as large spin orbit coupling (SOC) constant are obtained for designed molecules. Thus, by regulating the long-range and short-range charge transfer ratios, excited state properties are successfully modulated and new efficient TADF molecules are proposed. Our research aims to provide deeper insight into long-range and short-range charge transfer features in balancing small ΔEST and large f, which could facilitate the development of novel efficient TADF molecules.

Theoretical perspective for structural isomerism effect on photoelectric properties of organic room temperature phosphorescence molecules

Purely organic room temperature phosphorescence (RTP) materials have garnered extensive attentions in anti-counterfeiting and encryption, information display, biological imaging and organic light emitting diodes (OLEDs) due to the features of long lifetimes, low toxicity and good biocompatibility. Nevertheless, both the species and amounts of the efficient RTP molecules are far from meeting the requirements for practical applications, and the quantitative relationship between molecular structures and optoelectronic properties needs full elucidated. Herein, the photophysical properties and properties of three isomers (o-BA, m-BA and p-BA) are explored based on the first-principles calculations coupled with thermal vibration correlation function (TVCF) method and kinetic Monte Carlo simulations. The substituent effects on the molecular structures, intermolecular interactions, transition properties, Huang-Rhys factors and reorganization energies, excited state dynamics as well as transfer integrals and charge carrier mobilities are investigated in detail to clarify the structure-property relationships. Results show that o-BA achieves fast radiative rate on account of impressive transition dipole moment and oscillator strength, but equally large non-radiative decay rate leads to low RTP efficiency. Promisingly, the highest holes mobility is determined for o-BA due to the largest transfer integrals of holes originating from the strong intermolecular interactions. In addition, compared with o-BA and p-BA, m-BA could achieve fast intersystem crossing (ISC) rate with large spin orbit coupling constant and low non-radiative decay rate with small geometric structure changes. Relatively balanced holes and electrons mobilities of m-BA have been demonstrated, which contributes to the recombination of excitons and the improvement of luminescence efficiency. For p-BA, the strong intermolecular hydrogen bonding restricts the free rotation of single bonds and promotes the molecular coplanarity, which contributes to efficient emission. Furthermore, the charge mobility is calculated and the temperature dependence is investigated, the hopping mechanisms for studied isomers are illustrated. This work reveals the relationship among molecular structures, crystal packing modes, photophysical properties and charge transport properties of isomers, and provides an insight for molecular design and property prediction.

Long-Range Order for Critical Book-Ising and Book-Percolation

In this paper, we investigate the behaviour of statistical physics models on a book with pages that are isomorphic to half-planes. We show that even for models undergoing a continuous phase transition on Z2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${\\mathbb {Z}}^2$$\\end{document}, the phase transition becomes discontinuous as soon as the number of pages is sufficiently large. In particular, we prove that the Ising model on a three pages book has a discontinuous phase transition (if one allows oneself to consider large coupling constants along the line on which pages are glued). Our work confirms predictions in theoretical physics which relied on renormalization group, conformal field theory and numerics (Cardy in J Phys A Math Gen 24(22):L131, 1991; Iglói et al. in J Phys A Math Gen 24(17):L1031, 1991; Stéphan et al. in Phys Rev B 82(12):125455, 2010) some of which were motivated by the analysis of the Renyi entropy of certain quantum spin systems.

Few-Hydrogen High-Tc Superconductivity in (Be4)2H Nanosuperlattice with Promising Ductility under Ambient Pressure.

The multi-hydrogen lanthanum hydride LaH10 is well recognized as having the highest critical temperature (Tc) of 250-260 K under unrealistically ultrahigh pressures of about 170-200 GPa. Here, we propose a novel idea for designing a new ambient-pressure high-Tc superconductor by inserting a hexagonal H-monolayer into two close-packed Be monolayers to form a new and stable few-hydrogen metal-bonded layered beryllium hydride (Be4)2H nanosuperlattice, with better ductility than multi-hydrogen, cuprate, and iron-based superconductors, completely contrary to the conventional design strategy for multi-hydrogen covalent high-Tc superconductors with poor ductility at several hundred GPa. We find that (Be4)2H is a phonon-mediated Eliashberg superconductor with a large electron-phonon coupling constant of 1.41 and a high Tc of 84-72 K with Coulomb repulsion pseudopotential μ* = 0.07-0.13. Importantly, (Be4)2H is the only new high-Tc superconductor and fills the gap in the absence of ambient-pressure superconductors around the liquid-nitrogen temperature with good ductility, which is highly beneficial for practical applications.

Evidence for Band Renormalizations in Strong-Coupling Superconducting Alkali-Fulleride Films.

There has been a long-standing debate about the mechanism of the unusual superconductivity in alkali-intercalated fullerides. In this Letter, using high-resolution angle-resolved photoemission spectroscopy, we systematically investigate the electronic structures of superconducting K_{3}C_{60} thin films. We observe a dispersive energy band crossing the Fermi level with the occupied bandwidth of about 130meV. The measured band structure shows prominent quasiparticle kinks and a replica band involving the Jahn-Teller active phonon modes, which reflects strong electron-phonon coupling in the system. The electron-phonon coupling constant is estimated to be about 1.2, which dominates the quasiparticle mass renormalization. Moreover, we observe an isotropic nodeless superconducting gap beyond the mean-field estimation (2Δ/k_{B}T_{c}≈5). Both the large electron-phonon coupling constant and large reduced superconducting gap suggest a strong-coupling superconductivity in K_{3}C_{60}, while the electronic correlation effect is suggested by the observation of a waterfall-like band dispersion and the small bandwidth compared with the effective Coulomb interaction. Our results not only directly visualize the crucial band structure but also provide important insights into the mechanism of the unusual superconductivity of fulleride compounds.

