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Non-adiabatic dynamics simulations have become a standard approach to explore photochemical reactions. Such simulations require underlying potential energy surfaces and couplings between them, calculated at a chosen level of theory, yet…

Chemical Physics · Physics 2024-05-28 Thomas V. Papineau , Denis Jacquemin , Morgane Vacher

Intersystem crossing is a radiationless process that can take place in a molecule irradiated by UV-Vis light, thereby playing an important role in many environmental, biological and technological processes. This paper reviews different…

Chemical Physics · Physics 2017-03-29 Sebastian Mai , Philipp Marquetand , Leticia González

Nonadiabatic dynamics methods are an essential tool for investigating photochemical processes. In the context of employing first principles electronic structure techniques, such simulations can be carried out in a practical manner using…

Chemical Physics · Physics 2024-05-08 Jonathan R. Mannouch , Aaron Kelly

An extension of the CCS-method [Chem. Phys. 2004, 304, p. 103-120] for simulating non-adiabatic dynamics with quantum effects of the nuclei is put forward. The time-dependent Schr\"{o}dinger equation for the motion of the nuclei is solved…

Chemical Physics · Physics 2016-07-27 Alexander Humeniuk , Roland Mitrić

Surface hopping algorithms, as an important class of quantum dynamics simulation algorithms for non-adiabatic dynamics, are typically performed in the adiabatic representation, which can break down in the presence of ill-defined adiabatic…

Numerical Analysis · Mathematics 2022-05-06 Zhenning Cai , Di Fang , Jianfeng Lu

In this work, we employ trajectory-based simulations to predict the electronic coherences created by nonadiabatic dynamics near conical intersections. The mapping approach to surface hopping (MASH) is compared with standard fewest-switches…

Chemical Physics · Physics 2025-05-09 Daniele Furlanetto , Jeremy O. Richardson

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

Recently, the mapping approach to surface hopping (MASH) was proposed as a method to simulate the non-adiabatic dynamics of two-level systems. It was shown that the method possesses many desirable qualities, both theoretically and through…

Chemical Physics · Physics 2025-07-08 Jan Vavřín

We present algebraic diagrammatic construction theory for simulating spin-orbit coupling and electron correlation in charged electronic states and photoelectron spectra. Our implementation supports Hartree-Fock and multiconfigurational…

Chemical Physics · Physics 2025-05-12 Rajat Majumder , Alexander Yu. Sokolov

A semicalssical method based on surface-hopping techniques is developed to model the dynamics of radiative association with electronic transitions in arbitrary polyatomic systems. It can be proven that our method is an extension of the…

Chemical Physics · Physics 2017-10-11 Péter Szabó , Magnus Gustafsson

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

We present a multi-reference generalization of the algebraic diagrammatic construction theory (ADC) [J. Schirmer, Phys. Rev. A 26, 2395 (1982)] for excited electronic states. The resulting multi-reference ADC approach (MR-ADC) can be…

Chemical Physics · Physics 2018-12-27 Alexander Yu. Sokolov

Surface hopping algorithms are popular tools to study dynamics of the quantum-classical mixed systems. In this paper, we propose a surface hopping algorithm in diabatic representations, based on time dependent perturbation theory and…

Numerical Analysis · Mathematics 2022-10-19 Di Fang , Jianfeng Lu

In this work, we describe various improved implementations of the mapping approach to surface hopping (MASH) for simulating nonadiabatic dynamics. These include time-reversible and piecewise-continuous integrators, which is only formally…

Chemical Physics · Physics 2026-03-31 J. Amira Geuther , Kasra Asnaashari , Jeremy O. Richardson

For future use in modeling photoexcited dynamics and intersystem crossing, we calculate spin-adiabatic states and their analytical nuclear gradients within CIS the- ory. These energies and forces should be immediately useful for surface…

Chemical Physics · Physics 2019-01-30 Nicole Bellonzi , Gregory Medders , Evgeny Epifanovsky , Joseph E. Subotnik

We investigate a simple and robust scheme for choosing the phases of adiabatic electronic states smoothly (as a function of geometry) so as to maximize the performance of ab initio non-adiabatic dynamics methods. Our approach is based upon…

Chemical Physics · Physics 2019-09-26 Zeyu Zhou , Zuxin Jin , Tian Qiu , Andrew M. Rappe , Joseph Eli Subotnik

The gas phase relaxation dynamics of photoexcited 5-azacytosine has been investigated by means of SHARC (surface-hopping including arbitrary couplings) molecular dynamics, based on accurate multireference electronic structure computations.…

Chemical Physics · Physics 2021-03-16 Antonio Carlos Borin , Sebastian Mai , Philipp Marquetand , and Leticia González

We report a new implementation of multireference algebraic diagrammatic construction theory (MR-ADC) for simulations of electron attachment and ionization in strongly correlated molecular systems (EA/IP-MR-ADC). Following our recent work on…

Chemical Physics · Physics 2021-01-19 Koushik Chatterjee , Alexander Yu. Sokolov

We present an implementation and benchmark of new approximations in multireference algebraic diagrammatic construction theory for simulations of neutral electronic excitations and UV/Vis spectra of strongly correlated molecular systems…

Chemical Physics · Physics 2021-12-02 Ilia M. Mazin , Alexander Yu. Sokolov

We examine time-resolved X-ray diffraction from molecules in the gas phase which undergo nonadiabatic avoided-crossing dynamics involving strongly coupled electrons and nuclei. Several contributions to the signal are identified,…

Chemical Physics · Physics 2017-05-30 Markus Kowalewski , Kochise Bennett , Shaul Mukamel
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