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

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]
+ Show Author Affiliations
  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.
Copy to clipboard
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.
Copy to clipboard
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.
Copy to clipboard
@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}
}
Copy to clipboard
Journal Article:
DOI:  10.1039/c7cp03177g
Other availability
Find in Google Scholar Find in Google Scholar
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Development of a Polarizable Force Field for Molecular Dynamics Simulations of Poly (Ethylene Oxide) in Aqueous Solution
journal, April 2011

  • Starovoytov, Oleg N.; Borodin, Oleg; Bedrov, Dmitry
  • Journal of Chemical Theory and Computation, Vol. 7, Issue 6
  • DOI: 10.1021/ct200064u

Molecular Dynamics and Principal Components Analysis of Human Telomeric Quadruplex Multimers
journal, July 2008

Studies on Molecules with Five-membered Rings. II. An Electron Diffraction Investigation of Gaseous Tetrahydrofuran.
journal, January 1969

Development of AMOEBA Force Field for 1,3-Dimethylimidazolium Based Ionic Liquids
journal, June 2014

  • Starovoytov, Oleg N.; Torabifard, Hedieh; Cisneros, G. Andrés
  • The Journal of Physical Chemistry B, Vol. 118, Issue 25
  • DOI: 10.1021/jp503347f

Application of the multimolecule and multiconformational RESP methodology to biopolymers: Charge derivation for DNA, RNA, and proteins
journal, November 1995

  • Cieplak, Piotr; Cornell, Wendy D.; Bayly, Christopher
  • Journal of Computational Chemistry, Vol. 16, Issue 11
  • DOI: 10.1002/jcc.540161106

Molecular dynamics simulation studies of the influence of imidazolium structure on the properties of imidazolium/azide ionic liquids
journal, May 2012

  • Hooper, Justin B.; Starovoytov, Oleg N.; Borodin, Oleg
  • The Journal of Chemical Physics, Vol. 136, Issue 19
  • DOI: 10.1063/1.4718800

Molecular mimicry of photosynthetic energy and electron transfer
journal, April 1993

  • Gust, Devens; Moore, Thomas A.; Moore, Ana L.
  • Accounts of Chemical Research, Vol. 26, Issue 4
  • DOI: 10.1021/ar00028a010

The Vacuum Ultraviolet Absorption Spectra of Cyclic Compounds. II. Tetrahydrofuran, Tetrahydropyran, 1,4-Dioxane and Furan 1
journal, October 1951

  • Pickett, Lucy W.; Hoeflich, Nancy J.; Liu, Tien-Chuan
  • Journal of the American Chemical Society, Vol. 73, Issue 10
  • DOI: 10.1021/ja01154a117

Charge separation in carotenoporphyrin-quinone triads: synthetic, conformational, and fluorescence lifetime studies
journal, February 1987

  • Gust, Devens; Moore, Thomas A.; Liddell, Paul A.
  • Journal of the American Chemical Society, Vol. 109, Issue 3
  • DOI: 10.1021/ja00237a035

Electron diffraction study of gaseous tetrahydrofuran
journal, January 1969

Solubility of C 60 and PCBM in Organic Solvents
journal, November 2015

Convergence and sampling efficiency in replica exchange simulations of peptide folding in explicit solvent
journal, January 2007

  • Periole, Xavier; Mark, Alan E.
  • The Journal of Chemical Physics, Vol. 126, Issue 1
  • DOI: 10.1063/1.2404954

Structural consequences of porphyrin tautomerization. Molecular structure of a zinc isoporphyrin
journal, August 1993

  • Barkigia, K. M.; Renner, M. W.; Xie, H.
  • Journal of the American Chemical Society, Vol. 115, Issue 17
  • DOI: 10.1021/ja00070a052

Photoexcitation of a Light-Harvesting Supramolecular Triad: A Time-Dependent DFT Study
journal, April 2009

  • Spallanzani, N.; Rozzi, C. A.; Varsano, D.
  • The Journal of Physical Chemistry B, Vol. 113, Issue 16
  • DOI: 10.1021/jp900820q

Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989

  • Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 90, Issue 2
  • DOI: 10.1063/1.456153

Low-energy electron collisions with tetrahydrofuran
journal, January 2006

  • Bouchiha, D.; Gorfinkiel, J. D.; Caron, L. G.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 39, Issue 4
  • DOI: 10.1088/0953-4075/39/4/021

The Rotational Oscillations of Tetrahydrofuran in Tetrahydrofuran Clathrate Hydrate
journal, December 1973

  • Klug, D. D.; Whalley, E.
  • Canadian Journal of Chemistry, Vol. 51, Issue 24
  • DOI: 10.1139/v73-605