Comparison of methods for 14N-1H recoupling in 14N-1H HMQC MAS NMR

1H-detected 14N heteronuclear multiple-quantum coherence (HMQC) magic-angle-spinning (MAS) NMR experiments performed at fast magic-angle spinning (≥50 kHz) are finding increasing application, e.g., to pharmaceuticals. Of importance to the efficacy of these techniques is the recoupling technique applied to reintroduce the 1H-14N dipolar coupling. In this paper, we compare, by experiment and 2-spin density matrix simulations, two classes of recoupling scheme: first, those based on n = 2 rotary resonance, namely R3 and spin-polarisation inversion SPI-R3, and the symmetry based SR412 method and, second, the TRAPDOR method. Both classes require optimisation depending on the magnitude of the quadrupolar interaction, and thus there is a compromise choice for samples with more than one nitrogen site, as is the case for the studied dipeptide β-AspAla that contains two nitrogen sites with a small and large quadrupolar coupling constant. Considering this, we observe better sensitivity for the TRAPDOR method, though noting the marked sensitivity of TRAPDOR to the 14N transmitter offset, with both SPI-R3 and SR412 giving similar recoupling performance.

Fluorescence vs. Phosphorescence: Which Scenario Is Preferable in Au(I) Complexes with Benzothiadiazoles?

The photoluminescence of Au(I) complexes is generally characterized by long radiative lifetimes owing to the large spin-orbital coupling constant of the Au(I) ion. Herein, we report three brightly emissive Au(I) coordination compounds, 1, 2a, and 2b, that reveal unexpectedly short emission lifetimes of 10-20 ns. Polymorphs 2a and 2b exclusively exhibit fluorescence, which is quite rare for Au(I) compounds, while compound 1 reveals fluorescence as the major radiative pathway, and a minor contribution of a microsecond-scale component. The fluorescent behaviour for 1-2 is rationalized by means of quantum chemical (TD)-DFT calculations, which reveal the following: (1) S0-S1 and S0-T1 transitions mainly exhibit an intraligand nature. (2) The calculated spin-orbital coupling (SOC) between the states is small, which is a consequence of overall small metal contribution to the frontier orbitals. (3) The T1 state features much lower energy than the S1 state (by ca. 7000 cm-1), which hinders the SOC between the states. Thus, the S1 state decays in the form of fluorescence, rather than couples with T1. In the specific case of complex 1, the potential energy surfaces for the S1 and T2 states intersect, while the vibrationally resolved S1-S0 and T2-S0 calculated radiative transitions show substantial overlap. Thus, the microsecond-scale component for complex 1 can stem from the coupling between the S1 and T2 states.

Friction pressure on relativistic bubble walls

During a cosmological first-order phase transition, particles of the plasma crossing the bubble walls can radiate a gauge boson. The resulting pressure cannot be computed perturbatively for large coupling constant and/or large supercooling. We resum the real and virtual emissions at all leading-log orders, both analytically and numerically using a Monte-Carlo simulation. We find that radiated bosons are dominantly soft and that the resulting retarding pressure on relativistic bubble walls is linear both in the Lorentz boost and in the order parameter, up to a log. We further quantitatively discuss IR cut-offs, wall thickness effects, the impact of various approximations entering the calculation, and comment on the fate of radiated bosons that are reflected.

Quantifying the quadrupolar interaction by 45Sc-NMR spectroscopy of single crystals

Single crystals of the compound [{Sc(H2O)5(μ-OH)}2]Cl4 ⋅ 2H2O were studied by 45Sc-NMR, with the effect of the quadrupolar coupling interaction on the spectra of the spin-7/2 nucleus analysed in the hierarchical framework of perturbation theory. Orientation-dependent spectra acquired at B0 = 17.6 T showed strong second-order effects due to the comparatively large coupling constant of χ = |14.613 ± 0.006| MHz, with an associated asymmetry parameter of ηQ = 0.540 9 ± 0.000 4. By analysing the splittings of the ±3/2 satellites, which in good approximation are subjected to first-order effects only, the full quadrupolar coupling tensor could be determined. The second-order effects caused by this tensor were calculated according to theoretical predictions for all orientations, and subtracted from both the centres of gravity of the satellites, and the central transitions. This allowed extraction of the full chemical shift tensor, with the eigenvalues being δ11 = (5.6 ± 0.9) ppm, δ22 = (12.4 ± 0.9) ppm, and δ33 = (38.5 ± 0.9) ppm. In spectra acquired at a lower magnetic field of B0 = 9.4 T, third-order effects could be detected, and similarly quantified using analytical expressions.

Four-pomeron vertex

The four-pomeron vertex is studied in the perturbative QCD. Its dominating terms of the leading (zeroth and first) orders in the coupling constant and subdominant in the number of colors are constructed. The vertex consists of two terms, one with a derivative in rapidity partial _y and the other with the BFKL interaction between pomerons. The corresponding part of the action and equations of motion are found. The iterative solution of the latter is possible only for rapidities smaller than 2 and quite large coupling constant alpha _s, of the order or greater than unity, when the quadruple pomeron interaction is relatively small. Also iteration of the part with partial _y is unstable in the infrared region and compels to introduce an infrared cut. The variational approach with simple trying functions allows to find the minimum of the action at alpha _s of the order 0.2 and rapidities up to 25. Numerical estimates for O–O collisions show that actually the influence of the quadruple pomeron interaction turns out to be rather small.