Quantifying local exciton, charge resonance, and multiexciton character in correlated wave functions of multichromophoric systems

Casanova, David; Krylov, Anna I.

doi:10.1063/1.4939222

Title: Quantifying local exciton, charge resonance, and multiexciton character in correlated wave functions of multichromophoric systems

Journal Article · Tue Jan 05 00:00:00 EST 2016 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4939222· OSTI ID:1468795

^[1]; Krylov, Anna I. ^[2]

Universidad del País Vasco (UPV) Euskal Herriko Unibertsitatea (EHU), Donostia (Spain). Donostia International Physics Center; Basque Foundation for Science, Bilbao (Spain)
Univ. of Southern California, Los Angeles, CA (United States). Dept. of Chemistry

A new method for quantifying the contributions of local excitation, charge resonance, and multiexciton configurations in correlated wave functions of multichromophoric systems is presented. The approach relies on fragment-localized orbitals and employs spin correlators. Its utility is illustrated by calculations on model clusters of hydrogen, ethylene, and tetracene molecules using adiabatic restricted-active-space configuration interaction wave functions. In addition to the wave function analysis, this approach provides a basis for a simple state-specific energy correction accounting for insufficient description of electron correlation. The decomposition scheme also allows one to compute energies of the diabatic states of the local excitonic, charge-resonance, and multi-excitonic character. The new method provides insight into electronic structure of multichromophoric systems and delivers valuable reference data for validating excitonic models.

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Research Organization:: Univ. of Southern California, Los Angeles, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR); USDOE Office of Science (SC), Basic Energy Sciences (BES); Basque Government

Grant/Contract Number:: FG02-05ER15685

OSTI ID:: 1468795

Alternate ID(s):: OSTI ID: 1234175

Journal Information:: Journal of Chemical Physics, Vol. 144, Issue 1; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 28 works

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References (58)

