An Ab Initio Multiple Cloning Method for Non-Adiabatic Excited-State Molecular Dynamics in NWChem

Huajing Song, Victor M. Freixas, Sebastian Fernandez-Alberti, Alexander J. White, Yu Zhang, Shaul Mukamel, Niranjan Govind, Sergei Tretiak

Research output: Contribution to journalArticlepeer-review

8 Citations (Scopus)

Abstract

The recently developed ab initio multiple cloning (AIMC) approach based on the multiconfigurational Ehrenfest (MCE) method provides a powerful and accurate way of describing the excited-state dynamics of molecular systems. The AIMC method is a controlled approximation to nonadiabatic dynamics with a particular strength in the proper description of decoherence effects because of the branching of vibrational wavepackets at a level crossing. Here, we report a new implementation of the AIMC algorithm in the open source NWChem computational chemistry program. The framework combines linear-response time-dependent density functional theory with Ehrenfest mean-field theory to determine the equations of motion for classical trajectories. The multidimensional wave function is decomposed into a superposition of Gaussian coherent states guided by Ehrenfest trajectories (i.e., MCE approach), which can clone with fully quantum mechanical amplitudes and phases. By using an efficient time-derivative based nonadiabatic coupling approach within the AIMC method, all observables are calculated on-the-fly in the nonadiabatic molecular dynamics process. As a representative example, we apply our implementation to study the ultrafast photoinduced electronic and vibrational energy transfer in a pyridine molecule. The effects of the cloning procedure on electronic and vibrational coherence, relaxation and unidirectional energy transfer are discussed. This new AIMC implementation provides a high-level nonadiabatic molecular dynamics framework for simulating photoexcited dynamics in complex molecular systems and experimentally relevant ultrafast spectroscopic probes, such as nonlinear coherent optical and X-ray signals.

Original languageEnglish
Pages (from-to)3629-3643
Number of pages15
JournalJournal of Chemical Theory and Computation
Volume17
Issue number6
DOIs
Publication statusPublished - 8 Jun 2021
Externally publishedYes

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