Description of ground and excited electronic states by ensemble density functional method with extended active space

Filatov, Michael; Martínez, Todd J.; Kim, Kwang S.

doi:10.1063/1.4996873

Title: Description of ground and excited electronic states by ensemble density functional method with extended active space

Abstract

An extended variant of the spin-restricted ensemble-referenced Kohn-Sham (REKS) method, the REKS(4,4) method, designed to describe the ground electronic states of strongly multireference systems is modified to enable calculation of excited states within the time-independent variational formalism. The new method, the state-interaction state-averaged REKS(4,4), i.e., SI-SA-REKS(4,4), is capable of describing several excited states of a molecule involving double bond cleavage, polyradical character, or multiple chromophoric units.We demonstrate that the newmethod correctly describes the ground and the lowest singlet excited states of a molecule (ethylene) undergoing double bond cleavage. The applicability of the new method for excitonic states is illustrated with π stacked ethylene and tetracene dimers. We conclude that the new method can describe a wide range of multireference phenomena.

Authors:

Filatov, Michael ^[1];

^[2];

^[1]

Ulsan National Inst. of Science and Technology (Korea, Republic of)
Stanford Univ., CA (United States)

Publication Date:: Mon Aug 14 00:00:00 EDT 2017

Research Org.:: SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)

Sponsoring Org.:: USDOE

OSTI Identifier:: 1390629

Alternate Identifier(s):: OSTI ID: 1374479

Grant/Contract Number:: AC02-76SF00515

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Chemical Physics

Additional Journal Information:: Journal Volume: 147; Journal Issue: 6; Journal ID: ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)

Country of Publication:: United States

Language:: English

Subject:: 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats


                    Filatov, Michael, Martínez, Todd J., and Kim, Kwang S. Description of ground and excited electronic states by ensemble density functional method with extended active space.  United States: N. p., 2017. 
Web.  doi:10.1063/1.4996873.

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                    Filatov, Michael, Martínez, Todd J., & Kim, Kwang S. Description of ground and excited electronic states by ensemble density functional method with extended active space.  United States.  https://doi.org/10.1063/1.4996873

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                    Filatov, Michael, Martínez, Todd J., and Kim, Kwang S. Mon .  
"Description of ground and excited electronic states by ensemble density functional method with extended active space".  United States.  https://doi.org/10.1063/1.4996873.  https://www.osti.gov/servlets/purl/1390629.

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@article{osti_1390629,

  title        = {Description of ground and excited electronic states by ensemble density functional method with extended active space},

  author       = {Filatov, Michael and Martínez, Todd J. and Kim, Kwang S.},

  abstractNote = {An extended variant of the spin-restricted ensemble-referenced Kohn-Sham (REKS) method, the REKS(4,4) method, designed to describe the ground electronic states of strongly multireference systems is modified to enable calculation of excited states within the time-independent variational formalism. The new method, the state-interaction state-averaged REKS(4,4), i.e., SI-SA-REKS(4,4), is capable of describing several excited states of a molecule involving double bond cleavage, polyradical character, or multiple chromophoric units.We demonstrate that the newmethod correctly describes the ground and the lowest singlet excited states of a molecule (ethylene) undergoing double bond cleavage. The applicability of the new method for excitonic states is illustrated with π stacked ethylene and tetracene dimers. We conclude that the new method can describe a wide range of multireference phenomena.},

  doi          = {10.1063/1.4996873},

  journal      = {Journal of Chemical Physics},

  number       = 6,

  volume       = 147,

  place        = {United States},

  year         = {Mon Aug 14 00:00:00 EDT 2017},

  month        = {Mon Aug 14 00:00:00 EDT 2017}

}

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Works referenced in this record:

A spin-restricted ensemble-referenced Kohn–Sham method and its application to diradicaloid situations
journal, May 1999

Filatov, Michael; Shaik, Sason
Chemical Physics Letters, Vol. 304, Issue 5-6
DOI: 10.1016/s0009-2614(99)00336-x

Graphical Processing Units for Quantum Chemistry
journal, November 2008

Ufimtsev, Ivan S.; Martínez, Todd J.
Computing in Science & Engineering, Vol. 10, Issue 6
DOI: 10.1109/mcse.2008.148

Generating Efficient Quantum Chemistry Codes for Novel Architectures
journal, November 2012

Titov, Alexey V.; Ufimtsev, Ivan S.; Luehr, Nathan
Journal of Chemical Theory and Computation, Vol. 9, Issue 1
DOI: 10.1021/ct300321a

Rayleigh-Ritz variational principle for ensembles of fractionally occupied states
journal, April 1988

Gross, E. K. U.; Oliveira, L. N.; Kohn, W.
Physical Review A, Vol. 37, Issue 8
DOI: 10.1103/physreva.37.2805

