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A new methodology of simulating nonadiabatic dynamics using frozen-width Gaussian wavepackets within the moving crude adiabatic representation with the on-the-fly evaluation of electronic structure is presented. The main feature of the new…

化学物理 · 物理学 2018-04-04 Loïc Joubert-Doriol , Artur F. Izmaylov

Conical intersections are ubiquitous in polyatomic molecules and responsible for a wide range of phenomena in chemistry and physics. We introduce and implement a local diabatic representation for the correlated electron-nuclear dynamics…

量子物理 · 物理学 2023-10-18 Bing Gu

On-the-fly quantum nonadiabatic dynamics for large systems greatly benefits from the adiabatic representation readily available from the electronic structure programs. However, frequently occurring in this representation conical…

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…

化学物理 · 物理学 2016-07-27 Alexander Humeniuk , Roland Mitrić

Adequate simulation of non-adiabatic dynamics through conical intersection requires account for a non-trivial geometric phase (GP) emerging in electronic and nuclear wave-functions in the adiabatic representation. Popular mixed…

化学物理 · 物理学 2015-07-20 Rami Gherib , Ilya G. Ryabinkin , Artur F. Izmaylov

We review techniques for simulating fully quantum nonadiabatic dynamics using the frozen-width moving Gaussian basis functions to represent the nuclear wavefunction. A choice of these basis functions is primarily motivated by the idea of…

化学物理 · 物理学 2018-09-05 Loïc Joubert-Doriol , Artur F. Izmaylov

Conical intersections (CIs) are seen as the main mediators of nonadiabatic transitions; yet, mixed quantum-classical (MQC) simulations rarely, if ever, sample geometries with exactly degenerate electronic energies. Here we show that this…

化学物理 · 物理学 2026-02-03 Johannes C. B. Dietschreit , Sebastian Mai , Leticia González

We introduce multistate metadynamics for automatic exploration of conical intersection seams between adiabatic Born-Oppenheimer potential energy surfaces in molecular systems. By choosing the energy gap between the electronic states as a…

化学物理 · 物理学 2018-05-10 Joachim O. Lindner , Merle I. S. Röhr , Roland Mitrić

Ab initio modeling of conical intersection dynamics is crucial for various photochemical, photophysical, and biological processes. However, adiabatic electronic states obtained from electronic structure computations involve random phases,…

化学物理 · 物理学 2024-06-13 Xiaotong Zhu , Bing Gu

We present an approach for carrying out non-adiabatic molecular dynamics simulations of systems in which non-adiabatic transitions arise from the coupling between the classical atomic motions and a quasi-continuum of electronic quantum…

计算物理 · 物理学 2018-11-21 Jerome Daligault , Dmitry Mozyrsky

A non-adiabatic nuclear wavepacket dynamics simulation of the H$_2$O$^+$ de-excitation process is performed based on electronic structure calculations using the variational quantum eigensolver. The adiabatic potential energy surfaces and…

量子物理 · 物理学 2022-03-02 Hirotoshi Hirai , Sho Koh

We investigate the transition of a quantum wave-packet through a one-dimensional avoided crossing of molecular energy levels when the energy levels at the crossing point are tilted. Using superadiabatic representations, and an approximation…

数学物理 · 物理学 2010-07-16 Volker Betz , Benjamin D. Goddard

We present a means of studying rare reactive pathways in open quantum systems using Transition Path Theory and ensembles of quantum jump trajectories. This approach allows for elucidation of reactive paths for dissipative, nonadiabatic…

化学物理 · 物理学 2022-11-09 Michelle C. Anderson , Addison J. Schile , David T. Limmer

The (stationary) Schr\"{o}dinger equation for atomistic systems is solved using the adiabatic potential energy curves (PECs) and the associated adiabatic approximation. Despite being very simplistic, this approach is very powerful and used…

化学物理 · 物理学 2023-12-22 Ryan P. Brady , Charlie Drury , Sergei N. Yurchenko , Jonathan Tennyson

Electronic wave-functions in the adiabatic representation acquire nontrivial geometric phases (GPs) when corresponding potential energy surfaces undergo conical intersection (CI). These GPs have profound effects on the nuclear quantum…

化学物理 · 物理学 2016-07-04 Artur F. Izmaylov , Jiaru Li , Loic Joubert-Doriol

We consider non-adiabatic transitions in multiple dimensions, which occur when the Born-Oppenheimer approximation breaks down. We present a general, multi-dimensional algorithm which can be used to accurately and efficiently compute the…

化学物理 · 物理学 2018-04-16 V. Betz , B. D. Goddard , T. Hurst

The theoretical investigation of non-adiabatic processes is hampered by the complexity of the coupled electron-nuclear dynamics beyond the Born-Oppenheimer approximation. Classically, the simulation of such reactions is limited by the…

量子物理 · 物理学 2021-01-06 Pauline J. Ollitrault , Guglielmo Mazzola , Ivano Tavernelli

We demonstrate coherent control of motional dynamics in trapped Rydberg ions engineered to exhibit a conical intersection between adiabatic potential-energy surfaces. Using quantum optimal control, an optimally shaped electric field drives…

量子物理 · 物理学 2025-09-16 Abdessamad Belfakir , Yousra Bouasria , Herschel Rabitz , Ahmed Ratnani

Accurate description of nonadiabatic dynamics of molecules at metal surfaces involving electron transfer has been a longstanding challenge for theory. Here, we tackle this problem by first constructing high-dimensional neural network…

材料科学 · 物理学 2024-01-05 Gang Meng , James Gardner , Wenjie Dou , Reinhard J. Maurer , Bin Jiang

Mixed-quantum-classical molecular dynamics simulation implies an effective measurement on the electronic states owing to continuously tracking the atomic forces.Based on this insight, we propose a quantum trajectory mean-field approach for…

化学物理 · 物理学 2014-08-08 Wei Feng , Luting Xu , Xin-Qi Li , Weihai Fang , YiJing Yan
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