Simulation of the dynamics of vibrationally mediated photodissociation for deuterated pyrrole

Makhov, Dmitry V.; Adeyemi, Sian; Cowperthwaite, Mary; Shalashilin, Dmitrii V.

doi:10.1088/2399-6528/ac4d39

Cited by 6 publications

(3 citation statements)

References 41 publications

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“…Then, the time evolution of the basis is not variational anymore, and the solution to the SE is not optimal but is still variational. This decoupling is often employed for the time evolution of TDBFs associated with nuclear degrees of freedom, represented by Gaussians − or coherent states − whose centers follow classical trajectories: for example, using Erhenfest ,, or Born–Oppenheimer trajectories. ,, We can also mention that solving the electronic SE in mixed quantum-classical dynamics, such as Ehrenfest or surface hopping, requires propagating the electronic wavefunction expanded on a set of Gaussian TDBFs that follow nuclear motion…”

Section: Introductionmentioning

confidence: 99%

Variational Approach for Linearly Dependent Moving Bases in Quantum Dynamics: Application to Gaussian Functions

Joubert-Doriol

2022

J. Chem. Theory Comput.

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In this paper, we present a variational treatment of the linear dependence for a non-orthogonal time-dependent basis set in solving the Schrödinger equation. The method is based on (i) the definition of a linearly independent working space and (ii) a variational construction of the propagator over finite time steps. The second point allows the method to properly account for changes in the dimensionality of the working space along the time evolution. In particular, the time evolution is represented by a semi-unitary transformation. Tests are carried out on a quartic double-well potential with Gaussian basis functions whose centers evolve according to classical equations of motion. We show that the resulting dynamics converges to the exact one and is unitary by construction.

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Section: Introductionmentioning

confidence: 99%

Variational Approach for Linearly Dependent Moving Bases in Quantum Dynamics: Application to Gaussian Functions

Joubert-Doriol

2022

J. Chem. Theory Comput.

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“…Then, the time evolution of the basis is not variational anymore, and the solution to the SE is not optimal but is still variational. This decoupling is often employed for the time evolution of TDBFs associated with nuclear degrees of freedom (DOFs), represented by Gaussians [20][21][22][23] or coherent states [24][25][26] whose a) Electronic mail: loic.joubert-doriol@univ-eiffel.fr centers follow classical trajectories: for example using Erhenfest 17,27,28 , or Born-Oppenheimer trajectories. 15,29,30 The independent TDBFs approach projects the SE on a time-dependent (working) space spanned by the TDBFs.…”

Section: Introductionmentioning

confidence: 99%

A variational approach for linearly dependent moving bases in quantum dynamics: application to Gaussian functions

Joubert-Doriol

2022

Preprint

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In this paper, we present a variational treatment of the linear dependence for a non-orthogonal time-dependent basis set in solving the Schrödinger equation. The method is based on: i) the definition of a linearly independent working space, and ii) a variational construction of the propagator over finite time-steps. The second point allows the method to properly account for changes in the dimensionality of the working space along the time evolution. In particular, the time evolution is represented by a semi-unitary transformation. Tests are done on a quartic double-well potential with Gaussian basis function whose centers evolve according to classical equations of motion. We show that the resulting dynamics converges to the exact one and is unitary by construction.

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“…AIMC is a somewhat more rigorous way to treat nonadiabatic transitions than surface hopping employed in ref . It has been shown that AIMC can provide an accurate description of nonadiabatic dynamics from first principles. − The Quantemol Electron Collisions (QEC) code that interfaces with the UKRmol+ suite of molecular R-matrix codes is used to determine the initial triplet states created by electron impact in plasma. Although AIMC was originally developed for the simulation of nonadiabatic dynamics of excited molecules in singlet states in photochemistry, it can equally be used for the dynamics of molecules in low-energy triplet states produced by electron impact.…”

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confidence: 99%

Dissociation of Hydrofluorocarbon Molecules after Electron Impact in Plasma

Makhov,

Armstrong,

Chuang

et al. 2024

J. Phys. Chem. Lett.

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The process of dissociation for two hydrofluorocarbon molecules in low triplet states excited by electron impact in plasma is investigated by ab initio molecular dynamics (AIMD). The interest in the dissociation of hydrofluorocarbons in plasma is motivated by their role in plasma etching in microelectronic technologies. Dissociation of triplet states is very fast, and the reaction products can be predicted. In this work, it was found that higher triplet states relax into the lowest triplet state within a few femtoseconds due to nonadiabatic dynamics, such that the simplest ab initio MD on the lowest triplet state seems to give a reasonable estimate of the reaction channels branching ratios. We provide evidence of the existence of simple rules for the dissociation of hydrofluorocarbon molecules in triplet states. For molecules with a double bond, the bonds adjacent to the double bond dissociate faster than the other bonds.

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Simulation of the dynamics of vibrationally mediated photodissociation for deuterated pyrrole

Cited by 6 publications

References 41 publications

Variational Approach for Linearly Dependent Moving Bases in Quantum Dynamics: Application to Gaussian Functions

Variational Approach for Linearly Dependent Moving Bases in Quantum Dynamics: Application to Gaussian Functions

A variational approach for linearly dependent moving bases in quantum dynamics: application to Gaussian functions

Dissociation of Hydrofluorocarbon Molecules after Electron Impact in Plasma

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