An ab initio multiple cloning approach for the simulation of photoinduced dynamics in conjugated molecules

Victor M. Freixas, Sebastian Fernandez-Alberti*, Dmitry V. Makhov, Sergei Tretiak, Dmitrii Shalashilin

*Corresponding author for this work

Research output: Contribution to journalArticle (Academic Journal)peer-review

13 Citations (Scopus)
255 Downloads (Pure)

Abstract

We present a new implementation of the Ab Initio Multiple Cloning (AIMC) method, which is applied for non-adiabatic excited-state molecular dynamics simulations of photoinduced processes in conjugated molecules. Within our framework, the multidimensional wave-function is decomposed into a superposition of a number of Gaussian coherent states guided by Ehrenfest trajectories that are suited to clone and swap their electronic amplitudes throughout the simulation. New generalized cloning criteria are defined and tested. Because of sharp changes of the electronic states, which are common for conjugated polymers, the electronic parts of the Gaussian coherent states are represented in the Time Dependent Diabatic Basis (TDDB). The input to these simulations in terms of the excited-state energies, gradients and non-adiabatic couplings, is calculated on-the-fly using the Collective Electron Oscillator (CEO) approach. As a test case, we consider the photoinduced unidirectional electronic and vibrational energy transfer between two- and three-ring linear poly(phenylene ethynylene) units linked by meta-substitution. The effects of the cloning procedure on electronic and vibrational coherence, relaxation and unidirectional energy transfer between dendritic branches are discussed.

Original languageEnglish
Pages (from-to)17762-17772
Number of pages11
JournalPhysical Chemistry Chemical Physics
Volume20
Issue number26
Early online date19 Jun 2018
DOIs
Publication statusPublished - 4 Jul 2018

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