Understanding the Surface Hopping View of Electronic Transitions and Decoherence

Subotnik, Joseph E.; Jain, Amber; Landry, Brian R.; Petit, Andrew S.; Ouyang, Wenjun; Bellonzi, Nicole

doi:10.1146/annurev-physchem-040215-112245

Cited by 366 publications

(449 citation statements)

References 151 publications

Supporting

Mentioning

445

Contrasting

Unclassified

Order By: Relevance

“…Among others, the lack of communication between the evolving trajectories leads to overcoherence, and limitations in the energy conservation are hampering a description of superexchange processes. [18,20] On the other hand, also the SHT algorithm itself has been improved. In the so-called single switch surface hopping (SSSH) approaches, there is only a single switch decision required each time a trajectory passes a critical region, typically a (genuine or avoided) crossing seam or conical intersection.…”

Section: Introductionmentioning

confidence: 99%

WavePacket: A Matlab package for numerical quantum dynamics. III. Quantum‐classical simulations and surface hopping trajectories

2019

View full text Add to dashboard Cite

WavePacket is an open‐source program package for numerical simulations in quantum dynamics. Building on the previous Part I (Schmidt and Lorenz, Comput. Phys. Commun. 2017, 213, 223] and Part II (Schmidt and Hartmann, Comput. Phys. Commun. 2018, 228, 229] which dealt with quantum dynamics of closed and open systems, respectively, the present Part III adds fully classical and mixed quantum‐classical propagation techniques to WavePacket. There classical phase‐space densities are sampled by trajectories which follow (diabatic or adiabatic) potential energy surfaces. In the vicinity of (genuine or avoided) intersections of those surfaces, trajectories may switch between them. To model these transitions, two classes of stochastic algorithms have been implemented: (1) Tully's fewest switches surface hopping and (2) Landau–Zener‐based single switch surface hopping. The latter one offers the advantage of being based on adiabatic energy gaps only, thus not requiring nonadiabatic coupling information any more. The present work describes the MATLAB version of WavePacket 6.1.0, which is essentially an object‐oriented rewrite of previous versions, allowing to perform fully classical, quantum‐classical and quantum‐mechanical simulations on an equal footing, that is, for the same physical system described by the same WavePacket input. The software package is hosted and further developed at the Sourceforge platform, where also extensive Wiki‐documentation as well as numerous worked‐out demonstration examples with animated graphics are available. © 2019 Wiley Periodicals, Inc.

show abstract

Section: Introductionmentioning

confidence: 99%

WavePacket: A Matlab package for numerical quantum dynamics. III. Quantum‐classical simulations and surface hopping trajectories

2019

View full text Add to dashboard Cite

show abstract

“…Hopping schemes using Born-Oppenheimer surfaces or instantaneous Born-Oppenheimer surfaces fail completely. For more than two decades, surface hopping (SH) [1] has been among the most popular and successful methods to describe non-adiabatic phenomena in atomic manybody systems (for reviews see [2][3][4][5]). From the theoretical point of view, however, any SH scheme is inherently a phenomenological approach.…”

mentioning

confidence: 99%

Surface hopping in laser-driven molecular dynamics

et al. 2017

View full text Add to dashboard Cite

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 105, 123002 (2010)] in its quantum-classical limit. Employing an exactly solvable H + 2 -like model system, it is shown that the deterministic classical nuclear motion on a single timedependent surface in this approach describes the same physics as stochastic (hopping-induced) motion on several surfaces, provided Floquet surfaces are applied. Both quantum-classical methods do describe reasonably well the exact nuclear wavepacket dynamics for extremely different dissociation scenarios. Hopping schemes using Born-Oppenheimer surfaces or instantaneous Born-Oppenheimer surfaces fail completely. For more than two decades, surface hopping (SH) [1] has been among the most popular and successful methods to describe non-adiabatic phenomena in atomic manybody systems (for reviews see [2][3][4][5]). From the theoretical point of view, however, any SH scheme is inherently a phenomenological approach. The ad hoc assumption of stochastic jumps between electronic potential energy surfaces (PES) has, so far, never been rigorously deduced from the time-dependent Schrödinger equation (TDSE) for electrons and nuclei, and even the choice of the applied PES is ambiguous.Very recently, however, first attempts have been made to justify the SH methodology on Born-Oppenheimer surfaces (BOSs), solely for the laser-free non-adiabatic dynamics [6][7][8][9]. A close similarity between the exact wavepacket propagation and SH on BOSs has been found in the framework of the exact factorization of the molecular wavefunction [6]. In this theory, the so-called exact time-dependent potential energy surface (EPES), together with an exact time-dependent vector potential, governs the true nuclear wavepacket dynamics. The EPES can exhibit nearly discontinuous step-like features, just in the vicinity of avoided crossings between BOSs, leading simultaneously to acceleration and deceleration of certain parts of the quantum wavepacket and resulting in its splitting. In close analogy, the SH mechanism can create branches of classical trajectories at avoided crossings. The findings [6] justify, albeit qualitatively but anyhow convincingly, the SH methodology on BOSs, in the field-free case.For the laser-driven dynamics, any validation of SH is still lacking and the appropriate choice of the applicable PES is discussed controversially, at present [10][11][12]. In fact, the hitherto purely intuitively chosen PES in SH models are fundamentally different from each other, and include BOSs [10,[13][14][15][16][17], instantaneous BOSs (IBOSs) [18][19][20][21][22] as well as Floquet surfaces (FSs) [22][23][24]. From the massive differences in definition and properties of these PESs, one can hardly expect that the appendant SH schemes can describe the same physics. Obviously, the situation requires clarification and the general questions persist: Is ther...

show abstract

“…We think this is more advantageous than treating the electronic and nuclear degrees of freedom on the same footing, as it allows us to employ numerical strategies that exploit the scale separation between the nuclei and electrons and also offer more flexibility. As another advantage, since we use a surface hopping type dynamics to treat the discrete electronic states, it is more natural to combine the proposed thermal (imaginary time) sampling method with real time surface hopping dynamics [3,[28][29][30][31][32][33][34], which is one of the motivations of our development following our recent works in surface hopping dynamics [35,36]. Let us remark that there have been recent works trying to combine the path integral formulation and surface hopping dynamics [37], though it is unclear if the trajectory with hopping dynamics can preserve the thermal equilibrium.…”

Section: Introductionmentioning

confidence: 99%

Path integral molecular dynamics with surface hopping for thermal equilibrium sampling of nonadiabatic systems

Zhou

2017

The Journal of Chemical Physics

View full text Add to dashboard Cite

In this work, a novel ring polymer representation for multi-level quantum system is proposed for thermal average calculations. The proposed representation keeps the discreteness of the electronic states: besides position and momentum, each bead in the ring polymer is also characterized by a surface index indicating the electronic energy surface. A path integral molecular dynamics with surface hopping (PIMD-SH) dynamics is also developed to sample the equilibrium distribution of ring polymer configurational space. The PIMD-SH sampling method is validated theoretically and by numerical examples.

show abstract

Understanding the Surface Hopping View of Electronic Transitions and Decoherence

Cited by 366 publications

References 151 publications

WavePacket: A Matlab package for numerical quantum dynamics. III. Quantum‐classical simulations and surface hopping trajectories

WavePacket: A Matlab package for numerical quantum dynamics. III. Quantum‐classical simulations and surface hopping trajectories

Surface hopping in laser-driven molecular dynamics

Path integral molecular dynamics with surface hopping for thermal equilibrium sampling of nonadiabatic systems

Contact Info

Product

Resources

About