Communication: Global flux surface hopping in Liouville space

Wang, Linjun; Sifain, Andrew E.; Prezhdo, Oleg V.

doi:10.1063/1.4935971

Cited by 30 publications

(42 citation statements)

References 40 publications

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“…Note that Martens has recently derived a novel quantum trajectory surface hopping approach, which avoids frustrated hops by employing a more rigorous quantum force formalism and can also describe the superexchange dynamics . Besides, treating both populations and coherences on equal footing, the Liouville space formulation of surface hopping has shown its advantages to describe the complex population transfer channels . Constructing more consistent algorithms using the entire reduced density matrix should be promising for nonadiabatic dynamics simulations with better accuracy …”

Section: Discussionmentioning

confidence: 99%

“…We consider a general expression for the Hamiltonian of the system, Ĥ ( r ; R ), where r and R are coordinates of the quantum and classical degrees of freedom, respectively. It is well known that better performance of surface hopping is usually obtained in the adiabatic representation . At any given geometry R , the adiabatic eigenstates {| ϕ i ( r ; R )〉} and the corresponding eigenenergies { E i ( R )} can be obtained through solving the time independent Schrödinger equation.…”

Section: Fewest Switches Surface Hoppingmentioning

confidence: 99%

“…In this aspect, the converged results of GFSH can be different from those of FSSH‐like algorithms. Note that the algorithm of GFSH has been further extended from the traditional Hilbert space to the Liouville space, and even better description of superexchange has been achieved . Besides, as direct transitions between any two electronic states are allowed, GFSH can give better detailed balance, which is particularly important when studying relaxation and diffusion processes in extended systems .…”

Section: Problem C: Calculation Of Hopping Probabilitiesmentioning

confidence: 99%

See 2 more Smart Citations

Surface hopping methods for nonadiabatic dynamics in extended systems

Wang

Qiu

Bai

et al. 2019

WIREs Comput Mol Sci

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The review describes recent method developments toward application of the trajectory surface hopping approach for nonadiabatic dynamics simulations of extended systems. Due to the ease of implementation and good balance between efficiency and reliability, surface hopping has become one of the most widely used mixed quantum‐classical methods for studying general charge and exciton dynamics. In extended systems (e.g., aggregates, polymers, surfaces, interfaces, and solids), however, surface hopping suffers from the difficulty to treat complex surface crossings in the adiabatic representation, and thus the relevant applications have been limited in the past years. The latest studies have allowed us to make a systematic classification of the surface crossings and identify their different influence mechanisms on the traditional surface hopping machinery, including problems related to the phase uncertainty correction of adiabatic states, the wave function propagation, the calculation of hopping probabilities, the velocity adjustment after surface hops, and the artificial long‐range population transfer amplified by decoherence corrections. Elegant solutions to each of these problems have enabled us to get fast time step convergence and size independence even for very large systems with different strengths of electron–phonon couplings. Thereby, the recent theoretical progresses have opened the door to simulate the real‐time and real‐space dynamics (e.g., charge separation, recombination, relaxation, and diffusion) in realistic extended systems, and will generate comprehensive understanding to promote the development of many research fields in chemistry, physics, biology, and material sciences in the near future. This article is categorized under: Structure and Mechanism > Computational Materials Science Theoretical and Physical Chemistry > Reaction Dynamics and Kinetics Theoretical and Physical Chemistry > Statistical Mechanics Molecular and Statistical Mechanics > Molecular Dynamics and Monte‐Carlo Methods

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Section: Discussionmentioning

confidence: 99%

Section: Fewest Switches Surface Hoppingmentioning

confidence: 99%

Section: Problem C: Calculation Of Hopping Probabilitiesmentioning

confidence: 99%

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Surface hopping methods for nonadiabatic dynamics in extended systems

Wang

Qiu

Bai

et al. 2019

WIREs Comput Mol Sci

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“…It has been established recently that straightforward application of FSSH excludes superexchange effects, including important pathways of Auger‐type dynamics . Superexchange is captured at the Ehrenfest level, and can be recovered within the SH description by using global flux SH and second quantized SH, or by performing SH simulations in Liouville rather than Hilbert space . The following perspective article discusses recent progress in SH …”