Spin-flip configuration interaction: an electronic structure model that is both variational and size-consistent Krylov, Anna I. Chemical Physics Letters, Vol. 350, Issue 5-6 https://doi.org/10.1016/S0009-2614(01)01316-1	journal	December 2001
The Structure and Dynamics of Molecular Excitons Bardeen, Christopher J. Annual Review of Physical Chemistry, Vol. 65, Issue 1 https://doi.org/10.1146/annurev-physchem-040513-103654	journal	April 2014
Quantifying charge resonance and multiexciton character in coupled chromophores by charge and spin cumulant analysis Luzanov, Anatoliy V.; Casanova, David; Feng, Xintian The Journal of Chemical Physics, Vol. 142, Issue 22 https://doi.org/10.1063/1.4921635	journal	June 2015
Spin-Flip Equation-of-Motion Coupled-Cluster Electronic Structure Method for a Description of Excited States, Bond Breaking, Diradicals, and Triradicals Krylov, Anna I. Accounts of Chemical Research, Vol. 39, Issue 2 https://doi.org/10.1021/ar0402006	journal	February 2006
Recent Advances in Singlet Fission Smith, Millicent B.; Michl, Josef Annual Review of Physical Chemistry, Vol. 64, Issue 1 https://doi.org/10.1146/annurev-physchem-040412-110130	journal	April 2013
Dissecting the Effect of Morphology on the Rates of Singlet Fission: Insights from Theory Feng, Xintian; Kolomeisky, Anatoly B.; Krylov, Anna I. The Journal of Physical Chemistry C, Vol. 118, Issue 34 https://doi.org/10.1021/jp505942k	journal	August 2014
Theoretical analysis of spectra of short polyenes Orlandi, Giorgio.; Zerbetto, Francesco.; Zgierski, Marek Z. Chemical Reviews, Vol. 91, Issue 5 https://doi.org/10.1021/cr00005a012	journal	July 1991
A Simple Kinetic Model for Singlet Fission: A Role of Electronic and Entropic Contributions to Macroscopic Rates Kolomeisky, Anatoly B.; Feng, Xintian; Krylov, Anna I. The Journal of Physical Chemistry C, Vol. 118, Issue 10 https://doi.org/10.1021/jp4128176	journal	February 2014
Theoretical study of the ???* excited states of linear polyenes: The energy gap between 11Bu+ and 21Ag? states and their character Nakayama, Kenichi; Nakano, Haruyuki; Hirao, Kimihiko International Journal of Quantum Chemistry, Vol. 66, Issue 2 https://doi.org/10.1002/(SICI)1097-461X(1998)66:2<157::AID-QUA7>3.0.CO;2-U	journal	January 1998
New tools for the systematic analysis and visualization of electronic excitations. I. Formalism Plasser, Felix; Wormit, Michael; Dreuw, Andreas The Journal of Chemical Physics, Vol. 141, Issue 2 https://doi.org/10.1063/1.4885819	journal	July 2014
A spin-complete version of the spin-flip approach to bond breaking: What is the impact of obtaining spin eigenfunctions? Sears, John S.; Sherrill, C. David; Krylov, Anna I. The Journal of Chemical Physics, Vol. 118, Issue 20 https://doi.org/10.1063/1.1568735	journal	May 2003
Coexistence of Exciton Fission and Fusion in Tetracene Crystals Groff, R. P.; Avakian, P.; Merrifield, R. E. Physical Review B, Vol. 1, Issue 2 https://doi.org/10.1103/PhysRevB.1.815	journal	January 1970
Effect of Magnetic Field on the Fluorescence of Tetracene Crystals: Exciton Fission Geacintov, N.; Pope, M.; Vogel, F. Physical Review Letters, Vol. 22, Issue 12 https://doi.org/10.1103/PhysRevLett.22.593	journal	March 1969
Low-energy electron-impact spectroscopy on ethylene Van Veen, E. H. Chemical Physics Letters, Vol. 41, Issue 3 https://doi.org/10.1016/0009-2614(76)85412-7	journal	August 1976
Geometries and Vertical Excitation Energies in Retinal Analogues Resolved at the CASPT2 Level of Theory: Critical Assessment of the Performance of CASSCF, CC2, and DFT Methods Walczak, Elżbieta; Szefczyk, Borys; Andruniów, Tadeusz Journal of Chemical Theory and Computation, Vol. 9, Issue 11 https://doi.org/10.1021/ct400423u	journal	October 2013
How Proteins Trigger Excitation Energy Transfer in the FMO Complex of Green Sulfur Bacteria Adolphs, Julia; Renger, Thomas Biophysical Journal, Vol. 91, Issue 8 https://doi.org/10.1529/biophysj.105.079483	journal	October 2006
Evidence for wavelike energy transfer through quantum coherence in photosynthetic systems Engel, Gregory S.; Calhoun, Tessa R.; Read, Elizabeth L. Nature, Vol. 446, Issue 7137 https://doi.org/10.1038/nature05678	journal	April 2007
Singlet → triplet transitions in methyl-substituted ethylenes Flicker, W. M.; Mosher, O. A.; Kuppermann, A. Chemical Physics Letters, Vol. 36, Issue 1 https://doi.org/10.1016/0009-2614(75)85685-5	journal	October 1975
A new mixing of Hartree–Fock and local density‐functional theories Becke, Axel D. The Journal of Chemical Physics, Vol. 98, Issue 2 https://doi.org/10.1063/1.464304	journal	January 1993
Coherence in Energy Transfer and Photosynthesis Chenu, Aurélia; Scholes, Gregory D. Annual Review of Physical Chemistry, Vol. 66, Issue 1 https://doi.org/10.1146/annurev-physchem-040214-121713	journal	April 2015
