Article
Physics, Multidisciplinary
S. -a. Biehs, G. S. Agarwal
Summary: The possibility of nonreciprocity in heat transfer between two bodies has been extensively studied, especially the role of strong magnetic fields. A simpler approach would be to consider heat transfer in synthetic electric and magnetic fields. This study demonstrates the breakdown of detailed balance for the heat transfer function and the nonreciprocity induced by synthetic fields in graphene flakes and Casimir coupling between two objects. Synthetic fields also affect the mean occupation numbers of two membranes, which can be experimentally verified.
PHYSICAL REVIEW LETTERS
(2023)
Article
Chemistry, Physical
Ya Peng, Hui Zhang
Summary: This study provides a highly accurate investigation of the initial reaction in methane combustion, presenting a potential energy surface and revealing a detailed mechanism. The findings are significant for improving our understanding of the primary process in hydrocarbon combustion.
JOURNAL OF PHYSICAL CHEMISTRY A
(2022)
Editorial Material
Biochemistry & Molecular Biology
Nobuo Shimamoto
Summary: When a reaction is accompanied by a change that occurs at a speed close to or slower than the reaction rate, a circulating reaction flow can exist in the macroscopic stationary state. If the accompanying change is in equilibrium at the timescale of the relevant reaction, the transition-state theory can eliminate the flow.
Article
Chemistry, Inorganic & Nuclear
Kishalay Bhar, Wenbin Guo, Mathieu Gonidec, Venkata Nikhil M. Raj, Surabhi Bhatt, Franc Perdih, Philippe Guionneau, Guillaume Chastanet, Anuj K. Sharma
Summary: We synthesized a series of molecular complexes with spin crossover behavior and successfully observed their structures and transition processes in crystals. Complexes 1 and 2 exhibit complete and gradual spin crossover at higher temperatures, while complex 3 shows strong irreversible features at lower temperatures.
DALTON TRANSACTIONS
(2022)
Article
Optics
Eli Pollak, Jianshu Cao
Summary: This paper extends Wigner's quantum rate theory to asymmetric barriers and introduces a second-order correction. The derived analytical expression is calibrated with numerical calculations and shows excellent agreement. It is shown that semiclassical transition state theory fails to reproduce correct terms and further analysis reveals suppressed transmission due to quantum reflection.
Article
Chemistry, Physical
Adalberto Santana Lima Junior, Joel Leitao Nascimento, Daniel Moura, Tiago Vinicius Alves
Summary: The overall thermal rate coefficients for the CH2CO + O (P-3) -> CH2 + CO2 reaction were estimated using the canonical variational theory with multidimensional small-curvature tunneling corrections and multifaceted variable-reaction-coordinate transition state theory. The energies, equilibrium geometries, and harmonic vibrational frequencies were calculated using the M06-2X/aug-cc-pVTZ level of theory. The thermal rate constants showed excellent agreement with experimental data, confirming that the CH2 + CO2 channel is the most favorable pathway. Fitting the total thermal rate coefficients into a modified Arrhenius equation revealed a temperature-dependent activation energy.
COMPUTATIONAL AND THEORETICAL CHEMISTRY
(2023)
Article
Chemistry, Physical
Giacomo Mandelli, Luca Corneo, Chiara Aieta
Summary: In this study, the full-dimensional semiclassical transition state theory was applied to estimate the rate constant of glycine interconversion between different conformers. The results showed that the theoretical method used in this study improved upon previous methods and aligned well with experimental measurements. The study confirmed the accuracy and applicability of the theory, especially in cryogenic temperatures where deep tunneling regime is usually not considered.
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
(2023)
Article
Chemistry, Physical
Wei Fang, Pierre Winter, Jeremy O. Richardson
Summary: Semiclassical instanton theory is a useful tool for calculating thermal reaction rates, but previous formulations have limitations in computational feasibility and reliability. A new microcanonical formulation called density-of-states instanton theory is proposed in this paper, which overcomes these limitations by avoiding summing over states and achieving a balance between computational efficiency and reliability.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2021)
Article
Chemistry, Inorganic & Nuclear
Kosuke Kitase, Daisuke Akahoshi, Takafumi Kitazawa
Summary: The synthesis of a Fe-Ag Hofmann-type complex with unique Ag-N interactions and absence of Ag-Ag interactions is described, contrasting it with a previously synthesized Au complex with Au-Au interactions. Magnetic measurements show a scan-rate-dependent hysteresis, indicating a relatively slow spin transition.
INORGANIC CHEMISTRY
(2021)
Article
Chemistry, Physical
Evgenii Titov, Anjali Sharma, Nino Lomadze, Peter Saalfrank, Svetlana Santer, Marek Bekir
Summary: In this study, a combination of simulations and experimental measurements was used to uncover the reasons behind the deceleration of photoinduced trans -> cis switching in micelles of azobenzene-containing surfactants. The decrease in isomerization quantum yields for molecules inside the micelles and the reduction of extinction coefficients upon micellization were identified as the key factors responsible for the reaction slowdown. These findings provide a detailed explanation for the observed phenomenon.
Article
Chemistry, Physical
L. Bonnet, C. Crespos, M. Monnerville
Summary: Classical-limit quantum dynamics is used to explain the quantum thresholds of chemical reactions by studying vibrationally nonadiabatic behavior across the interaction region in a basic model of chemical reactions.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Mechanics
B. Parent, P. Thoguluva Rajendran, A. Omprakas
Summary: The study reveals that the coupling between plasma sheaths, non-equilibrium electron temperature, and ambipolar diffusion in quasi-neutral plasma flows are critical for accurately predicting electron losses.
Article
Chemistry, Physical
Eli Pollak, Jianshu Cao
Summary: This paper answers Wigner's challenge from ninety years ago by deriving the h(2) expansion term for the tunneling rate through an asymmetric barrier. It is shown that the expansion derived in this paper should be used for heavy atom tunneling instead of the parabolic barrier approximation. The results of this study provide critical insights into the validity of approximate theories such as classical Wigner theory.
JOURNAL OF CHEMICAL PHYSICS
(2022)
Article
Chemistry, Physical
Daniel R. Moberg, Ahren W. Jasper
Summary: A general strategy for constructing and validating permutationally invariant polynomial expansions for chemical systems is presented, demonstrating its application to gas-phase dynamics and kinetics. The strategy enforces permutational invariance in PIP expansions with millions of terms and permutationally distinct atom types, showing systematic convergence in training data quantity and expansion order. The quality of the PIP expansions is demonstrated through predicting errors in dynamics for both reactive and nonreactive applications.
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
(2021)
Article
Chemistry, Multidisciplinary
Margherita Verrucchi, Gina Elena Giacomazzo, Patrick Severin Sfragano, Serena Laschi, Luca Conti, Marco Pagliai, Cristina Gellini, Marilena Ricci, Enrico Ravera, Barbara Valtancoli, Claudia Giorgi, Ilaria Palchetti
Summary: A water-soluble ruthenium(II) complex (L) was used to modify the surface of an indium-tin oxide (ITO) electrode decorated with a nanostructured layer of TiO2 (TiO2/ITO). Singlet oxygen (O-1(2)) produced by the complex under visible light irradiation triggers a cathodic photocurrent when the electrode is illuminated and biased at a proper reduction potential. The L/TiO2/ITO electrode was characterized and demonstrated efficient oxidation of phenolic compounds, with a limit of detection (LOD) of 0.3 mu mol dm(-3).
