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

Title: Non-adiabatic excited state molecular dynamics of phenylene ethynylene dendrimer using a multiconfigurational Ehrenfest approach

Abstract

Photoinduced dynamics of electronic and vibrational unidirectional energy transfer between meta-linked building blocks in a phenylene ethynylene dendrimer is simulated using a multiconfigurational Ehrenfest in time-dependent diabatic basis (MCE-TDDB) method, a new variant of the MCE approach developed by us for dynamics involving multiple electronic states with numerous abrupt crossings. Excited-state energies, gradients and non-adiabatic coupling terms needed for dynamics simulation are calculated on-the-fly using the Collective Electron Oscillator (CEO) approach. In conclusion, a comparative analysis of our results obtained using MCE-TDDB, the conventional Ehrenfest method and the surface-hopping approach with and without decoherence corrections is presented.

Authors:
 [1];  [2];  [3];  [2]
  1. Universidad Nacional de Quilmes, Roque Saenz Pena (Argentina)
  2. University of Leeds (United Kingdom)
  3. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC); USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1337089
Report Number(s):
LA-UR-15-29142
Journal ID: ISSN 1463-9076
Grant/Contract Number:  
AC52-06NA25396
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 18; Journal Issue: 15; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

Fernandez-Alberti, Sebastian, Makhov, Dmitry V., Tretiak, Sergei, and Shalashilin, Dmitrii V. Non-adiabatic excited state molecular dynamics of phenylene ethynylene dendrimer using a multiconfigurational Ehrenfest approach. United States: N. p., 2016. Web. doi:10.1039/C5CP07332D.
Fernandez-Alberti, Sebastian, Makhov, Dmitry V., Tretiak, Sergei, & Shalashilin, Dmitrii V. Non-adiabatic excited state molecular dynamics of phenylene ethynylene dendrimer using a multiconfigurational Ehrenfest approach. United States. https://doi.org/10.1039/C5CP07332D
Fernandez-Alberti, Sebastian, Makhov, Dmitry V., Tretiak, Sergei, and Shalashilin, Dmitrii V. 2016. "Non-adiabatic excited state molecular dynamics of phenylene ethynylene dendrimer using a multiconfigurational Ehrenfest approach". United States. https://doi.org/10.1039/C5CP07332D. https://www.osti.gov/servlets/purl/1337089.
@article{osti_1337089,
title = {Non-adiabatic excited state molecular dynamics of phenylene ethynylene dendrimer using a multiconfigurational Ehrenfest approach},
author = {Fernandez-Alberti, Sebastian and Makhov, Dmitry V. and Tretiak, Sergei and Shalashilin, Dmitrii V.},
abstractNote = {Photoinduced dynamics of electronic and vibrational unidirectional energy transfer between meta-linked building blocks in a phenylene ethynylene dendrimer is simulated using a multiconfigurational Ehrenfest in time-dependent diabatic basis (MCE-TDDB) method, a new variant of the MCE approach developed by us for dynamics involving multiple electronic states with numerous abrupt crossings. Excited-state energies, gradients and non-adiabatic coupling terms needed for dynamics simulation are calculated on-the-fly using the Collective Electron Oscillator (CEO) approach. In conclusion, a comparative analysis of our results obtained using MCE-TDDB, the conventional Ehrenfest method and the surface-hopping approach with and without decoherence corrections is presented.},
doi = {10.1039/C5CP07332D},
url = {https://www.osti.gov/biblio/1337089}, journal = {Physical Chemistry Chemical Physics. PCCP},
issn = {1463-9076},
number = 15,
volume = 18,
place = {United States},
year = {Thu Mar 10 00:00:00 EST 2016},
month = {Thu Mar 10 00:00:00 EST 2016}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 43 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Starburst dendrimers. 5. Molecular shape control
journal, March 1989


Electronic Spectra of the Nanostar Dendrimer: Theory and Experiment
journal, October 2010


Recent Progress in Dendrimer-Based Nanocarriers
journal, January 2006


Spectroscopic Evidence for Excitonic Localization in Fractal Antenna Supermolecules
journal, February 1997


Correlated Excimer Formation and Molecular Rotational Dynamics in Phenylacetylene Dendrimers
journal, April 2000


Functional dendrimers, hyperbranched and star polymers
journal, May 2000


Molecular Understanding of Organic Solar Cells: The Challenges
journal, November 2009


