Surface Hopping Dynamics with DFT Excited States

Barbatti, Mario; Crespo‐Otero, Rachel

doi:10.1007/128_2014_605

Cited by 72 publications

(100 citation statements)

References 182 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…These methods have been discussed and reviewed in detail in Refs. 16,[27][28][29][30][31][32] . In this section, we only outline their main features, which will be useful to discuss the new developments that have been recently proposed.…”

Section: Standard Methods For Na-mqc Dynamicsmentioning

confidence: 99%

See 1 more Smart Citation

Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

2018

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Section: Standard Methods For Na-mqc Dynamicsmentioning

confidence: 99%

“…KL ODC KL   FF (28) Such insight has given rise to a series of overlap-based decoherence corrections (ODC), which are based on approximated estimates of wave packet overlap decay. Granucci and Persico, 66 for instance, have proposed an ODC approach dependent on two parameters, the wave packet width and the minimum overlap threshold.…”

mentioning

confidence: 99%

Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

2018

Self Cite

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

“…[37][38] Thus, TSH coupled to LR-TDDFT has been used for a variety of applications. [39][40][41][42] More recently, AIMS was interfaced with GPU-accelerated LR-TDDFT and applied to study the photophysics of 4-(dimethylamino)benzonitrile (DMABN) (unpublished results). Despite its successes, LR-TDDFT has some well-known shortcomings that are due to practical approximations required to make the method tractable.…”

mentioning

confidence: 99%

GPU-Accelerated State-Averaged Complete Active Space Self-Consistent Field Interfaced with Ab Initio Multiple Spawning Unravels the Photodynamics of Provitamin D₃

Snyder

Curchod

Martı́nez

2016

J. Phys. Chem. Lett.

View full text Add to dashboard Cite

Excited-state molecular dynamics is essential to the study of photochemical reactions, which occur under nonequilibrium conditions. However, the computational cost of such simulations has often dictated compromises between accuracy and efficiency. The need for an accurate description of both the molecular electronic structure and nuclear dynamics has historically stymied the simulation of medium- to large-size molecular systems. Here, we show how to alleviate this problem by combining ab initio multiple spawning (AIMS) for the nuclear dynamics and GPU-accelerated state-averaged complete active space self-consistent field (SA-CASSCF) for the electronic structure. We demonstrate the new approach by first-principles SA-CASSCF/AIMS nonadiabatic dynamics simulation of photoinduced electrocyclic ring-opening in the 51-atom provitamin D3 molecule.

show abstract

Surface Hopping Dynamics with DFT Excited States

Cited by 72 publications

References 182 publications

Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

Surface hopping in laser-driven molecular dynamics

GPU-Accelerated State-Averaged Complete Active Space Self-Consistent Field Interfaced with Ab Initio Multiple Spawning Unravels the Photodynamics of Provitamin D₃

Contact Info

Product

Resources

About

Surface Hopping Dynamics with DFT Excited States

Cited by 72 publications

References 182 publications

Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

Recent Advances and Perspectives on Nonadiabatic Mixed Quantum–Classical Dynamics

Surface hopping in laser-driven molecular dynamics

GPU-Accelerated State-Averaged Complete Active Space Self-Consistent Field Interfaced with Ab Initio Multiple Spawning Unravels the Photodynamics of Provitamin D3

Contact Info

Product

Resources

About

GPU-Accelerated State-Averaged Complete Active Space Self-Consistent Field Interfaced with Ab Initio Multiple Spawning Unravels the Photodynamics of Provitamin D₃