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This work identifies geometric effects on dynamics due to nonadiabatic couplings in Born Oppenheimer systems and provides a systematic method for deriving corrections to mixed quantum-classical methods. Specifically, an exact path integral…

Chemical Physics · Physics 2007-05-23 Vinod Krishna

We introduce an improved semiclassical dynamics approach to quantum vibrational spectroscopy. In this method, a harmonic-based phase space sampling is preliminarily driven toward non-harmonic quantization by slowly switching on the actual…

Chemical Physics · Physics 2019-12-09 Riccardo Conte , Lorenzo Parma , Chiara Aieta , Alessandro Rognoni , Michele Ceotto

We explain the concept of superadiabatic approximations and show how in the context of the Born- Oppenheimer approximation they lead to an explicit formula that can be used to predict transitions at avoided crossings. Based on this formula,…

Chemical Physics · Physics 2016-06-29 Volker Betz , Benjamin D. Goddard , Uwe Manthe

We derive an exact solution of an explicitly time-dependent multichannel model of quantum mechanical nonadiabatic transitions. Our model corresponds to the case of a single linear diabatic energy level interacting with a band of an…

Quantum Physics · Physics 2017-02-27 J Lin , N A Sinitsyn

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…

Computational Physics · Physics 2018-11-21 Jerome Daligault , Dmitry Mozyrsky

The Weyl-Wigner representation of quantum mechanics allows one to map the density operator in a function in phase space - the Wigner function - which acts like a probability distribution. In the context of statistical mechanics, this…

Quantum Physics · Physics 2023-08-31 Marcos Gil de Oliveira , Alfredo Miguel Ozorio de Almeida

In quantum mechanics it is often required to describe in a semiclassical approximation the motion of particles moving within a given energy band. Such a representation leads to the appearance of an analogues of fictitious forces in the…

Statistical Mechanics · Physics 2017-10-11 Eldad Bettelheim

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

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

Trajectory surface hopping (TSH) is one of the most widely used quantum-classical algorithms for nonadiabatic molecular dynamics. Despite its empirical effectiveness and popularity, a rigorous derivation of TSH as the classical limit of a…

Chemical Physics · Physics 2013-01-11 J. M. Escartín , P. Romaniello , L. Stella , P. -G. Reinhard , E. Suraud

We study non--adiabatic transitions in scattering theory for the time dependent molecular Schroedinger equation in the Born--Oppenheimer limit. We assume the electron Hamiltonian has finitely many levels and consider the propagation of…

Mathematical Physics · Physics 2009-11-10 G. A. Hagedorn , A. Joye

In open quantum systems decoherence occurs through interaction of a quantum subsystem with its environment. The computation of expectation values requires a knowledge of the quantum dynamics of operators and sampling from initial states of…

Statistical Mechanics · Physics 2009-11-13 Robbie Grunwald , Hyojoon Kim , Raymond Kapral

This paper provides the first ab-initio on-the-fly example of using the Quasi-Diabatic (QD) scheme for non-adiabatic simulations with diabatic dynamics approaches. The QD scheme provides a seamless interface between diabatic quantum…

Computational Physics · Physics 2019-08-15 Wanghuai Zhou , Arkajit Mandal , Pengfei Huo

Viewed as approximations to quantum mechanics, classical evolutions can violate the positive-semidefiniteness of the density matrix. The nature of this violation suggests a classification of dynamical systems based on classical-quantum…

Quantum Physics · Physics 2009-11-06 Salman Habib , Kurt Jacobs , Hideo Mabuchi , Robert Ryne , Kosuke Shizume , Bala Sundaram

Quantum transport of charge or energy in networks with discrete sites is central to diverse quantum technologies, from molecular electronics to light harvesting and quantum opto-mechanical metamaterials. A one dimensional network can be…

Quantum Physics · Physics 2024-02-13 Ajith Ramachandran , Alexander Eisfeld , Sebastian Wüster , Jan-Michael Rost

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

Traditional theories of electron transport in crystals are based on the Boltzmann equation and do not capture physics arising from quantum coherence. We introduce a transport formalism based on ''orbital Wigner functions'', which accurately…

We present a method to study rare nonadiabatic dynamics in open quantum systems using transition path sampling and quantum jump trajectories. As with applications of transition path sampling to classical dynamics, the method does not rely…

Statistical Mechanics · Physics 2021-12-08 Addison J. Schile , David T. Limmer

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

We generalise the celebrated semiclassical wavepacket approach from the adiabatic to the non-adiabatic regime. A unified description covering both of these regimes is particularly desired for systems with spatially varying band structures…

Mesoscale and Nanoscale Physics · Physics 2020-07-29 Matisse Wei-Yuan Tu , Ci Li , Wang Yao