skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

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

Abstract

Here in this paper, 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.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [3];  [4]
  1. Univ. Nacional de Quilmes, Bernal (Argentina)
  2. Univ. of Leeds, Leeds (United Kingdom). School of Chemistry; Univ. of Bristol, Bristol (United Kingdom). School of Mathematics
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  4. Univ. of Leeds, Leeds (United Kingdom). School of Chemistry
Publication Date:
Research Org.:
Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC). Basic Energy Sciences (BES) (SC-22); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1454892
Alternate Identifier(s):
OSTI ID: 1483522
Report Number(s):
LA-UR-18-23123
Journal ID: ISSN 1463-9076; PPCPFQ
Grant/Contract Number:  
89233218CNA000001; EP/P021123/1; EP/N007549/1; AC52-06NA25396
Resource Type:
Journal Article: Published Article
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Volume: 20; Journal Issue: 26; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

Citation Formats

Freixas, Victor M., Fernandez-Alberti, Sebastian, Makhov, Dmitry V., Tretiak, Sergei, and Shalashilin, Dmitrii. An ab initio multiple cloning approach for the simulation of photoinduced dynamics in conjugated molecules. United States: N. p., 2018. Web. doi:10.1039/C8CP02321B.
Freixas, Victor M., Fernandez-Alberti, Sebastian, Makhov, Dmitry V., Tretiak, Sergei, & Shalashilin, Dmitrii. An ab initio multiple cloning approach for the simulation of photoinduced dynamics in conjugated molecules. United States. doi:10.1039/C8CP02321B.
Freixas, Victor M., Fernandez-Alberti, Sebastian, Makhov, Dmitry V., Tretiak, Sergei, and Shalashilin, Dmitrii. Tue . "An ab initio multiple cloning approach for the simulation of photoinduced dynamics in conjugated molecules". United States. doi:10.1039/C8CP02321B.
@article{osti_1454892,
title = {An ab initio multiple cloning approach for the simulation of photoinduced dynamics in conjugated molecules},
author = {Freixas, Victor M. and Fernandez-Alberti, Sebastian and Makhov, Dmitry V. and Tretiak, Sergei and Shalashilin, Dmitrii},
abstractNote = {Here in this paper, 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.},
doi = {10.1039/C8CP02321B},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
issn = {1463-9076},
number = 26,
volume = 20,
place = {United States},
year = {2018},
month = {6}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1039/C8CP02321B

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

High-Resolution Inkjet Printing of All-Polymer Transistor Circuits
journal, December 2000