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We propose to measure the importance of spin-orbit couplings (SOCs) in the nonadiabatic molecular quantum dynamics rigorously with quantum fidelity. To make the criterion practical, quantum fidelity is estimated efficiently with the…

Chemical Physics · Physics 2013-01-15 Tomas Zimmermann , Jiri Vanicek

We propose an approximate method for evaluating the importance of non-Born-Oppenheimer effects on the quantum dynamics of nuclei. The method uses a generalization of the dephasing representation (DR) of quantum fidelity to several diabatic…

Chemical Physics · Physics 2013-01-15 Tomas Zimmermann , Jiri Vanicek

A first principles quantum formalism to describe the non-adiabatic dynamics of electrons and nuclei based on a second quantization representation (SQR) of the electronic motion combined with the usual representation of the nuclear…

Chemical Physics · Physics 2020-11-06 Sudip Sasmal , Oriol Vendrell

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…

Chemical Physics · Physics 2014-08-08 Wei Feng , Luting Xu , Xin-Qi Li , Weihai Fang , YiJing Yan

Modeling many-body quantum systems with strong interactions is one of the core challenges of modern physics. A range of methods has been developed to approach this task, each with its own idiosyncrasies, approximations, and realm of…

Statistical Mechanics · Physics 2018-11-21 Brett Larder , Dirk Gericke , Scott Richardson , Paul Mabey , Thomas White , Gianluca Gregori

Nonadiabatic molecular dynamics is an effective method for modeling nonradiative decay in electronically excited molecules. Its accuracy depends strongly on the quality of the potential energy surfaces, and its affordability for long…

Chemical Physics · Physics 2024-10-11 Matthew R. Hennefarth , Donald G. Truhlar , Laura Gagliardi

The combined quantum electron-nuclear dynamics is often associated with the Born-Huang expansion of the molecular wave function and the appearance of nonadiabatic effects as a perturbation. On the other hand, native multicomponent…

Quantum molecular dynamics requires an accurate representation of the molecular potential energy surface from a minimal number of electronic structure calculations, particularly for nonadiabatic dynamics where excited states are required.…

Chemical Physics · Physics 2016-08-24 Charles W. Heaps , David A. Mazziotti

Excited-state molecular dynamics (ESMD) simulations near conical intersections (CIs) pose significant challenges when using machine learning potentials (MLPs). Although MLPs have gained recognition for their integration into mixed…

Chemical Physics · Physics 2025-01-17 Sung Wook Moon , Soohaeng Yoo Willow , Tae Hyeon Park , Seung Kyu Min , Chang Woo Myung

Diabatization of the molecular Hamiltonian is a standard approach to removing the singularities of nonadiabatic couplings at conical intersections of adiabatic potential energy surfaces. In general, it is impossible to eliminate the…

Chemical Physics · Physics 2021-03-26 Seonghoon Choi , Jiří Vaníček

A general theoretical framework is derived for the recently developed multi-state trajectory (MST) approach from the time dependent Schr\"odinger equation, resulting in equations of motion for coupled nuclear-electronic dynamics equivalent…

Chemical Physics · Physics 2017-09-13 Guohua Tao

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…

A generalized formalism of the so-called non-adiabatic quantum molecular dynamics is presented, which applies for atomic many-body systems in external laser fields. The theory treats the nuclear dynamics and electronic transitions…

Atomic Physics · Physics 2007-05-23 Thomas Kunert , Ruediger Schmidt

We extend the Mixed Quantum-Classical Initial Value Representation (MQC-IVR), a semiclassical method for computing real-time correlation functions, to electronically nonadiabatic systems using the Meyer-Miller-Stock-Thoss (MMST) Hamiltonian…

Chemical Physics · Physics 2018-01-17 Matthew S. Church , Timothy J. H. Hele , Gregory S. Ezra , Nandini Ananth

We propose a trajectory-based method for simulating nonadiabatic dynamics in molecular systems with two coupled electronic states. Employing a quantum-mechanically exact mapping of the two-level problem to a spin-1/2 coherent state, we…

Chemical Physics · Physics 2020-03-03 Johan E. Runeson , Jeremy O. Richardson

Every physical regime is some sort of approximation of reality. One lesser-known realm that is the semiquantal regime, which may be used to describe systems with both classical and quantum subcomponents. In the present review, we discuss…

Chaotic Dynamics · Physics 2009-11-07 Mason A. Porter

A mixed quantum-classical approach to simulate the coupled dynamics of electrons and nuclei in nanoscale molecular systems is presented. The method relies on a second order expansion of the Lagrangian in time-dependent density functional…

Chemical Physics · Physics 2009-11-10 T. A. Niehaus , D. Heringer , B. Torralva , Th. Frauenheim

Ab initio methods for electronic structure of molecules have reached a satisfactory accuracy for calculation of static properties, but remain too expensive for quantum dynamical calculations. We propose an efficient semiclassical method for…

Chemical Physics · Physics 2015-05-13 Baiqing Li , Cesare Mollica , Jiri Vanicek

The quantum adiabatic theorem is a fundamental result in quantum mechanics, with a multitude of applications, both theoretical and practical. Here, we investigate the dynamics of adiabatic processes for quantum many-body systems %in detail…

Quantum Physics · Physics 2025-08-15 Vibhu Mishra , Salvatore Manmana , Stefan Kehrein

A novel mixed quantum-classical approach to simulating nonadiabatic dynamics of molecules at metal surfaces is presented. The method combines the numerically exact hierarchical equations of motion approach for the quantum electronic degrees…

Mesoscale and Nanoscale Physics · Physics 2024-05-06 Samuel L. Rudge , Christoph Kaspar , Robin L. Grether , Steffen Wolf , Gerhard Stock , Michael Thoss
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