Intramolecular Polarization Induces Electron–Hole Charge Separation in Light-Harvesting Molecular Triads
journal, December 2013

  • Rego, Luis G. C.; Hames, Bruno C.; Mazon, Kahio T.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 1
  • DOI: 10.1021/jp408955e

Density functional study on a light-harvesting carotenoid-porphyrin-C60 molecular triad
journal, October 2006

  • Baruah, Tunna; Pederson, Mark R.
  • The Journal of Chemical Physics, Vol. 125, Issue 16
  • DOI: 10.1063/1.2360265

Development and testing of a general amber force field
journal, January 2004

  • Wang, Junmei; Wolf, Romain M.; Caldwell, James W.
  • Journal of Computational Chemistry, Vol. 25, Issue 9
  • DOI: 10.1002/jcc.20035

Protein dynamics derived from clusters of crystal structures
journal, December 1997

All-Photonic Multifunctional Molecular Logic Device
journal, August 2011

  • Andréasson, Joakim; Pischel, Uwe; Straight, Stephen D.
  • Journal of the American Chemical Society, Vol. 133, Issue 30
  • DOI: 10.1021/ja203456h

A Second Generation Force Field for the Simulation of Proteins, Nucleic Acids, and Organic Molecules
journal, May 1995

  • Cornell, Wendy D.; Cieplak, Piotr; Bayly, Christopher I.
  • Journal of the American Chemical Society, Vol. 117, Issue 19
  • DOI: 10.1021/ja00124a002

Twist Conformation of Tetrahydrofuran in the Crystal
journal, May 1983

  • Luger, Peter; Buschmann, J�rgen
  • Angewandte Chemie International Edition in English, Vol. 22, Issue 5
  • DOI: 10.1002/anie.198304101

Photoinduced Electron Transfer in Carotenoporphyrin−Fullerene Triads:  Temperature and Solvent Effects
journal, May 2000

  • Kuciauskas, Darius; Liddell, Paul A.; Lin, Su
  • The Journal of Physical Chemistry B, Vol. 104, Issue 18
  • DOI: 10.1021/jp9935135

Fast, efficient generation of high-quality atomic charges. AM1-BCC model: II. Parameterization and validation
journal, October 2002

  • Jakalian, Araz; Jack, David B.; Bayly, Christopher I.
  • Journal of Computational Chemistry, Vol. 23, Issue 16
  • DOI: 10.1002/jcc.10128

A well-behaved electrostatic potential based method using charge restraints for deriving atomic charges: the RESP model
journal, October 1993

  • Bayly, Christopher I.; Cieplak, Piotr; Cornell, Wendy
  • The Journal of Physical Chemistry, Vol. 97, Issue 40
  • DOI: 10.1021/j100142a004

Molecular dynamics simulation of rigid molecules
journal, September 1986

Molecular All-Photonic Encoder−Decoder
journal, August 2008

  • Andréasson, Joakim; Straight, Stephen D.; Moore, Thomas A.
  • Journal of the American Chemical Society, Vol. 130, Issue 33
  • DOI: 10.1021/ja802845z

Solar Fuels via Artificial Photosynthesis
journal, December 2009

  • Gust, Devens; Moore, Thomas A.; Moore, Ana L.
  • Accounts of Chemical Research, Vol. 42, Issue 12
  • DOI: 10.1021/ar900209b

Magnetic Switching of Charge Separation Lifetimes in Artificial Photosynthetic Reaction Centers
journal, October 1998

  • Kuciauskas, Darius; Liddell, Paul A.; Moore, Ana L.
  • Journal of the American Chemical Society, Vol. 120, Issue 42
  • DOI: 10.1021/ja981848e

Ring Puckering in Five‐Membered Rings. II. The Microwave Spectrum, Dipole Moment, and Barrier to Pseudorotation in Tetrahydrofuran
journal, March 1969

  • Engerholm, Gail G.; Luntz, Alan C.; Gwinn, W. D.
  • The Journal of Chemical Physics, Vol. 50, Issue 6
  • DOI: 10.1063/1.1671401

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

Multiscale Simulation of the Ground and Photo-Induced Charge-Separated States of a Molecular Triad in Polar Organic Solvent: Exploring the Conformations, Fluctuations, and Free Energy Landscapes
journal, October 2013

  • Balamurugan, D.; Aquino, Adelia J. A.; de Dios, Francis
  • The Journal of Physical Chemistry B, Vol. 117, Issue 40
  • DOI: 10.1021/jp4026927