A Correlated Electron View of Singlet Fission Zimmerman, Paul M.; Musgrave, Charles B.; Head-Gordon, Martin Accounts of Chemical Research, Vol. 46, Issue 6 https://doi.org/10.1021/ar3001734	journal	February 2013
Restricted active space spin-flip (RAS-SF) with arbitrary number of spin-flips Bell, Franziska; Zimmerman, Paul M.; Casanova, David Phys. Chem. Chem. Phys., Vol. 15, Issue 1 https://doi.org/10.1039/C2CP43293E	journal	January 2013
Ab Initio Nonadiabatic Dynamics of Multichromophore Complexes: A Scalable Graphical-Processing-Unit-Accelerated Exciton Framework Sisto, Aaron; Glowacki, David R.; Martinez, Todd J. Accounts of Chemical Research, Vol. 47, Issue 9 https://doi.org/10.1021/ar500229p	journal	July 2014
Bright Fission: Singlet Fission into a Pair of Emitting States Casanova, David Journal of Chemical Theory and Computation, Vol. 11, Issue 6 https://doi.org/10.1021/acs.jctc.5b00144	journal	May 2015
Advances in molecular quantum chemistry contained in the Q-Chem 4 program package Shao, Yihan; Gan, Zhengting; Epifanovsky, Evgeny Molecular Physics, Vol. 113, Issue 2 https://doi.org/10.1080/00268976.2014.952696	journal	September 2014
Local spin Clark, Aurora E.; Davidson, Ernest R. The Journal of Chemical Physics, Vol. 115, Issue 16 https://doi.org/10.1063/1.1407276	journal	October 2001
On the Electronically Excited States of Uracil Epifanovsky, Evgeny; Kowalski, Karol; Fan, Peng-Dong The Journal of Physical Chemistry A, Vol. 112, Issue 40 https://doi.org/10.1021/jp803758q	journal	October 2008
A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP) Yanai, Takeshi; Tew, David P.; Handy, Nicholas C. Chemical Physics Letters, Vol. 393, Issue 1-3, p. 51-57 https://doi.org/10.1016/j.cplett.2004.06.011	journal	July 2004
Harvesting Singlet Fission for Solar Energy Conversion: One- versus Two-Electron Transfer from the Quantum Mechanical Superposition Chan, Wai-Lun; Tritsch, John R.; Zhu, X. -Y. Journal of the American Chemical Society, Vol. 134, Issue 44 https://doi.org/10.1021/ja306271y	journal	October 2012
Mechanism for Singlet Fission in Pentacene and Tetracene: From Single Exciton to Two Triplets Zimmerman, Paul M.; Bell, Franziska; Casanova, David Journal of the American Chemical Society, Vol. 133, Issue 49 https://doi.org/10.1021/ja208431r	journal	December 2011
Efficiency Enhancement of Organic and Thin-Film Silicon Solar Cells with Photochemical Upconversion Schulze, Tim F.; Czolk, Jens; Cheng, Yuen-Yap The Journal of Physical Chemistry C, Vol. 116, Issue 43 https://doi.org/10.1021/jp309636m	journal	October 2012
Singlet Fission Smith, Millicent B.; Michl, Josef Chemical Reviews, Vol. 110, Issue 11 https://doi.org/10.1021/cr1002613	journal	November 2010
A Structural Model for a Self-Assembled Nanotube Provides Insight into Its Exciton Dynamics Gao, Min; Paul, Subhradip; Schwieters, Charles D. The Journal of Physical Chemistry C, Vol. 119, Issue 24 https://doi.org/10.1021/acs.jpcc.5b03398	journal	June 2015
Conical Intersection and Potential Energy Surface Features of a Model Retinal Chromophore: Comparison of EOM-CC and Multireference Methods Gozem, Samer; Krylov, Anna I.; Olivucci, Massimo Journal of Chemical Theory and Computation, Vol. 9, Issue 1 https://doi.org/10.1021/ct300759z	journal	November 2012
The Dynamics of Singlet Fission in Crystalline Tetracene and Covalent Analogs Burdett, Jonathan J.; Bardeen, Christopher J. Accounts of Chemical Research, Vol. 46, Issue 6 https://doi.org/10.1021/ar300191w	journal	January 2013
Fission of Entangled Spins: An Electronic Structure Perspective Feng, Xintian; Luzanov, Anatoliy V.; Krylov, Anna I. The Journal of Physical Chemistry Letters, Vol. 4, Issue 22 https://doi.org/10.1021/jz402122m	journal	November 2013
Q-Chem: an engine for innovation: Q-Chem: an engine for innovation Krylov, Anna I.; Gill, Peter M. W. Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 3, Issue 3 https://doi.org/10.1002/wcms.1122	journal	November 2012
What We Can Learn from the Norms of One-Particle Density Matrices, and What We Can’t: Some Results for Interstate Properties in Model Singlet Fission Systems Matsika, Spiridoula; Feng, Xintian; Luzanov, Anatoliy V. The Journal of Physical Chemistry A, Vol. 118, Issue 51 https://doi.org/10.1021/jp506090g	journal	August 2014
Ab Initio Implementation of the Frenkel–Davydov Exciton Model: A Naturally Parallelizable Approach to Computing Collective Excitations in Crystals and Aggregates Morrison, Adrian F.; You, Zhi-Qiang; Herbert, John M. Journal of Chemical Theory and Computation, Vol. 10, Issue 12 https://doi.org/10.1021/ct500765m	journal	November 2014
