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Excited state dynamics initiated by an electromagnetic field within the Variational Multi-Configurational Gaussian (vMCG) method

Lookup NU author(s): Professor Thomas Penfold



This work is licensed under a Creative Commons Attribution-NonCommercial-NoDerivatives 4.0 International License (CC BY-NC-ND).


The Variational Multi-Configurational Gaussian (vMCG) approach offers a framework to perform exact trajectory-based quantum dynamics. Herein we use two model vibronic coupling Hamiltonians of pyrazine to explore, for the first time, the influence of the coupling between the external field and the Gaussian basis functions (GBFs) in vMCG on the dynamics. We show that when the excitation pulse is short compared to the nuclear dynamics, vertical projection without a field and explicit description of the external field converge. For longer pulses, a sizeable change is observed. We demonstrate that comparatively few GBFs are sufficient to provide qualitative agreement to MCTDH dynamics and a quantitative agreement can be achieved using 100 GBFs. Longer pulses require more GBFs due to the prolonged coupling between the ground and excited states. Throughout this work the single set formalism offers the fastest convergence.

Publication metadata

Author(s): Penfold TJ, Pápai M, Møller KB, Worth GA

Publication type: Article

Publication status: Published

Journal: Computational and Theoretical Chemistry

Year: 2019

Volume: 1160

Pages: 24-30

Print publication date: 15/07/2019

Online publication date: 30/05/2019

Acceptance date: 28/05/2019

Date deposited: 01/06/2019

ISSN (print): 2210-271X

ISSN (electronic): 2210-2728

Publisher: Elsevier


DOI: 10.1016/j.comptc.2019.05.012


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