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Title: Coherent exciton-vibrational dynamics and energy transfer in conjugated organics

Abstract

Coherence, signifying concurrent electron-vibrational dynamics in complex natural and man-made systems, is currently a subject of intense study. Understanding this phenomenon is important when designing carrier transport in optoelectronic materials. Here, excited state dynamics simulations reveal a ubiquitous pattern in the evolution of photoexcitations for a broad range of molecular systems. Symmetries of the wavefunctions define a specific form of the non-adiabatic coupling that drives quantum transitions between excited states, leading to a collective asymmetric vibrational excitation coupled to the electronic system. This promotes periodic oscillatory evolution of the wavefunctions, preserving specific phase and amplitude relations across the ensemble of trajectories. The simple model proposed here explains the appearance of coherent exciton-vibrational dynamics due to non-adiabatic transitions, which is universal across multiple molecular systems. The observed relationships between electronic wavefunctions and the resulting functionalities allows us to understand, and potentially manipulate, excited state dynamics and energy transfer in molecular materials.

Authors:
 [1];  [2];  [2];  [2];  [2]; ORCiD logo [3];  [4];  [2];  [4]; ORCiD logo [1]
  1. Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
  2. National Univ. of Quilmes, Bernal (Argentina)
  3. National Univ. of Colombia, Bogotá (Colombia). Dept. of Chemistry
  4. Univ. of Florida, Gainesville, FL (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Los Alamos National Laboratory (LANL), Los Alamos, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE National Nuclear Security Administration (NNSA); LANL Laboratory Directed Research and Development (LDRD) Program; National Scientific and Technical Research Council (CONICET) (Argentina); National Univ. of Quilmes (UNQ) (Argentina); National Agency of Scientific and Technological Promotion (ANPCyT) (Argentina)
OSTI Identifier:
1457307
Report Number(s):
LA-UR-17-30143
Journal ID: ISSN 2041-1723
Grant/Contract Number:  
AC52-06NA25396; PICT- 2014–2662
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Inorganic and Physical Chemistry

Citation Formats

Nelson, Tammie R., Ondarse-Alvarez, Dianelys, Oldani, Nicolas, Rodriguez-Hernandez, Beatriz, Alfonso-Hernandez, Laura, Galindo, Johan F., Kleiman, Valeria D., Fernandez-Alberti, Sebastian, Roitberg, Adrian E., and Tretiak, Sergei. Coherent exciton-vibrational dynamics and energy transfer in conjugated organics. United States: N. p., 2018. Web. doi:10.1038/s41467-018-04694-8.
Nelson, Tammie R., Ondarse-Alvarez, Dianelys, Oldani, Nicolas, Rodriguez-Hernandez, Beatriz, Alfonso-Hernandez, Laura, Galindo, Johan F., Kleiman, Valeria D., Fernandez-Alberti, Sebastian, Roitberg, Adrian E., & Tretiak, Sergei. Coherent exciton-vibrational dynamics and energy transfer in conjugated organics. United States. https://doi.org/10.1038/s41467-018-04694-8
Nelson, Tammie R., Ondarse-Alvarez, Dianelys, Oldani, Nicolas, Rodriguez-Hernandez, Beatriz, Alfonso-Hernandez, Laura, Galindo, Johan F., Kleiman, Valeria D., Fernandez-Alberti, Sebastian, Roitberg, Adrian E., and Tretiak, Sergei. 2018. "Coherent exciton-vibrational dynamics and energy transfer in conjugated organics". United States. https://doi.org/10.1038/s41467-018-04694-8. https://www.osti.gov/servlets/purl/1457307.
@article{osti_1457307,
title = {Coherent exciton-vibrational dynamics and energy transfer in conjugated organics},
author = {Nelson, Tammie R. and Ondarse-Alvarez, Dianelys and Oldani, Nicolas and Rodriguez-Hernandez, Beatriz and Alfonso-Hernandez, Laura and Galindo, Johan F. and Kleiman, Valeria D. and Fernandez-Alberti, Sebastian and Roitberg, Adrian E. and Tretiak, Sergei},
abstractNote = {Coherence, signifying concurrent electron-vibrational dynamics in complex natural and man-made systems, is currently a subject of intense study. Understanding this phenomenon is important when designing carrier transport in optoelectronic materials. Here, excited state dynamics simulations reveal a ubiquitous pattern in the evolution of photoexcitations for a broad range of molecular systems. Symmetries of the wavefunctions define a specific form of the non-adiabatic coupling that drives quantum transitions between excited states, leading to a collective asymmetric vibrational excitation coupled to the electronic system. This promotes periodic oscillatory evolution of the wavefunctions, preserving specific phase and amplitude relations across the ensemble of trajectories. The simple model proposed here explains the appearance of coherent exciton-vibrational dynamics due to non-adiabatic transitions, which is universal across multiple molecular systems. The observed relationships between electronic wavefunctions and the resulting functionalities allows us to understand, and potentially manipulate, excited state dynamics and energy transfer in molecular materials.},
doi = {10.1038/s41467-018-04694-8},
url = {https://www.osti.gov/biblio/1457307}, journal = {Nature Communications},
issn = {2041-1723},
number = ,
volume = 9,
place = {United States},
year = {Wed Jun 13 00:00:00 EDT 2018},
month = {Wed Jun 13 00:00:00 EDT 2018}
}

