Article
Chemistry, Multidisciplinary
Eric R. Heller, Jeremy O. Richardson
Summary: This study simulates two recent matrix-isolation experiments at cryogenic temperatures, revealing the failure of the commonly used weak-coupling method in describing deep-tunneling reactions. However, the more rigorous approach of semiclassical golden-rule instanton theory combined with double-hybrid density-functional theory and multireference perturbation theory successfully reproduces rate constants and kinetic isotope effects in good agreement with experiment. Additionally, these calculations identify the optimal tunnelling pathways, providing a molecular picture of the reaction mechanism.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2022)
Article
Materials Science, Multidisciplinary
Luke J. Wirth, Christopher Woodward, Amir A. Farajian
Summary: Advances in first principles methods are used to study the atom-vacancy exchanges near a screw dislocation in fcc Ni, revealing direction-dependent free energy profiles and temperature-dependent correlation effects. The dynamic approach shows intra-cell energy profile asymmetry related to dynamic geometry rearrangements. Despite absolute values of rate constants being similar, the HTST method generally underestimates rates by a factor of 2-5, partially explaining discrepancies between theoretical works and experiments in pipe diffusion diffusivities.
Article
Chemistry, Physical
Xiang Yuan, Lucas Visscher, Andre Severo Pereira Gomes
Summary: This paper presents the implementation of a module for generating natural orbitals (NOs) for correlated wavefunctions, particularly the second order Moller-Plesset perturbation frozen natural orbitals (MP2FNOs), as part of a novel implementation of relativistic coupled cluster theory. The study finds that MP2FNOs accelerate the convergence of correlation energy uniformly across the Periodic Table and reliable estimates for energy and molecular properties can be obtained by truncating the virtual molecular orbital spaces to about half their original size.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Multidisciplinary Sciences
Elena Molteni, Giovanni Onida, Matteo Ceccarelli, Giancarlo Cappellini
Summary: The study utilized a self-developed code to investigate the optical properties of several fundamental molecules in medical and pharmaceutical research, as well as their conformational and chemical sensitivity in absorption and CD spectra.
Article
Chemistry, Multidisciplinary
J. Patrick Zobel, Anna M. Wernbacher, Leticia Gonzalez
Summary: The mechanism of reverse intersystem crossing (rISC) in metal-based TADF emitters is still not clear, as the small singlet/triplet energy gaps necessary for thermal rISC in donor-acceptor systems with charge-transfer excited states have spin-orbit couplings that are too small for effective rISC. In this study, the first nonadiabatic dynamics simulation of rISC process in a carbene-copper(I)-carbazolyl TADF emitter is reported. Efficient rISC on a picosecond time scale is demonstrated, involving an intermediate higher-lying triplet state of metal-to-ligand charge transfer character ((MLCT)-M-3) that enables large spin-orbit couplings with the lowest singlet charge transfer state. The mechanism is completed in the S-1 state where the complex can return to a co-planar coordination geometry with high fluorescence efficiency.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Spectroscopy
Zhen Wang, Yugao Xu, Wenqin Li, Tao Lu, Gang Feng
Summary: In this study, the 1,4-pentadien-3-ol and its monohydrate were characterized using microwave spectroscopy and theoretical computations. The research revealed the characteristics of hydrogen bonds in the compounds.
SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY
(2022)
Article
Chemistry, Physical
Juan J. J. Aucar, Alejandro F. F. Maldonado, Juan I. I. Melo
Summary: In this work, relativistic corrections to the electric field gradient (EFG) are presented, including spin-dependent corrections for the first time. The results show that these new corrections significantly improve the performance of the existing method and are in close agreement with calculations at the four-component Dirac-Hartree-Fock (4c-DHF) level. The accuracy of the EFG values obtained with this new method allows for the analysis of the electronic origin of relativistic effects using well-known nonrelativistic operators.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Multidisciplinary
Sascha Jahnigen, Katia Le Barbu-Debus, Regis Guillot, Rodolphe Vuilleumier, Anne Zehnacker
Summary: In this study, the effect of a twofold screw axis on the solid-state VCD spectrum was investigated using both experimental and theoretical analysis. It was found that the VCD spectrum can reflect the supramolecular chirality of the crystal.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Physical
Jing Shang, Congxin Xia, Chun Tang, Chun Li, Yandong Ma, Yuantong Gu, Liangzhi Kou
Summary: The bending deformation of AgBiP2Se6 monolayers can manipulate the polarization direction and domain size, significantly improving the ferroelectric stability. This mechano-ferroelectric coupling represents a new mechanism for stabilization and polarization flip in 2D ferroelectrics, with potential applications in next-generation non-volatile storage devices.
NANOSCALE HORIZONS
(2021)
Article
Chemistry, Multidisciplinary
Solana Di Pino, Yamila A. Peerez A. Sirkin, Uriel N. Morzan, Veronica M. Sanchez, Ali Hassanali, Damian A. Scherlis
Summary: Nanoconfinement effects on water dissociation and reactivity at interfaces, pores, or aerosols remain controversial. Using ab initio simulations, we demonstrate that water dissociation is conserved intact to unexpectedly small length-scales, down to aggregates of only a dozen molecules or pores of widths below 2 nm. This work provides a fundamental description of water dissociation at different scales with implications on reactivity at the air-liquid interface.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Nicolas Montenegro-Pohlhammer, Rocio Sanchez-de-Armas, Carmen J. Calzado
Summary: The study investigates the molecular level interaction of the spin-crossover (SCO) Fe-II((3,5-(CH3)(2)Pz)(3)BH)(2) complex with the Au(111) surface, revealing that adsorption on the metallic surface enhances transition energy and increases the relative stability of the low spin state, with a spin-dependent interaction stronger for low spin than high spin. The different strength of the Fe ligand field at low and high temperatures is reflected in the nature of states close to the Fermi level, with larger metal-ligand hybridization in the low spin state.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Abhishek Kundu, Baishanal Mandal, Biplab Maji, Debashis Adhikari
Summary: This study investigates the solvent-dependent chemodivergence in the nitrile reduction reaction using density functional theory (DFT). The results reveal that a polar protic solvent, isopropanol, promotes the formation of secondary amines through proton hopping, while a nonpolar solvent, n-hexane, inhibits the reaction and leads to the formation of primary amines.
JOURNAL OF PHYSICAL CHEMISTRY A
(2023)
Article
Chemistry, Multidisciplinary
Rodolphe Pollet, Wutharath Chin
Summary: The photochemistry of oxocarboxylic acids plays a significant role in atmospheric chemistry. Pyruvic acid, when in the presence of sodium cation or its conjugate base, shows altered hydration equilibrium and photosensitivity to UV-visible light. Through ab initio metadynamics simulation, we reveal the reversible hydration reaction mechanism between the keto and diol forms of pyruvic acid, influenced by sodium, and provide insights into the photoactivity of these forms in the actinic region through calculations of electronic transition energies.
CHEMISTRY-A EUROPEAN JOURNAL
(2023)
Article
Chemistry, Physical
V Jambur, C. Tangpatjaroen, J. Xi, J. Tarnsangpradit, M. Gao, H. Sheng, J. H. Perepezko, I Szlufarska
Summary: This study shows that minor alloying can enhance the strength of metallic glasses by increasing the chemical bond strength, which is distinct from changes in topological ordering. The addition of transition metals to Al-Sm based metallic glasses increased their hardness, mainly due to the strong bonding between transition metals and aluminum atoms. The effects of topology and chemistry on the mechanical properties of metallic glasses are independent of each other, providing insights for the design of metallic glasses with improved mechanical properties.
JOURNAL OF ALLOYS AND COMPOUNDS
(2021)
Article
Physics, Particles & Fields
Si-wen Li
Summary: This study analyzes the holographic Schwinger effect in confining D3- and D4-brane backgrounds with D-instantons, showing that the presence of D-instantons increases the potential barrier and suppresses the pair production/decay rate.Particles in the dual field theory could acquire an effective mass through the Chern-Simons interaction or the theta term due to the presence of D-instantons.
EUROPEAN PHYSICAL JOURNAL C
(2021)
Review
Chemistry, Multidisciplinary
Attila G. Csaszar, Csaba Fabri, Janos Sarka
WILEY INTERDISCIPLINARY REVIEWS-COMPUTATIONAL MOLECULAR SCIENCE
(2020)
Article
Chemistry, Physical
Csaba Fabri, Benjamin Lasorne, Gabor J. Halasz, Lorenz S. Cederbaum, Agnes Vibok
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2020)
Article
Chemistry, Physical
Csaba Fabri, Benjamin Lasorne, Gabor J. Halasz, Lorenz S. Cederbaum, Agnes Vibok
JOURNAL OF CHEMICAL PHYSICS
(2020)
Article
Chemistry, Physical
Csaba Fabri, Gabor J. Halasz, Lorenz S. Cederbaum, Agnes Vibok
Summary: This study explores light-induced nonadiabaticity in formaldehyde by inducing conical intersections between the X and A states using laser fields. The field-dressed spectrum is probed by a weak laser pulse and analyzed using a full-dimensional ab initio approach in the Floquet-state representation. The resulting spectra are highly influenced by the frequency of the dressing light, allowing for the isolation of different nonadiabatic phenomena.
JOURNAL OF CHEMICAL PHYSICS
(2021)
Article
Chemistry, Physical
Peter Badanko, Otabek Umarov, Csaba Fabri, Gabor J. Halasz, Agnes Vibok
Summary: Conical intersections are degeneracies between multidimensional potential energy surfaces of molecular systems, which not only significantly alter the spectroscopic and dynamical properties of molecules but also have noticeable topological implications. Such intersections can be created by light, including classical laser light or quantum light in an optical cavity. An example study of placing formaldehyde (H2CO) molecule into a cavity has investigated the topological properties of the emerging light-induced conical intersection under different cavity parameters and geometrical arrangements.
INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY
(2022)
Article
Chemistry, Physical
Csaba Fabri, Gabor J. Halasz, Agnes Vibok
Summary: The interaction between a molecule and the quantized electromagnetic field of a nanocavity can create light-induced conical intersections between polaritonic potential energy surfaces. By using time-resolved ultrafast radiative emission of the cavity, we can observe the nuclear wavepacket dynamics and nonadiabatic population transfer between polaritonic surfaces without a probe pulse, providing a clear dynamical fingerprint of light-induced conical intersections.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2022)
Article
Chemistry, Physical
Iren Simko, Csaba Fabri, Attila G. Csaszar
Summary: Experimental and computational results have challenged traditional chemical concepts regarding the structure, dynamics, and rovibrational spectra of protonated methane. Theoretical and computational results provide insight into the dynamical structure of CH5+. The findings reveal similarities in the structures of the ground vibrational state and other vibrational states below 200 cm-1, confirming the effective structure of CH5+ as a CH3+ tripod with a H2 unit on top.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2023)
Article
Optics
Meissa L. Diouf, Roland Tobias, Frank M. J. Cozijn, Edcel J. Salumbides, Csaba Fabri, Cristina Puzzarini, Attila G. Csaszar, Wim Bachs
Summary: A non-linear spectroscopic study of the HDO molecule was performed using noise-immune cavity-enhanced optical-heterodyne molecular spectroscopy. Spectral perturbations, including distortions, shifts, and splittings, were observed, which were attributed to the AC-Stark effect and parity-pair mixing. The study achieved higher precision compared to Doppler-limited techniques.
Article
Chemistry, Multidisciplinary
Iren Simko, Christoph Schran, Fabien Brieuc, Csaba Fabri, Oskar Asvany, Stephan Schlemmer, Dominik Marx, Attila G. Csaszar
Summary: This work discusses the emergence of quantum nuclear delocalization and its rovibrational fingerprints in the van der Waals complex HHe3+. The results reveal that during the vibrations of the molecule, the solvating He is not restricted to be in a certain plane, but freely orbits the central proton, forming a three-dimensional torus.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Csaba Fabri, Gabor J. Halasz, Lorenz S. Cederbaum, Agnes Vibok
Summary: Research shows that the interaction between molecules and the quantized radiation field leads to the appearance of light-induced conical intersections, which greatly affect the nuclear dynamics of polaritons. The new finding reveals the process of ultrafast radiative emission under the control of the geometric phase imposed by LICI.
CHEMICAL COMMUNICATIONS
(2022)
Article
Chemistry, Physical
Jonathan I. Rawlinson, Csaba Fabri, Attila G. Csaszar
Summary: The Aharonov-Bohm effect has another application in chemistry, specifically in nuclear quantum dynamics and high-resolution molecular spectroscopy. The overall rotation of a symmetric-top molecule can influence internal vibrational motion dynamics similar to a solenoid carrying magnetic flux, and this effect can be used to understand the low-energy rovibrational energy-level structure of certain molecular ions.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Jonathan I. Rawlinson, Csaba Fabri, Attila G. Csaszar
Summary: This study presents a new one-dimensional model for the low-energy vibrational quantum dynamics of CH5+, based on the motion of an effective particle on a 60-vertex graph Gamma(60) with a single edge length parameter. The quantum states of CH5+ are obtained analytically within this model and are linked to combinatorial properties of Gamma(60). The bipartite structure of Gamma(60) provides a simple explanation for the curious symmetries observed in numerically exact variational calculations on CH5+.
CHEMICAL COMMUNICATIONS
(2021)
Article
Chemistry, Physical
Yue Liang, Yichi Zhang, Csaba Fabri, Jiarui Ma, Jianbao Zhao, Brant Billinghurst, Ziqiu Chen
Summary: This study reports the torsional vibrational spectra of benzaldehyde based on high resolution spectroscopic investigation, aiming to eliminate experimental ambiguity. The experimental determination of the barrier to internal rotation was lower compared to theoretical calculations, indicating the discrepancy between theory and experiment remains despite best efforts.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2021)
Article
Chemistry, Multidisciplinary
Csaba Fabri, Gabor J. Halasz, Lorenz S. Cederbaum, Agnes Vibok
Summary: The coupling of a molecule and a cavity leads to nonadiabaticity in the molecule, making the description of its dynamics complex. Reduced-dimensional models and the Born-Oppenheimer approximation are commonly used to address this issue, but they may not always be effective due to the presence of conical intersections induced by the cavity.
Article
Chemistry, Physical
Jan Smydke, Csaba Fabri, Janos Sarka, Attila G. Csaszar
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2019)