Constrained Density Functional Theory and Its Application in Long-Range Electron Transfer Wu, Qin; Van Voorhis, Troy Journal of Chemical Theory and Computation, Vol. 2, Issue 3 https://doi.org/10.1021/ct0503163	journal	May 2006
Light-Harvesting Antennas in Photosynthesis Green, Beverley R.; Parson, William W. Advances in Photosynthesis and Respiration https://doi.org/10.1007/978-94-017-2087-8	book	January 2003
The electronic structure of some polyenes and aromatic molecules III—Bonds of fractional order by the pair method Penney, William George Proceedings of the Royal Society of London. Series A - Mathematical and Physical Sciences, Vol. 158, Issue 894, p. 306-324 https://doi.org/10.1098/rspa.1937.0022	journal	January 1937
High Yield Ultrafast Intramolecular Singlet Exciton Fission in a Quinoidal Bithiophene Varnavski, Oleg; Abeyasinghe, Neranga; Aragó, Juan The Journal of Physical Chemistry Letters, Vol. 6, Issue 8 https://doi.org/10.1021/acs.jpclett.5b00198	journal	April 2015
Exciton delocalization, charge transfer, and electronic coupling for singlet excitation energy transfer between stacked nucleobases in DNA: An MS-CASPT2 study Blancafort, Lluís; Voityuk, Alexander A. The Journal of Chemical Physics, Vol. 140, Issue 9 https://doi.org/10.1063/1.4867118	journal	March 2014
A Quasidegenerate Second-Order Perturbation Theory Approximation to RAS- n SF for Excited States and Strong Correlations Mayhall, Nicholas J.; Goldey, Matthew; Head-Gordon, Martin Journal of Chemical Theory and Computation, Vol. 10, Issue 2 https://doi.org/10.1021/ct400898p	journal	January 2014
Dynamics of Light Harvesting in Photosynthesis Cheng, Yuan-Chung; Fleming, Graham R. Annual Review of Physical Chemistry, Vol. 60, Issue 1 https://doi.org/10.1146/annurev.physchem.040808.090259	journal	May 2009
Ab Initio Frozen Density Functional Calculations of Proton Transfer Reactions in Solution Wesolowski, Tomasz; Muller, Richard P.; Warshel, Arieh The Journal of Physical Chemistry, Vol. 100, Issue 38 https://doi.org/10.1021/jp961068x	journal	January 1996
Implementation of renormalized excitonic method at ab initio level Zhang, Hongjiang; Malrieu, Jean-Paul; Ma, Haibo Journal of Computational Chemistry, Vol. 33, Issue 1 https://doi.org/10.1002/jcc.21941	journal	September 2011
A theoretical study of the diffuseness of theV(1B1u) state of planar ethylene Lindh, Roland; Roos, Bj�rn O. International Journal of Quantum Chemistry, Vol. 35, Issue 6 https://doi.org/10.1002/qua.560350617	journal	June 1989
The Role of Chromophore Coupling in Singlet Fission Johnson, Justin C.; Nozik, Arthur J.; Michl, Josef Accounts of Chemical Research, Vol. 46, Issue 6 https://doi.org/10.1021/ar300193r	journal	January 2013
Double spin-flip approach within equation-of-motion coupled cluster and configuration interaction formalisms: Theory, implementation, and examples Casanova, David; Slipchenko, Lyudmila V.; Krylov, Anna I. The Journal of Chemical Physics, Vol. 130, Issue 4 https://doi.org/10.1063/1.3066652	journal	January 2009
C ONJUGATED P OLYMERS AS M OLECULAR M ATERIALS : How Chain Conformation and Film Morphology Influence Energy Transfer and Interchain Interactions Schwartz, Benjamin J. Annual Review of Physical Chemistry, Vol. 54, Issue 1 https://doi.org/10.1146/annurev.physchem.54.011002.103811	journal	October 2003
Restricted active space spin-flip configuration interaction approach: theory, implementation and examples Casanova, David; Head-Gordon, Martin Physical Chemistry Chemical Physics, Vol. 11, Issue 42 https://doi.org/10.1039/b911513g	journal	January 2009
Communication: Active-space decomposition for molecular dimers Parker, Shane M.; Seideman, Tamar; Ratner, Mark A. The Journal of Chemical Physics, Vol. 139, Issue 2 https://doi.org/10.1063/1.4813827	journal	July 2013
Quasi-diabatic States from Active Space Decomposition Parker, Shane M.; Shiozaki, Toru Journal of Chemical Theory and Computation, Vol. 10, Issue 9 https://doi.org/10.1021/ct5004753	journal	July 2014
Computational quantum chemistry for single Heisenberg spin couplings made simple: Just one spin flip required Mayhall, Nicholas J.; Head-Gordon, Martin The Journal of Chemical Physics, Vol. 141, Issue 13 https://doi.org/10.1063/1.4896659	journal	October 2014
Electronic Structure Study of Singlet Fission in Tetracene Derivatives Casanova, David Journal of Chemical Theory and Computation, Vol. 10, Issue 1 https://doi.org/10.1021/ct4007635	journal	November 2013
Configuration interaction based on constrained density functional theory: A multireference method Wu, Qin; Cheng, Chiao-Lun; Van Voorhis, Troy The Journal of Chemical Physics, Vol. 127, Issue 16 https://doi.org/10.1063/1.2800022	journal	October 2007

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