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A new scheme is proposed for modeling molecular nonadiabatic dynamics near metal surfaces. The charge-transfer character of such dynamics is exploited to construct an efficient reduced representation for the electronic structure. In this…

Chemical Physics · Physics 2020-09-24 Zuxin Jin , Joseph E. Subotnik

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

We develop a semi-classical method to simulate the motion of atoms in a dissipative optical lattice. Our method treats the internal states of the atom quantum mechanically, including all nonadiabatic couplings, while position and momentum…

Atomic Physics · Physics 2009-11-11 S. Jonsell , C. M. Dion , M. Nylén , S. J. H. Petra , P. Sjölund , A. Kastberg

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

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

Mixed-quantum classical (MQC) methods for simulating the dynamics of molecules at metal surfaces have the potential to accurately and efficiently provide mechanistic insight into reactive processes. Here, we introduce simple two-dimensional…

Chemical Physics · Physics 2023-08-02 James Gardner , Scott Habershon , Reinhard J. Maurer

Trajectory-based mixed quantum-classical approaches to coupled electron-nuclear dynamics suffer from well-studied problems such as the lack of (or incorrect account for) decoherence in the trajectory surface hopping method and the inability…

Quantum Physics · Physics 2016-02-29 Federica Agostini , Seung Kyu Min , Ali Abedi , E. K. U. Gross

Accurate simulation the many-electronic nonadiabatic dynamics process at metal surfaces remains as a significant task. In this work, we present an orbital surface hopping (OSH) algorithm rigorously derived from the orbital quantum classical…

Chemical Physics · Physics 2025-11-24 Yong-Tao Ma , Rui-Hao Bi , Wenjie Dou

We use the effective Hamiltonian that we recently fitted against the first 306 experimentally observed vibronic transitions of NO2 [J. Chem. Phys. 119, 5923 (2003)] to investigate the time domain nonadiabatic dynamics of this molecule on…

Chemical Physics · Physics 2011-11-09 Michaël Sanrey , Marc Joyeux

We perform on-the-fly non-adiabatic molecular dynamics simulations using the symmetrical quasi-classical (SQC) approach with the recently suggested molecular Tully models: ethylene and fulvene. We attempt to provide benchmarks of the SQC…

Chemical Physics · Physics 2021-09-15 Braden M. Weight , Arkajit Mandal , Pengfei Huo

Attochemistry aims to exploit the properties of coherent electronic wavepackets excited via attosecond pulses, to control the formation of photoproducts. Such molecular processes can in principle be simulated with various nonadiabatic…

Chemical Physics · Physics 2024-05-28 Thierry Tran , Anthony Ferté , Morgane Vacher

WavePacket is an open-source program package for numerical simulations in quantum dynamics. Building on the previous Part I [Comp. Phys. Comm. 213, 223-234 (2017)] and Part II [Comp. Phys. Comm. 228, 229-244 (2018)] which dealt with quantum…

Computational Physics · Physics 2023-02-09 Burkhard Schmidt , Rupert Klein , Leonardo Cancissu Araujo

Nuclear Berry curvature effects emerge from electronic spin degeneracy and canlead to non-trivial spin-dependent (nonadiabatic) nuclear dynamics. However, such effects are completely neglected in all current mixed quantum-classical methods…

Chemical Physics · Physics 2022-08-29 Xuezhi Bian , Yanze Wu , Jonathan Rawlinson , Robert G. Littlejohn , Joseph E. Subotnik

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

We present a new method, called SISYPHUS (Stochastic Iterations to Strengthen Yield of Path Hopping over Upper States), for extending accessible time-scales in atomistic simulations. The method proceeds by separating phase space into…

Materials Science · Physics 2015-03-12 Pratyush Tiwary , Axel van de Walle

A theoretical justification of the empirical surface hopping method for the laser-driven molecular dynamics is given utilizing the formalism of the exact factorization of the molecular wavefunction [Abedi et al., PRL $\textbf{105}$, 123002…

Chemical Physics · Physics 2017-07-05 T. Fiedlschuster , J. Handt , E. K. U. Gross , R. Schmidt

An approach to the quantum-classical mechanics of phase space dependent operators, which has been proposed recently, is remodeled as a formalism for wave fields. Such wave fields obey a system of coupled non-linear equations that can be…

Quantum Physics · Physics 2007-05-23 Alessandro Sergi

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

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…

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…

Chemical Physics · Physics 2018-09-05 Loïc Joubert-Doriol , Artur F. Izmaylov