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

Lu, Jianfeng; Zhou, Zhennan

doi:10.1063/1.4981021

Cited by 24 publications

(59 citation statements)

References 45 publications

(100 reference statements)

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“…Ehrenfest and TSH schemes for the electronic represent an alternative for the treatment of such quantum effects, as discussed below. [88][89][90][91] In RPMD, quantum particles are mapped onto a closed flexible polymer of P beads, profiting from an isomorphism between the quantum-statistical problem formulated in terms of a discretized version of Feynman's path integral and a classical problem. RPMD is derived for equilibrium processes, its use for non-equilibrium processes such as excited state dynamics, is done ad hoc.…”

Section: Incorporating Tunnellingmentioning

confidence: 99%

“…Lu and Zhou 88 have developed a conceptually different version of RPMD with TSH named path integral molecular dynamics with surface hopping (PIMD-SH). While in the RPSH the ring is treated as a molecule (each bead is an atom) that moves on a single potential energy surface, in the PIMD-SH, each bead may occupy a different state, directly related to the actual electronic states.…”

Section: Incorporating Tunnellingmentioning

confidence: 99%

“…All methods discussed above are related to the time-dependent approach to the spectrum, as given by Eq. (88). TSH has also been used to provide complementary information to the conventional energy-eigenvalue approach, where the spectrum is evaluated as a sum over all (91) In this equation, 0…”

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confidence: 99%

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Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

2018

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Nonadiabatic mixed quantum-classical (NA-MQC) dynamics methods form a class of computational theoretical approaches in quantum chemistry tailored to investigate the time evolution of nonadiabatic phenomena in molecules and supramolecular assemblies. NA-MQC is characterized by a partition of the molecular system into two subsystems: one to be treated quantum mechanically (usually but not restricted to electrons) and another to be dealt with classically (nuclei). The two subsystems are connected through nonadiabatic couplings terms to enforce self-consistency. A local approximation underlies the classical subsystem, implying that direct dynamics can be simulated, without needing precomputed potential energy surfaces. The NA-MQC split allows reducing computational costs, enabling the treatment of realistic molecular systems in diverse fields. Starting from the three most well-established methods-mean-field Ehrenfest, trajectory surface hopping, and multiple spawning-this review focuses on the NA-MQC dynamics methods and programs developed in the last 10 years. It stresses the relations between approaches and their domains of application. The electronic structure methods most commonly used together with NA-MQC dynamics are reviewed as well. The accuracy and precision of NA-MQC simulations are critically discussed, and general guidelines to choose an adequate method for each application are delivered.

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Section: Incorporating Tunnellingmentioning

confidence: 99%

Section: Incorporating Tunnellingmentioning

confidence: 99%

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Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

2018

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“…290 Recently, though, this limitation has been lifted and nuclear quantum effects have been incorporated into the method by combining it with ring polymer MD. [327][328][329] Additionally, the essential asymmetry between quantum and classical degrees of freedom in this approach can lead to an overly coherent electron dynamics often termed the "decoherence-problem", which can lead to spurious results. 323,330,331 The latter can have an especially large impact on charge-transfer rates to the point where SH dynamics is not able to recover the Marcus limit if applied to the respective hopping regime.…”

Section: Surface Hopping Approachesmentioning

confidence: 99%

Charge Transport in Molecular Materials: An Assessment of Computational Methods

2017

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The booming field of molecular electronics has fostered a surge of computational research on electronic properties of organic molecular solids. In particular, with respect to a microscopic understanding of transport and loss mechanisms, theoretical studies assume an ever-increasing role. Owing to the tremendous diversity of organic molecular materials, a great number of computational methods have been put forward to suit every possible charge transport regime, material, and need for accuracy. With this review article we aim at providing a compendium of the available methods, their theoretical foundations, and their ranges of validity. We illustrate these through applications found in the literature. The focus is on methods available for organic molecular crystals, but mention is made wherever techniques are suitable for use in other related materials such as disordered or polymeric systems.

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“…Instead of the diabatic representation, the adiabatic one was employed by Schmidt and Tully in 2007 to express the Boltzmann operator, where each path integral bead was associated with a surface index that represents which adiabatic potential energy surface the bead lies on 29 . Lu and Zhou further extended the idea to combine PIMD with surface hopping for sampling thermal equilibrium nonadiabatic systems 30 .…”

Section: Introductionmentioning

confidence: 99%

Path integral molecular dynamics for exact quantum statistics of multi-electronic-state systems

Liu

2017

The Journal of Chemical Physics

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An exact approach to compute physical properties for general multi-electronic-state (MES) systems in thermal equilibrium is presented. The approach is extended from our recent progress on path integral molecular dynamics (PIMD), Liu et al. [J. Chem. Phys. 145, 024103 (2016)] and Zhang et al. [J. Chem. Phys. 147, 034109 (2017)], for quantum statistical mechanics when a single potential energy surface is involved. We first define an effective potential function that is numerically favorable for MES-PIMD and then derive corresponding estimators in MES-PIMD for evaluating various physical properties. Its application to several representative one-dimensional and multi-dimensional models demonstrates that MES-PIMD in principle offers a practical tool in either of the diabatic and adiabatic representations for studying exact quantum statistics of complex/large MES systems when the Born-Oppenheimer approximation, Condon approximation, and harmonic bath approximation are broken.

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

Cited by 24 publications

References 45 publications

Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

Charge Transport in Molecular Materials: An Assessment of Computational Methods

Path integral molecular dynamics for exact quantum statistics of multi-electronic-state systems

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