Mapping Excited-State Dynamics by Coherent Control of a Dendrimer's Photoemission Efficiency
journal, October 2009


Double time window targeting technique: Real-time DMRG dynamics in the Pariser-Parr-Pople model
journal, July 2010


Intrachain exciton dynamics in conjugated polymer chains in solution
journal, August 2015


Exciton Dynamics in Disordered Poly( p -phenylenevinylene). 1. Ultrafast Interconversion and Dynamical Localization
journal, October 2012


Density matrix formulation for quantum renormalization groups
journal, November 1992


Density-matrix algorithms for quantum renormalization groups
journal, October 1993


Cazalilla and Marston Reply:
journal, July 2003


Dynamical density-matrix renormalization-group method
journal, July 2002


Theory of Molecular Excitons
book, January 1971


Exciton-scaling and optical excitations of self-similar phenylacetylene dendrimers
journal, April 1999


Density Matrix Analysis and Simulation of Electronic Excitations in Conjugated and Aggregated Molecules
journal, September 2002


Localized Electronic Excitations in Phenylacetylene Dendrimers
journal, April 1998


Nonadiabatic excited-state molecular dynamics: Treatment of electronic decoherence
journal, June 2013


Semiclassical evaluation of nonadiabatic rates in condensed phases
journal, July 1993


Improvement of the Internal Consistency in Trajectory Surface Hopping
journal, November 1999


Basics of Surface Hopping in Mixed Quantum/Classical Simulations
journal, August 1999


Quantum decoherence in mixed quantum‐classical systems: Nonadiabatic processes
journal, November 1995


Critical appraisal of the fewest switches algorithm for surface hopping
journal, April 2007


Including quantum decoherence in surface hopping
journal, October 2010


Evaluation of quantum transition rates from quantum-classical molecular dynamics simulations
journal, October 1997


Quantum decoherence and the isotope effect in condensed phase nonadiabatic molecular dynamics simulations
journal, April 1996


A new approach to decoherence and momentum rescaling in the surface hopping algorithm
journal, January 2011


Fewest-Switches Surface Hopping and Decoherence in Multiple Dimensions
journal, November 2011


Simultaneous-trajectory surface hopping: A parameter-free algorithm for implementing decoherence in nonadiabatic dynamics
journal, April 2011


Coherent switching with decay of mixing: An improved treatment of electronic coherence for non-Born–Oppenheimer trajectories
journal, January 2004


Using the MCTDH wavepacket propagation method to describe multimode non-adiabatic dynamics
journal, July 2008


Ultrafast Charge Separation in Organic Photovoltaics Enhanced by Charge Delocalization and Vibronically Hot Exciton Dissociation
journal, October 2013


Unified Approach for Molecular Dynamics and Density-Functional Theory
journal, November 1985


Ab Initio Molecular Dynamics Simulations
journal, January 1996


Quantum dynamics simulations using Gaussian wavepackets: the vMCG method
journal, April 2015


Classical/quantal method for multistate dynamics: A computational study
journal, February 1996


Quantum mechanics with the basis set guided by Ehrenfest trajectories: Theory and application to spin-boson model
journal, June 2009


Nonadiabatic dynamics by mean-field and surface-hopping approaches: energy conservation considerations
journal, June 2010


On-the-fly ab initio molecular dynamics with multiconfigurational Ehrenfest method
journal, December 2012


Ab initio multiple cloning algorithm for quantum nonadiabatic molecular dynamics
journal, August 2014


Ab initio multiple cloning simulations of pyrrole photodissociation: TKER spectra and velocity map imaging
journal, January 2015


A classical analog for electronic degrees of freedom in nonadiabatic collision processes
journal, April 1979


On the use of Ehrenfest's theorem in molecular scattering
journal, September 1983


The mean-field theory of nuclear structure and dynamics
journal, October 1982


Identification of unavoided crossings in nonadiabatic photoexcited dynamics involving multiple electronic states in polyatomic conjugated molecules
journal, July 2012


Energy Transfer in Dendritic Macromolecules:  Molecular Size Effects and the Role of an Energy Gradient
journal, January 1996


Phenylacetylene Dendrimers by the Divergent, Convergent, and Double-Stage Convergent Methods
journal, June 1994