Robustness in the fitting of molecular mechanics parameters
journal, March 2015

  • Vanommeslaeghe, Kenno; Yang, Mingjun; MacKerell, Alexander D.
  • Journal of Computational Chemistry, Vol. 36, Issue 14
  • DOI: 10.1002/jcc.23897

The influence of polarization functions on molecular orbital hydrogenation energies
journal, January 1973

  • Hariharan, P. C.; Pople, J. A.
  • Theoretica Chimica Acta, Vol. 28, Issue 3
  • DOI: 10.1007/BF00533485

Polarizabilities of Solvents from the Chemical Composition
journal, September 2002

  • Bosque, Ramón; Sales, Joaquim
  • Journal of Chemical Information and Computer Sciences, Vol. 42, Issue 5
  • DOI: 10.1021/ci025528x

Development of an AMOEBA water model using GEM distributed multipoles
journal, August 2015

  • Torabifard, Hedieh; Starovoytov, Oleg N.; Ren, Pengyu
  • Theoretical Chemistry Accounts, Vol. 134, Issue 8
  • DOI: 10.1007/s00214-015-1702-y

All-Photonic Molecular Half-Adder
journal, December 2006

  • Andréasson, Joakim; Straight, Stephen D.; Kodis, Gerdenis
  • Journal of the American Chemical Society, Vol. 128, Issue 50
  • DOI: 10.1021/ja0654579

Quantum coherence controls the charge separation in a prototypical artificial light-harvesting system
journal, March 2013

  • Andrea Rozzi, Carlo; Maria Falke, Sarah; Spallanzani, Nicola
  • Nature Communications, Vol. 4, Issue 1
  • DOI: 10.1038/ncomms2603

General definition of ring puckering coordinates
journal, March 1975

  • Cremer, D.; Pople, J. A.
  • Journal of the American Chemical Society, Vol. 97, Issue 6
  • DOI: 10.1021/ja00839a011

GEM*: A Molecular Electronic Density-Based Force Field for Molecular Dynamics Simulations
journal, March 2014

  • Duke, Robert E.; Starovoytov, Oleg N.; Piquemal, Jean-Philip
  • Journal of Chemical Theory and Computation, Vol. 10, Issue 4
  • DOI: 10.1021/ct500050p

Atomic charges derived from semiempirical methods
journal, May 1990

  • Besler, Brent H.; Merz, Kenneth M.; Kollman, Peter A.
  • Journal of Computational Chemistry, Vol. 11, Issue 4
  • DOI: 10.1002/jcc.540110404

Characterization of the Giant Transient Dipole Generated by Photoinduced Electron Transfer in a Carotene−Porphyrin−Fullerene Molecular Triad
journal, September 2003

  • Smirnov, Sergei N.; Liddell, Paul A.; Vlassiouk, Ivan V.
  • The Journal of Physical Chemistry A, Vol. 107, Issue 38
  • DOI: 10.1021/jp034532o

Excess molar volumes of binary mixtures containing dimethyl carbonate + linear and cyclic ethers
journal, January 1994

  • Francesconi, Romolo; Comelli, Fabio
  • Journal of Chemical & Engineering Data, Vol. 39, Issue 1
  • DOI: 10.1021/je00013a028

Multiscale Simulation on a Light-Harvesting Molecular Triad
journal, February 2012

  • Su, Guoxiong; Czader, Arkadiusz; Homouz, Dirar
  • The Journal of Physical Chemistry B, Vol. 116, Issue 29
  • DOI: 10.1021/jp212273n

Cooperativity and hydrogen bonding network in water clusters
journal, August 2000

Atom dipole interaction model for molecular polarizability. Application to polyatomic molecules and determination of atom polarizabilities
journal, May 1972

  • Applequist, Jon; Carl, James R.; Fung, Kwok-Kueng
  • Journal of the American Chemical Society, Vol. 94, Issue 9
  • DOI: 10.1021/ja00764a010

Electric Moments of Polar Polymers in Relation to Their Structure
journal, May 1951

  • Debye, P.; Bueche, F.
  • The Journal of Chemical Physics, Vol. 19, Issue 5
  • DOI: 10.1063/1.1748297

The excess volumes of (tributylamine + an ether) at the temperature 298.15 K
journal, November 1994

  • Letcher, T. M.; Domańska, U.
  • The Journal of Chemical Thermodynamics, Vol. 26, Issue 11
  • DOI: 10.1006/jcht.1994.1141

Molecular orbital theory of the electronic structure of organic compounds. XXIII. Pseudorotation in saturated five-membered ring compounds
journal, March 1975

  • Cremer, D.; Pople, J. A.
  • Journal of the American Chemical Society, Vol. 97, Issue 6
  • DOI: 10.1021/ja00839a012

