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Title: Induced polarization restricts the conformational distribution of a light-harvesting molecular triad in the ground state

Abstract

The light-harvesting molecular triad consisting of carotenoid polyene (C), diaryl-porphyrin (P) and pyrrole-fullerene (C60) is a donor–acceptor molecule capable of absorbing incident light in the visible range. Its ability to convert solar energy to electrical excitation and charge separation energy suggests a great potential in real-world applications. The ensemble of its conformations under ambient conditions varies widely according to its electronic state. In previous work, we applied a non-polarizable model to study the conformational distribution of the molecular triad in the ground and charge separated states. However, due to the lack of polarization, which imparts subtle changes in the charge distribution on atoms, molecular simulations fail to produce accurate average dipole moments. We developed the first polarizable model for a molecular triad to investigate the structural and dynamic properties of a molecular triad in the ground state in an explicit organic solvent, tetrahydrofuran (THF). We performed first-principles electronic structure calculations of the individual components in the triad as well as THF and then fit the partial atomic charges to the electrostatic potential using the i-RESP methodology. We validated these force field parameters by comparing the thermodynamic and dynamic properties obtained from molecular dynamics simulations with those from experiments. We enhancedmore » the sampling of the triad conformations with replica exchange molecular dynamics simulations. We characterized the effects of induced polarization on the structural stability of the triad by analyzing the free energy landscapes constructed with polarizable force fields. Furthermore, by using principal component analysis, we found that the molecular triad conformations adopted a small range of torsional angles with induced polarization. The triad conformation solvated in polar solvent with a polarizable force field qualitatively agrees with that obtained from nuclear magnetic resonance spectroscopy.« less

Authors:
 [1];  [1];  [2]; ORCiD logo [3]
  1. Department of Physics; University of Houston; Houston; USA
  2. Sanford Burnham Prebys Medical Discovery Institute; La Jolla; USA
  3. Department of Physics; University of Houston; Houston; USA; Center for Theoretical Biological Physics
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1492414
DOE Contract Number:  
SC0016501; FG02-10ER16175; SC0004832; AC02-05CH11231
Resource Type:
Journal Article
Journal Name:
Physical Chemistry Chemical Physics
Additional Journal Information:
Journal Volume: 19; Journal Issue: 34; Journal ID: ISSN 1463-9076
Country of Publication:
United States
Language:
English

Citation Formats

Starovoytov, Oleg N., Zhang, Pengzhi, Cieplak, Piotr, and Cheung, Margaret S. Induced polarization restricts the conformational distribution of a light-harvesting molecular triad in the ground state. United States: N. p., 2017. Web. doi:10.1039/c7cp03177g.
Starovoytov, Oleg N., Zhang, Pengzhi, Cieplak, Piotr, & Cheung, Margaret S. Induced polarization restricts the conformational distribution of a light-harvesting molecular triad in the ground state. United States. doi:10.1039/c7cp03177g.
Starovoytov, Oleg N., Zhang, Pengzhi, Cieplak, Piotr, and Cheung, Margaret S. Sun . "Induced polarization restricts the conformational distribution of a light-harvesting molecular triad in the ground state". United States. doi:10.1039/c7cp03177g.
@article{osti_1492414,
title = {Induced polarization restricts the conformational distribution of a light-harvesting molecular triad in the ground state},
author = {Starovoytov, Oleg N. and Zhang, Pengzhi and Cieplak, Piotr and Cheung, Margaret S.},
abstractNote = {The light-harvesting molecular triad consisting of carotenoid polyene (C), diaryl-porphyrin (P) and pyrrole-fullerene (C60) is a donor–acceptor molecule capable of absorbing incident light in the visible range. Its ability to convert solar energy to electrical excitation and charge separation energy suggests a great potential in real-world applications. The ensemble of its conformations under ambient conditions varies widely according to its electronic state. In previous work, we applied a non-polarizable model to study the conformational distribution of the molecular triad in the ground and charge separated states. However, due to the lack of polarization, which imparts subtle changes in the charge distribution on atoms, molecular simulations fail to produce accurate average dipole moments. We developed the first polarizable model for a molecular triad to investigate the structural and dynamic properties of a molecular triad in the ground state in an explicit organic solvent, tetrahydrofuran (THF). We performed first-principles electronic structure calculations of the individual components in the triad as well as THF and then fit the partial atomic charges to the electrostatic potential using the i-RESP methodology. We validated these force field parameters by comparing the thermodynamic and dynamic properties obtained from molecular dynamics simulations with those from experiments. We enhanced the sampling of the triad conformations with replica exchange molecular dynamics simulations. We characterized the effects of induced polarization on the structural stability of the triad by analyzing the free energy landscapes constructed with polarizable force fields. Furthermore, by using principal component analysis, we found that the molecular triad conformations adopted a small range of torsional angles with induced polarization. The triad conformation solvated in polar solvent with a polarizable force field qualitatively agrees with that obtained from nuclear magnetic resonance spectroscopy.},
doi = {10.1039/c7cp03177g},
journal = {Physical Chemistry Chemical Physics},
issn = {1463-9076},
number = 34,
volume = 19,
place = {United States},
year = {2017},
month = {1}
}

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