Directed Energy Transfer Funnels in Dendrimeric Antenna Supermolecules
journal, August 1997


Basis set sampling in the method of coupled coherent states: Coherent state swarms, trains, and pancakes
journal, February 2008


Krylov-space algorithms for time-dependent Hartree–Fock and density functional computations
journal, July 2000


Representation independent algorithms for molecular response calculations in time-dependent self-consistent field theories
journal, February 2009


Nonadiabatic Excited-State Molecular Dynamics Modeling of Photoinduced Dynamics in Conjugated Molecules
journal, May 2011


Adiabatic time-dependent density functional methods for excited state properties
journal, October 2002


Resonant nonlinear polarizabilities in the time-dependent density functional theory
journal, November 2003


Electronic density-matrix algorithm for nonadiabatic couplings in molecular dynamics simulations
journal, January 2001


Density-matrix representation of nonadiabatic couplings in time-dependent density functional (TDDFT) theories
journal, February 2000


Recursive density‐matrix‐spectral‐moment algorithm for molecular nonlinear polarizabilities
journal, November 1996


Excitonic couplings and electronic coherence in bridged naphthalene dimers
journal, November 1999


Nonadiabatic Excited-State Molecular Dynamics: Modeling Photophysics in Organic Conjugated Materials
journal, February 2014


Proton transfer in solution: Molecular dynamics with quantum transitions
journal, September 1994


Molecular dynamics with electronic transitions
journal, July 1990


Nonadiabatic molecular dynamics
journal, January 1991


Nonadiabatic Molecular Dynamics Simulations of the Energy Transfer between Building Blocks in a Phenylene Ethynylene Dendrimer
journal, July 2009


Unidirectional Energy Transfer in Conjugated Molecules: The Crucial Role of High-Frequency C≡C Bonds
journal, September 2010


Shishiodoshi unidirectional energy transfer mechanism in phenylene ethynylene dendrimers
journal, December 2012


Development and use of quantum mechanical molecular models. 76. AM1: a new general purpose quantum mechanical molecular model
journal, June 1985


CEO/semiempirical calculations of UV–visible spectra in conjugated molecules
journal, December 2000


Conformational Dynamics of Photoexcited Conjugated Molecules
journal, August 2002


Electron-Vibrational Dynamics of Photoexcited Polyfluorenes
journal, September 2004


Ultrafast Dynamics of Electronic Excitations in a Light-Harvesting Phenylacetylene Dendrimer
journal, June 2001


Theoretical analysis of excited states and energy transfer mechanism in conjugated dendrimers
journal, November 2014


Dynamics of Energy Transfer in a Conjugated Dendrimer Driven by Ultrafast Localization of Excitations
journal, July 2015


Analysis of State-Specific Vibrations Coupled to the Unidirectional Energy Transfer in Conjugated Dendrimers
journal, October 2012


Signature of Nonadiabatic Coupling in Excited-State Vibrational Modes
journal, June 2014


A computer simulation method for the calculation of equilibrium constants for the formation of physical clusters of molecules: Application to small water clusters
journal, January 1982


Optimization of width parameters for quantum dynamics with frozen Gaussian basis sets
journal, May 2010


Collective electronic oscillators for nonlinear optical response of conjugated molecules
journal, August 1996


Two-Dimensional Real-Space Analysis of Optical Excitations in Acceptor-Substituted Carotenoids
journal, November 1997


Analysis of Excitonic and Charge Transfer Interactions from Quantum Chemical Calculations
journal, July 2012


New tools for the systematic analysis and visualization of electronic excitations. I. Formalism
journal, July 2014


New tools for the systematic analysis and visualization of electronic excitations. II. Applications
journal, July 2014


Fragment transition density method to calculate electronic coupling for excitation energy transfer
journal, June 2014


A general ansatz for constructing quasi-diabatic states in electronically excited aggregated systems
journal, August 2015


Exciton scattering and localization in branched dendrimeric structures
journal, August 2006


Molecular Orbital Interactions in the Nanostar Dendrimer
journal, December 2003


Works referencing / citing this record:

Different flavors of nonadiabatic molecular dynamics
journal, April 2019


Exciton localization in excited-state dynamics of a tetracene trimer: a surface hopping LC-TDDFTB study
journal, January 2018


Photoinduced non-adiabatic energy transfer pathways in dendrimer building blocks
journal, March 2019