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

Title: Molecular Excited States: Accurate Calculation of Relative Energies and Electronic Coupling Between Charge Transfer and Non-Charge Transfer States

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
DOI:https://doi.org/10.1021/jp508337x· OSTI ID:1386318
 [1];  [2];  [1];  [2];  [1]
  1. Northwestern Univ., Evanston, IL (United States)
  2. Univ. of Pennsylvania, Philadelphia, PA (United States)
+ Show Author Affiliations

We show for a series of six small donor–acceptor dyads that the energy difference between non-charge transfer (non-CT) and charge transfer (CT) excited states, as well as the squares of the electronic couplings between these states, can be predicted from first-principles using variational orbital adapted configuration interaction singles (VOA-CIS) theory. VOA-CIS correctly predicts the observed experimental trends in these values and provides quantitative accuracy roughly on par with a modern long-range corrected density functional, ωB97X. Using VOA-CIS and ωB97X, the experimental energy difference between the non-CT and CT excited states is predicted with root mean squared errors of 0.22 eV and 0.21 eV, respectively. The square of the electronic coupling between these states is predicted with root mean squared errors of 0.08 eV2 and 0.07 eV2, respectively. Here, orbital optimized CIS (OO-CIS) and CIS(D), two perturbative corrections to CIS, provide a significant correction to the errant relative energies predicted by CIS, but the correction is insufficient to recover the experimentally observed trend.

Research Organization:
Energy Frontier Research Centers (EFRC) (United States). Argonne-Northwestern Solar Energy Research Center (ANSER)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Grant/Contract Number:
SC0001059; AC05-06OR23100; FG02-99ER14999; 2011509
OSTI ID:
1386318
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 119, Issue 2; Related Information: ANSER partners with Northwestern University (lead); Argonne National Laboratory; University of Chicago; University of Illinois, Urbana-Champaign; Yale University; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 8 works
Citation information provided by
Web of Science

References (40)

