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Partial atomic charges are a useful and intuitive concept for understanding molecular properties and chemical reaction mechanisms, showing how changes in molecular geometry can affect the flow of electronic charge within a molecule.…

Chemical Physics · Physics 2022-01-14 Ryan J. MacDonell , Serguei Patchkovskii , Michael S. Schuurman

Stochastic systems often exhibit multiple viable metastable states that are long-lived. Over very long timescales, fluctuations may push the system to transition between them, drastically changing its macroscopic configuration. In realistic…

Statistical Mechanics · Physics 2023-04-14 Tobias Grafke , Alessandro Laio

Mean-Field Ring Polymer Molecular Dynamics (MF-RPMD) is a powerful, efficient, and accurate method for approximate quantum dynamic simulations of multi-level system dynamics. Initial efforts to compute nonadiabatic reaction rates using…

Chemical Physics · Physics 2021-04-29 Britta Ann Johnson , Nandini Ananth

The Nonequilibrium Fermi's Golden Rule (NE-FGR) provides a convenient theoretical framework for calculating the charge transfer rate between a photoexcited bright donor electronic state and a dark acceptor electronic state, when the nuclear…

Quantum Physics · Physics 2025-09-17 Pouya Khazaei , Eitan Geva

This study address the computational determination of catalytic reaction rates by moving beyond traditional Transition State Theory (TST), addressing its limitations in complex systems. The Hill relation framework, integrated with Adaptive…

Chemical Physics · Physics 2025-11-25 Thomas Pigeon , Manuel Corral Valero , Pascal Raybaud

Charge transfer (CT) processes that are electronically non-adiabatic are ubiquitous in chemistry, biology, and materials science, but their theoretical description requires diabatic states or adiabatic excited states. For complex systems,…

Chemical Physics · Physics 2024-11-08 Sohang Kundu , Hong-Zhou Ye , Timothy C. Berkelbach

We implement a rare-event sampling scheme for quantifying the rate of thermally-activated nonadiabatic transitions in the condensed phase. Our QM/MM methodology uses the recently developed INAQS package to interface between an elementary…

Chemical Physics · Physics 2023-03-23 Alec J. Coffman , Zuxin Jin , Junhan Chen , Joseph E. Subotnik , D. Vale Cofer-Shabica

It has been shown that both the electron-transfer rate constant of an electrochemical reaction and the conductance quantum are correlated with the concept of quantum capacitance. This simple association between the two separate concepts has…

General Physics · Physics 2024-01-12 Paulo Roberto Bueno

Excited state proton transfer is an ubiquitous phenomenon in biology and chemistry, spanning from the ultrafast reactions of photo-bases and acids to light-driven, enzymatic catalysis and photosynthesis. However, the simulation of such…

Chemical Physics · Physics 2024-10-18 Brieuc Le Dé , Simon Huppert , Riccardo Spezia , Alex W. Chin

Chemical relaxation phenomena, including photochemistry and electron transfer processes, form a vigorous area of research in which nonadiabatic dynamics plays a fundamental role. Here, we show that for nonadiabatic dynamics with two…

Chemical Physics · Physics 2022-07-20 Yanze Wu , Xuezhi Bian , Jonathan Rawlinson , Robert G. Littlejohn , Joseph E. Subotnik

While the variational principle for excited-state energies leads to a route to obtaining excited-state densities from time-dependent density functional theory, relatively little attention has been paid to the quality of the resulting…

Chemical Physics · Physics 2025-09-12 Anna Baranova , Neepa T. Maitra

Time-dependent electronic structure methods provide an efficient, accurate, and robust alternative to traditional time dependent methods for computing both linear and non-linear optical properties. With this in mind, we have developed the…

Chemical Physics · Physics 2026-01-26 Thomas Knoll , Benjamin G. Levine

Non-Hermitian systems have attracted much interest in recent decades, driven partly by the existence of exotic spectral singularities, known as exceptional points (EPs), where the dimensionality of the system evolution operator is reduced.…

Reliably predicting the products of chemical reactions presents a fundamental challenge in synthetic chemistry. Existing machine learning approaches typically produce a reaction product by sequentially forming its subparts or intermediate…

Chemical Physics · Physics 2021-06-16 Hangrui Bi , Hengyi Wang , Chence Shi , Connor Coley , Jian Tang , Hongyu Guo

In this work, we propose a path integral-inspired formalism for computing the quantum thermal expectation values of spin systems, when subject to magnetic fields that can be time-dependent and can accommodate the presence of Heisenberg…

Quantum Physics · Physics 2025-06-18 Thomas Nussle , Stam Nicolis , Iason Sofos , Joseph Barker

The charging of insulating samples degrades the quality and complicates the interpretation of images in scanning electron microscopy and is important in other applications, such as particle detectors. In this paper we analyze this…

Classical Physics · Physics 2020-06-19 Behrouz Raftari , Neil Budko , Kees Vuik

In this work, we use path integral techniques to predict the switching rate in a single-mode bistable open quantum system. While analytical expressions are well-known to be accessible for systems subject to Gaussian noise obeying classical…

The essence of a chemical reaction lies in the redistribution and reorganization of electrons, which is often manifested through electron transfer or the migration of electron pairs. These changes are inherently discrete and abrupt in the…

Machine Learning · Computer Science 2025-07-14 Haitao Lin , Junjie Wang , Zhifeng Gao , Xiaohong Ji , Rong Zhu , Linfeng Zhang , Guolin Ke , Weinan E

The rate constants required to model the OH$^+$ observations in different regions of the interstellar medium have been determined using state of the art quantum methods. First, state-to-state rate constants for the H$_2(v=0,J=0,1)$+…

Solar and Stellar Astrophysics · Physics 2015-06-19 S. Gomez-Carrasco , B. Godard , F. Lique , N. Bulut , J. Klos , O. Roncero , A. Aguado , F. J. Aoiz , J. F. Castillo , J. R. Goicoechea , M. Etxaluze , J. Cernicharo

We present extensive new \textit{ab intio} path integral Monte Carlo results for the momentum distribution function $n(\mathbf{k})$ of the uniform electron gas (UEG) in the warm dense matter (WDM) regime over a broad range of densities and…

Computational Physics · Physics 2021-05-26 Tobias Dornheim , Maximilian Böhme , Burkhard Militzer , Jan Vorberger