Section: Discussionmentioning

confidence: 99%

Nonadiabatic charge dynamics in novel solar cell materials

Long

Prezhdo

Fang

2017

WIREs Comput Mol Sci

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The review describes recent research into the nonequilibrium phenomena in nanoscale materials, with focus on charge separation and recombination, that form the basis for photovoltaic and photocatalytic devices. Nonadiabatic molecular dynamics combined with ab initio real-time time-dependent density functional theory enable us to model time-resolved laser experiments at the atomistic level, emphasizing realistic aspects of the materials, such as defects, dopants, boundaries, chemical bonding, etc. A variety of systems have been considered, including bulk semiconductors sensitized by semiconducting/metallic nanoparticles and graphene, nanocrystal/molecule junctions, polymer interfaces with carbon nanotubes and nanoclusters, van der Waals heterojunctions, black phosphorus, and hybrid organic-inorganic perovskites. The detailed atomistic knowledge obtained from the explicit time-domain modeling generates comprehensive understanding of electron-vibrational dynamics in complex multicomponent systems, provides critical insights into quantum mechanical transport of energy and charge, and leads to valuable guidelines for improvement of solarto-electric power conversion in photovoltaic and photocatalytic applications and for efficient performance of transport devices. FIGURE 14 | Decay of populations of the first excited state in bilayer black phosphorus (BP) and at the BP/MoS 2 interface. BP/MoS 2 shows slower decay because of electron-hole separation across the interface.

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“…Note that similar algorithms have been utilized in the Liouville space surface hopping. 68,69 A slow decoherence effect due to traditional decay of mixing may be responsible for this. [31][32][33][34][35][36] Relevant studies are currently under way.…”

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confidence: 99%

Branching Corrected Mean Field Method for Nonadiabatic Dynamics

Wang

2020

J. Phys. Chem. Lett.

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When describing nonadiabatic dynamics based on trajectories, severe trajectory branching occurs when the nuclear wave packets on some potential energy surfaces are reflected while those on the remaining surfaces are not. As a result, the traditional Ehrenfest mean field (EMF) approximation breaks down. In this study, two versions of the branching corrected mean field (BCMF) method are proposed. Namely, when trajectory branching is identified, BCMF stochastically selects either the reflected or the non-reflected group to build the new mean field trajectory or splits the mean field trajectory into two new trajectories with the corresponding weights. As benchmarked in six standard model systems and an extensive model base with two hundred diverse scattering models, BCMF significantly improves the accuracy while retaining the high efficiency of the traditional EMF. In fact, BCMF closely reproduces the exact quantum dynamics in all investigated systems, thus highlighting the essential role of branching correction in nonadiabatic dynamics simulations of general systems. 2Nonadiabatic dynamics have attracted substantial interest in the past decades.Many important phenomena in chemistry, physics, biology, and material sciences (e.g., proton transfer, 1,2 photoisomerization, 3,4 charge transport, 5,6 exciton dissociation, 7,8 and nonradiative energy relaxation 9,10 ) all fall into the category of nonadiabatic dynamics.Compared with adiabatic dynamics, nonadiabatic dynamics involve strongly coupled electronic and nuclear motion, and thus are generally difficult to deal with theoretically.The fully quantum simulations give accurate description but are normally too expensive to carry out in complex systems. Comparatively, mixed quantum-classical dynamics (MQCD) methods are widely utilized due to the potentially good balance between efficiency and reliability. Nowadays, the Ehrenfest mean field (EMF), 11 Tully's fewest switches surface hopping (FSSH), 12 and their many variants have become the most popular approaches for nonadiabatic dynamics simulations in different fields. [13][14][15][16][17][18][19][20] Both EMF and FSSH utilize the time-dependent Schrödinger equation (TDSE) to characterize the electronic wavefunction evolution. 11,12 Their major difference lies in the description of nuclear motion. In EMF, the nuclei evolve on a single effective potential energy surface (PES), which is obtained through averaging over all the electronic states and using the quantum populations as weights. In comparison, FSSH forces the nuclei to move on an active PES at any time and allows stochastic surface hops between PESs according to the nonadiabatic coupling. As a result, FSSH can take into account the different motion of nuclear wave packets (WPs) on different PESs.FSSH has shown higher reliability, 12,21,22 better detailed balance, [23][24][25] and the ability to describe both strong and weak polaronic effects, [26][27][28] implying that surface hops play an

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Communication: Global flux surface hopping in Liouville space

Abstract: Quantum decoherence and the isotope effect in condensed phase nonadiabatic molecular dynamics

Cited by 30 publications

References 40 publications

Surface hopping methods for nonadiabatic dynamics in extended systems

Surface hopping methods for nonadiabatic dynamics in extended systems

Nonadiabatic charge dynamics in novel solar cell materials

Branching Corrected Mean Field Method for Nonadiabatic Dynamics

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