Molecular Understanding of Organic Solar Cells: The Challenges journal November 2009
Energy Conversion in Photosynthesis: A Paradigm for Solar Fuel Production journal March 2011
Chemical Approaches to Artificial Photosynthesis. 2 journal October 2005
Solar Fuels via Artificial Photosynthesis journal December 2009
Energy, Charge, and Spin Transport in Molecules and Self-Assembled Nanostructures Inspired by Photosynthesis journal July 2006
Modeling geminate pair dissociation in organic solar cells: high power conversion efficiencies achieved with moderate optical bandgaps journal January 2012
Molecular Mechanisms of Photosynthesis book December 2002
Charge Carrier Formation in Polythiophene/Fullerene Blend Films Studied by Transient Absorption Spectroscopy journal March 2008
On the Theory of Oxidation‐Reduction Reactions Involving Electron Transfer. I journal May 1956
Temperature dependent activation energy for electron transfer between biological molecules journal June 1976
Predicting Accurate Electronic Excitation Transfer Rates via Marcus Theory with Boys or Edmiston−Ruedenberg Localized Diabatization † journal August 2010
Communication: Configuration interaction singles has a large systematic bias against charge-transfer states journal August 2011
Ab Initio Characterization of Electron Transfer Coupling in Photoinduced Systems:  Generalized Mulliken−Hush with Configuration-Interaction Singles journal December 2005
Communication: Adjusting charge transfer state energies for configuration interaction singles: Without any parameterization and with minimal cost journal April 2012
Communication: An inexpensive, variational, almost black-box, almost size-consistent correction to configuration interaction singles for valence excited states journal June 2013
The Variationally Orbital-Adapted Configuration Interaction Singles (VOA-CIS) Approach to Electronically Excited States journal February 2014
A doubles correction to electronic excited states from configuration interaction in the space of single substitutions journal March 1994
The second-order approximate coupled cluster singles and doubles model CC2 journal September 1995
Unrestricted algebraic diagrammatic construction scheme of second order for the calculation of excited states of medium-sized and large molecules journal January 2009
Equation-of-Motion Coupled-Cluster Methods for Open-Shell and Electronically Excited Species: The Hitchhiker's Guide to Fock Space journal May 2008
Inclusion of second-order correlation effects for the ground and singly-excited states suitable for the study of conical intersections: The CIS(2) model journal November 2007
Long-range charge-transfer excited states in time-dependent density functional theory require non-local exchange journal August 2003
Failure of Time-Dependent Density Functional Theory for Long-Range Charge-Transfer Excited States:  The Zincbacteriochlorin−Bacteriochlorin and Bacteriochlorophyll−Spheroidene Complexes journal March 2004
A long-range-corrected density functional that performs well for both ground-state properties and time-dependent density functional theory excitation energies, including charge-transfer excited states journal February 2009
Simultaneous benchmarking of ground- and excited-state properties with long-range-corrected density functional theory journal July 2008
A long-range-corrected time-dependent density functional theory journal May 2004
A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP) journal July 2004
Systematic optimization of long-range corrected hybrid density functionals journal February 2008
The Electronic Couplings in Electron Transfer and Excitation Energy Transfer journal April 2009
Generalization of the Mulliken-Hush treatment for the calculation of electron transfer matrix elements journal January 1996
Calculation of electronic coupling matrix elements for ground and excited state electron transfer reactions: Comparison of the generalized Mulliken–Hush and block diagonalization methods journal June 1997
Constructing diabatic states from adiabatic states: Extending generalized Mulliken–Hush to multiple charge centers with Boys localization journal December 2008
The initial and final states of electron and energy transfer processes: Diabatization as motivated by system-solvent interactions journal June 2009
Fragment charge difference method for estimating donor–acceptor electronic coupling: Application to DNA π-stacks journal September 2002
Direct optimization method to study constrained systems within density-functional theory journal August 2005
Constrained Density Functional Theory and Its Application in Long-Range Electron Transfer journal May 2006
Direct Calculation of Electron Transfer Parameters through Constrained Density Functional Theory journal July 2006
Extracting electron transfer coupling elements from constrained density functional theory journal October 2006
Intramolecular charge-transfer absorption and emission resulting from through-bond interaction in bichromophoric molecules journal September 1982
Multistate Treatments of the Electronic Coupling in Donor–Bridge–Acceptor Systems: Insights and Caveats from a Simple Model journal December 2013

Cited By (2)

Communication: A mean field platform for excited state quantum chemistry journal August 2018
Quantum chemical calculations of tryptophan → heme electron and excitation energy transfer rates in myoglobin journal April 2017

Similar Records

Predicting Excitation Energies of Twisted Intramolecular Charge-Transfer States with the Time-Dependent Density Functional Theory: Comparison with Experimental Measurements in the Gas Phase and Solvents Ranging from Hexanes to Acetonitrile
Journal Article · Thu Aug 20 00:00:00 EDT 2020 · Journal of Chemical Theory and Computation · OSTI ID:1386318
Highly Accurate Prediction of Core Spectra of Molecules at Density Functional Theory Cost: Attaining Sub-electronvolt Error from a Restricted Open-Shell Kohn–Sham Approach
Journal Article · Thu Jan 09 00:00:00 EST 2020 · Journal of Physical Chemistry Letters · OSTI ID:1386318
A DFT analysis of the ground and charge-transfer excited states of Sc3N@Ih–C80 fullerene coupled with metal-free and zinc-phthalocyanine
Journal Article · Fri Sep 14 00:00:00 EDT 2018 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:1386318
+2 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
catalysis (homogeneous)
catalysis (heterogeneous)
solar (photovoltaic)
solar (fuels)
photosynthesis (natural and artificial)
bio-inspired
hydrogen and fuel cells
electrodes - solar
defects
charge transport
spin dynamics
membrane
materials and chemistry by design
optics
synthesis (novel materials)
synthesis (self-assembly)
electrical energy
energy
phase transitions
molecular oscillation