Solving the time-dependent Schrödinger equation for nuclear motion in one step: direct dynamics of non-adiabatic systems

Worth, Graham A.; Robb, Michael A.; Lasorne, Benjamin

doi:10.1080/00268970802172503

Cited by 180 publications

(173 citation statements)

References 86 publications

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“…14 One therefore expects larger effects when the nuclei can move in different directions on different potential energy surfaces. Ways to go beyond the approximation we have used would be to work with an exact factorization of the total wavefunction [30][31][32] or to use a Hellertype Gaussian wavepacket representation [33][34][35] of the nuclear wavepacket.…”

Section: B Classical Nuclear Dynamicsmentioning

confidence: 99%

Electron dynamics upon ionization: Control of the timescale through chemical substitution and effect of nuclear motion

Vacher

Mendive-Tapia

Bearpark

et al. 2015

The Journal of Chemical Physics

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Articles you may be interested inPhotoelectron spectroscopic study of the E⊗e Jahn-Teller effect in the presence of a tunable spin-orbit interaction. I. Photoionization dynamics of methyl iodide and rotational fine structure of CH3I+ and CD3I+ J. Chem. Phys. 134, 054308 (2011) Photoionization can generate a non-stationary electronic state, which leads to coupled electronnuclear dynamics in molecules. In this article, we choose benzene cation as a prototype because vertical ionization of the neutral species leads to a Jahn-Teller degeneracy between ground and first excited states of the cation. Starting with equal populations of ground and first excited states, there is no electron dynamics in this case. However, if we add methyl substituents that break symmetry but do not radically alter the electronic structure, we see charge migration: oscillations in the spin density that we can correlate with particular localized electronic structures, with a period depending on the gap between the states initially populated. We have also investigated the effect of nuclear motion on electron dynamics using a complete active space self-consistent field (CASSCF) implementation of the Ehrenfest method, most previous theoretical studies of electron dynamics having been carried out with fixed nuclei. In toluene cation for instance, simulations where the nuclei are allowed to move show significant differences in the electron dynamics after 3 fs, compared to simulations with fixed nuclei. C 2015 AIP Publishing LLC. [http://dx

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Section: B Classical Nuclear Dynamicsmentioning

confidence: 99%

Electron dynamics upon ionization: Control of the timescale through chemical substitution and effect of nuclear motion

Vacher

Mendive-Tapia

Bearpark

et al. 2015

The Journal of Chemical Physics

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“…29 Therefore, the present work proposes to relate the vibrational motions of the PPE units with their efficiency in the unidirectional energy transfer by using direct nonadiabatic molecular dynamics simulations. 30 Previous works have already shown the usefulness of these methods in the study of photochemical reaction mechanisms in organic compounds. [31][32][33][34][35] In particular, direct dynamics studies using trajectory surface hopping have been applied to the photochemistry of a wide variety of organic molecules: benzene, 36 fulvene, azulene, 37 guanine-cytocine, 38 formamide, 39 silaethylene, 40 ethylene, 41 and pyrrole, 42 among others.…”

Section: Introductionmentioning

confidence: 99%

Nonadiabatic Molecular Dynamics Simulations of the Energy Transfer between Building Blocks in a Phenylene Ethynylene Dendrimer

et al. 2009

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The ultrafast dynamics of electronic and vibrational energy transfer between two-and three-ring linear poly(phenylene ethynylene) units linked by meta-substitution is studied by nonadiabatic molecular dynamics simulations. The molecular dynamics with quantum transitions 1,2 method is used including an "on the fly" calculation of the potential energy surfaces and electronic couplings. The results show that during the first 40 fs after a vertical photoexcitation to the S 2 state, the nonadiabatic coupling between S 2 and S 1 states causes a fast transfer of the electronic populations. A rapid decrease of the S 1 -S 2 energy gap is observed, reaching a first conical intersection at ≈5 fs. Therefore, the first hopping events take place, and the S 2 state starts to depopulate. The analysis of the structural and energetic properties of the molecule during the jumps reveals the main role that the ethynylene triple bond plays in the unidirectional energy transfer process.

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“…Nevertheless an ab initio on-the-fly direct dynamics version of vMCG does exist. 33 The AIMS 10,24,[34][35][36] method uses a much simpler choice for the evolution of the TBFs: their phase space centers evolve classically on a specific electronic state and the basis set is expanded adaptively as needed, in a process called spawning. The spawning becomes particularly important near the intersection with another electronic state, where more Gaussians are spawned on the second PES.…”

Section: Introductionmentioning

confidence: 99%

Ab initio multiple cloning algorithm for quantum nonadiabatic molecular dynamics

Makhov

Glover

Martı́nez

et al. 2014

The Journal of Chemical Physics

196

245

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An atomic orbital-based formulation of analytical gradients and nonadiabatic coupling vector elements for the state-averaged complete active space self-consistent field method on graphical processing units We present a new algorithm for ab initio quantum nonadiabatic molecular dynamics that combines the best features of ab initio Multiple Spawning (AIMS) and Multiconfigurational Ehrenfest (MCE) methods. In this new method, ab initio multiple cloning (AIMC), the individual trajectory basis functions (TBFs) follow Ehrenfest equations of motion (as in MCE). However, the basis set is expanded (as in AIMS) when these TBFs become sufficiently mixed, preventing prolonged evolution on an averaged potential energy surface. We refer to the expansion of the basis set as "cloning," in analogy to the "spawning" procedure in AIMS. This synthesis of AIMS and MCE allows us to leverage the benefits of mean-field evolution during periods of strong nonadiabatic coupling while simultaneously avoiding mean-field artifacts in Ehrenfest dynamics. We explore the use of time-displaced basis sets, "trains," as a means of expanding the basis set for little cost. We also introduce a new bra-ket averaged Taylor expansion (BAT) to approximate the necessary potential energy and nonadiabatic coupling matrix elements. The BAT approximation avoids the necessity of computing electronic structure information at intermediate points between TBFs, as is usually done in saddle-point approximations used in AIMS. The efficiency of AIMC is demonstrated on the nonradiative decay of the first excited state of ethylene. The AIMC method has been implemented within the AIMS-MOLPRO package, which was extended to include Ehrenfest basis functions.

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Solving the time-dependent Schrödinger equation for nuclear motion in one step: direct dynamics of non-adiabatic systems

Cited by 180 publications

References 86 publications

Electron dynamics upon ionization: Control of the timescale through chemical substitution and effect of nuclear motion

Electron dynamics upon ionization: Control of the timescale through chemical substitution and effect of nuclear motion

Nonadiabatic Molecular Dynamics Simulations of the Energy Transfer between Building Blocks in a Phenylene Ethynylene Dendrimer

Ab initio multiple cloning algorithm for quantum nonadiabatic molecular dynamics

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