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Cited by: 57 works
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Nonadiabatic excited-state molecular dynamics: Numerical tests of convergence and parameters
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Photonics meets excitonics: natural and artificial molecular aggregates
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Nonadiabatic molecular dynamics
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A b initio quantum direct dynamics simulations of ultrafast photochemistry with Multiconfigurational Ehrenfest approach
journal, August 2017


Role of interface in stability of perovskite solar cells
journal, February 2017


Light-Driven and Phonon-Assisted Dynamics in Organic and Semiconductor Nanostructures
journal, May 2015


Light Absorption and Energy Transfer in the Antenna Complexes of Photosynthetic Organisms
journal, March 2016


Internal Conversion and Vibrational Energy Redistribution in Chlorophyll A
journal, December 2015


Recent Progress in Surface Hopping: 2011–2015
journal, May 2016


Electronic Delocalization, Vibrational Dynamics, and Energy Transfer in Organic Chromophores
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Photosensitization by reversible electron transfer: theories, experimental evidence, and examples
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Density Matrix Analysis and Simulation of Electronic Excitations in Conjugated and Aggregated Molecules
journal, September 2002


Multiconfiguration Self-Consistent Field and Multireference Configuration Interaction Methods and Applications
journal, December 2011


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


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


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


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


Photoexcited Energy Transfer in a Weakly Coupled Dimer
journal, December 2014


Use of Modern Electron Transfer Theories To Determine Electronic Coupling Matrix Elements in Intramolecular Systems
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Evidence for wavelike energy transfer through quantum coherence in photosynthetic systems
journal, April 2007


Using coherence to enhance function in chemical and biophysical systems
journal, March 2017


Lessons from nature about solar light harvesting
journal, September 2011


Identifying electron transfer coordinates in donor-bridge-acceptor systems using mode projection analysis
journal, February 2017


Optical determination of crystal phase in semiconductor nanocrystals
journal, May 2017


Photovoltaic concepts inspired by coherence effects in photosynthetic systems
journal, December 2016


Femtosecond torsional relaxation
journal, February 2012


Real-time observation of nonlinear coherent phonon dynamics in single-walled carbon nanotubes
journal, July 2006


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


Evidence for a vibrational phase-dependent isotope effect on the photochemistry of vision
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Resonant nonlinear polarizabilities in the time-dependent density functional theory
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Environment-assisted quantum walks in photosynthetic energy transfer
journal, November 2008


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


Accuracy of perturbation theory for nonadiabatic effects in adsorbate-surface dynamics
journal, May 2010


Recursive density‐matrix‐spectral‐moment algorithm for molecular nonlinear polarizabilities
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Identification of unavoided crossings in nonadiabatic photoexcited dynamics involving multiple electronic states in polyatomic conjugated molecules
journal, July 2012


Nonadiabatic dynamics in open quantum-classical systems: Forward-backward trajectory solution
journal, December 2012


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


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


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


Surface hopping outperforms secular Redfield theory when reorganization energies range from small to moderate (and nuclei are classical)
journal, March 2015


Electronic resonance with anticorrelated pigment vibrations drives photosynthetic energy transfer outside the adiabatic framework
journal, December 2012


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


Coherence Dynamics in Photosynthesis: Protein Protection of Excitonic Coherence
journal, June 2007


Coherent Intrachain Energy Migration in a Conjugated Polymer at Room Temperature
journal, January 2009


L ONG -R ANGE R ESONANCE E NERGY T RANSFER IN M OLECULAR S YSTEMS
journal, October 2003


Photonics meets excitonics: natural and artificial molecular aggregates
journal, January 2013


Origin of Long Lived Coherences in Light-Harvesting Complexes
text, January 2012


Works referencing / citing this record:

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A cruciform phthalocyanine pentad-based NIR-II photothermal agent for highly efficient tumor ablation
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Non-adiabatic molecular dynamics of molecules in the presence of strong light-matter interactions
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Benchmark ab initio calculations on intermolecular structures and the exciton character of poly( p -phenylenevinylene) dimers
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Signatures of Strong Vibronic Coupling Mediating Coherent Charge Transfer in Two-Dimensional Electronic Spectroscopy
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Vibronic coherence contributes to photocurrent generation in organic semiconductor heterojunction diodes
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