Automated conformational energy fitting for force-field development
journal, May 2008

The Structure of Liquid Tetrahydrofuran
journal, April 2006

  • Bowron, Daniel T.; Finney, John L.; Soper, Alan K.
  • Journal of the American Chemical Society, Vol. 128, Issue 15
  • DOI: 10.1021/ja0583057

Conformational analysis of tetrahydrofuran and tetrahydrothiopene using 1H NMR spectroscopy and ab initio calculations
journal, May 2008

  • Chertkov, A. V.; Pokrovskiy, O. I.; Shestakova, A. K.
  • Chemistry of Heterocyclic Compounds, Vol. 44, Issue 5
  • DOI: 10.1007/s10593-008-0083-8

Unraveling the Mechanism of Photoinduced Charge Transfer in Carotenoid–Porphyrin–C 60 Molecular Triad
journal, March 2015

  • Manna, Arun K.; Balamurugan, D.; Cheung, Margaret S.
  • The Journal of Physical Chemistry Letters, Vol. 6, Issue 7
  • DOI: 10.1021/acs.jpclett.5b00074

An All-Photonic Molecular Keypad Lock
journal, April 2009

  • Andréasson, Joakim; Straight, Stephen D.; Moore, Thomas A.
  • Chemistry - A European Journal, Vol. 15, Issue 16
  • DOI: 10.1002/chem.200900043

Exchange frequency in replica exchange molecular dynamics
journal, January 2008

  • Sindhikara, Daniel; Meng, Yilin; Roitberg, Adrian E.
  • The Journal of Chemical Physics, Vol. 128, Issue 2
  • DOI: 10.1063/1.2816560

Synthesis and photochemistry of a carotene–porphyrin–fullerene model photosynthetic reaction center
journal, August 2004

  • Kodis, Gerdenis; Liddell, Paul A.; Moore, Ana L.
  • Journal of Physical Organic Chemistry, Vol. 17, Issue 9
  • DOI: 10.1002/poc.787

The effect of structural changes on charge transfer states in a light-harvesting carotenoid-diaryl-porphyrin-C 60 molecular triad
journal, May 2014

  • Olguin, Marco; Basurto, Luis; Zope, Rajendra R.
  • The Journal of Chemical Physics, Vol. 140, Issue 20
  • DOI: 10.1063/1.4876075

DFT Calculations on Charge-Transfer States of a Carotenoid-Porphyrin-C 60 Molecular Triad
journal, March 2009

  • Baruah, Tunna; Pederson, Mark R.
  • Journal of Chemical Theory and Computation, Vol. 5, Issue 4
  • DOI: 10.1021/ct900024f

Polarizable Force Field Development and Molecular Dynamics Simulations of Ionic Liquids
journal, August 2009

  • Borodin, Oleg
  • The Journal of Physical Chemistry B, Vol. 113, Issue 33
  • DOI: 10.1021/jp905220k

Extension of the Karplus Relationship for NMR Spin-Spin Coupling Constants to Nonplanar Ring Systems: Pseudorotation of Tetrahydrofuran
journal, April 2003

  • Wu, Anan; Cremer, Dieter
  • International Journal of Molecular Sciences, Vol. 4, Issue 4
  • DOI: 10.3390/i4040158

Molecular dynamics simulation of a polymer chain in solution
journal, November 1993

  • Dünweg, Burkhard; Kremer, Kurt
  • The Journal of Chemical Physics, Vol. 99, Issue 9
  • DOI: 10.1063/1.465445

Mimicking Photosynthetic Solar Energy Transduction
journal, January 2001

  • Gust, Devens; Moore, Thomas A.; Moore, Ana L.
  • Accounts of Chemical Research, Vol. 34, Issue 1
  • DOI: 10.1021/ar9801301

A Second Generation Force Field for the Simulation of Proteins, Nucleic Acids, and Organic Molecules J . Am . Chem . Soc . 1995 , 117 , 5179−5197
journal, January 1996

  • Cornell, Wendy D.; Cieplak, Piotr; Bayly, Christopher I.
  • Journal of the American Chemical Society, Vol. 118, Issue 9
  • DOI: 10.1021/ja955032e

Photoinduced Charge Separation and Charge Recombination to a Triplet State in a Carotene−Porphyrin−Fullerene Triad
journal, February 1997

  • Liddell, Paul A.; Kuciauskas, Darius; Sumida, John P.
  • Journal of the American Chemical Society, Vol. 119, Issue 6
  • DOI: 10.1021/ja9631054
    [ × clear filter / sort ]

    Similar records in OSTI.GOV collections: