Mixed quantum-classical dynamics with time-dependent external fields: A time-dependent density-functional-theory approach

Tavernelli, Ivano; Curchod, Basile F. E.; Röthlisberger, Ursula

doi:10.1103/physreva.81.052508

Cited by 59 publications

(56 citation statements)

References 70 publications

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“…where H SO LM are the spin-orbit couplings [46] and the last term accounts for the dipole interaction of the molecule with the field (μ ML is the transition dipole moment between the L and M and A 0 is the vector potential) [49]. In Sect.…”

Section: Surface Hopping Overviewmentioning

confidence: 99%

Surface Hopping Dynamics with DFT Excited States

Barbatti

Crespo‐Otero

2014

Topics in Current Chemistry

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Nonadiabatic dynamics simulation of electronically-excited states has been a research area of fundamental importance, providing support for spectroscopy, explaining photoinduced processes, and predicting new phenomena in a variety of specialties, from basic physical-chemistry, through molecular biology, to materials engineering. The demands in the field, however, are quickly growing, and the development of surface hopping based on density functional theory (SH/DFT) has been a major advance in the field. In this contribution, the surface hopping approach, the methods for computation of excited states based on DFT, the connection between these methodologies, and their diverse implementations are reviewed. The shortcomings of the methods are critically addressed and a number of case studies from diverse fields are surveyed.

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Section: Surface Hopping Overviewmentioning

confidence: 99%

Surface Hopping Dynamics with DFT Excited States

Barbatti

Crespo‐Otero

2014

Topics in Current Chemistry

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“…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.…”

mentioning

confidence: 99%

Surface hopping in laser-driven molecular dynamics

et al. 2017

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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...

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“…the development of a coupling scheme for the inclusion of external timedependent electric fields (in particular laser fields) [255].…”

Section: Methods Based On Density Functional Theorymentioning

confidence: 99%

Quantum modeling of ultrafast photoinduced charge separation

Rozzi

Troiani

Tavernelli

2017

J. Phys.: Condens. Matter

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Phenomena involving electron transfer are ubiquitous in nature, photosynthesis and enzymes or protein activity being prominent examples. Their deep understanding thus represents a mandatory scientific goal. Moreover, controlling the separation of photogenerated charges is a crucial prerequisite in many applicative contexts, including quantum electronics, photo-electrochemical water splitting, photocatalytic dye degradation, and energy conversion. In particular, photoinduced charge separation is the pivotal step driving the storage of sun light into electrical or chemical energy. If properly mastered, these processes may also allow us to achieve a better command of information storage at the nanoscale, as required for the development of molecular electronics, optical switching, or quantum technologies, amongst others.In this Topical review we survey recent progress in the understanding of ultrafast charge separation from photoexcited states. We report the state-of-the-art of the observation and theoretical description of charge separation phenomena in the ultrafast regime mainly focusing on molecularand nano-sized solar energy conversion systems. In particular, we examine different proposed mechanisms driving ultrafast charge dynamics, with particular regard to the role of quantum coherence and electron-nuclear coupling, and link experimental observations to theoretical approaches based either on model Hamiltonians or on first principles simulations.

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Mixed quantum-classical dynamics with time-dependent external fields: A time-dependent density-functional-theory approach

Cited by 59 publications

References 70 publications

Surface Hopping Dynamics with DFT Excited States

Surface Hopping Dynamics with DFT Excited States

Surface hopping in laser-driven molecular dynamics

Quantum modeling of ultrafast photoinduced charge separation

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