Quantifying charge resonance and multiexciton character in coupled chromophores by charge and spin cumulant analysis
journal, June 2015

Luzanov, Anatoliy V.; Casanova, David; Feng, Xintian
The Journal of Chemical Physics, Vol. 142, Issue 22
DOI: 10.1063/1.4921635

Density-functional theory for ensembles of fractionally occupied states. I. Basic formalism
journal, April 1988

Gross, E. K. U.; Oliveira, L. N.; Kohn, W.
Physical Review A, Vol. 37, Issue 8
DOI: 10.1103/physreva.37.2809

Automated Code Engine for Graphical Processing Units: Application to the Effective Core Potential Integrals and Gradients
journal, December 2015

Song, Chenchen; Wang, Lee-Ping; Martínez, Todd J.
Journal of Chemical Theory and Computation, Vol. 12, Issue 1
DOI: 10.1021/acs.jctc.5b00790

Quantum Chemistry on Graphical Processing Units. 1. Strategies for Two-Electron Integral Evaluation
journal, January 2008

Ufimtsev, Ivan S.; Martínez, Todd J.
Journal of Chemical Theory and Computation, Vol. 4, Issue 2
DOI: 10.1021/ct700268q

Electronic coupling in the excited electronic state of stacked DNA base homodimers
journal, January 2007

Ritze, Hans-Hermann; Hobza, Pavel; Nachtigallov?, Dana
Physical Chemistry Chemical Physics, Vol. 9, Issue 14
DOI: 10.1039/b618382d

The Theory of Complex Spectra
journal, April 1932

Shortley, George H.
Physical Review, Vol. 40, Issue 2
DOI: 10.1103/physrev.40.185

A perspective on the CASPT2 method
journal, April 2011

Pulay, Peter
International Journal of Quantum Chemistry, Vol. 111, Issue 13
DOI: 10.1002/qua.23052

Assessment of density functional theory based ΔSCF (self-consistent field) and linear response methods for longest wavelength excited states of extended π-conjugated molecular systems
journal, July 2014

Filatov, Michael; Huix-Rotllant, Miquel
The Journal of Chemical Physics, Vol. 141, Issue 2
DOI: 10.1063/1.4887087

A new mixing of Hartree–Fock and local density‐functional theories
journal, January 1993

Becke, Axel D.
The Journal of Chemical Physics, Vol. 98, Issue 2
DOI: 10.1063/1.464304

A combination of Kohn–Sham density functional theory and multi-reference configuration interaction methods
journal, October 1999

Grimme, Stefan; Waletzke, Mirko
The Journal of Chemical Physics, Vol. 111, Issue 13
DOI: 10.1063/1.479866

Excitation Energies from Spin-Restricted Ensemble-Referenced Kohn−Sham Method: A State-Average Approach ^†
journal, December 2008

Kazaryan, Andranik; Heuver, Jeroen; Filatov, Michael
The Journal of Physical Chemistry A, Vol. 112, Issue 50
DOI: 10.1021/jp8033837

A theoretical study of the structure of cyclobutadiene
journal, March 1977

Kollmar, H.; Staemmler, V.
Journal of the American Chemical Society, Vol. 99, Issue 11
DOI: 10.1021/ja00453a009

Classification of Spectra of Cata‐Condensed Hydrocarbons
journal, May 1949

Platt, John R.
The Journal of Chemical Physics, Vol. 17, Issue 5
DOI: 10.1063/1.1747293

Progress in Time-Dependent Density-Functional Theory
text, January 2011

Casida, M. E.; Huix-Rotllant, M.
arXiv
DOI: 10.48550/arxiv.1108.0611

The radical character of the acenes: A density matrix renormalization group study
journal, October 2007

Hachmann, Johannes; Dorando, Jonathan J.; Avilés, Michael
The Journal of Chemical Physics, Vol. 127, Issue 13
DOI: 10.1063/1.2768362

Synthesis, Stability, and Photochemistry of Pentacene, Hexacene, and Heptacene: A Matrix Isolation Study
journal, October 2009

Mondal, Rajib; Tönshoff, Christina; Khon, Dmitriy
Journal of the American Chemical Society, Vol. 131, Issue 40
DOI: 10.1021/ja901841c

Progress in Time-Dependent Density-Functional Theory
journal, May 2012

Casida, M. E.; Huix-Rotllant, M.
Annual Review of Physical Chemistry, Vol. 63, Issue 1
DOI: 10.1146/annurev-physchem-032511-143803

Singlet Fission
journal, November 2010

Smith, Millicent B.; Michl, Josef
Chemical Reviews, Vol. 110, Issue 11
DOI: 10.1021/cr1002613

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

Rohrdanz, Mary A.; Martins, Katie M.; Herbert, John M.
The Journal of Chemical Physics, Vol. 130, Issue 5
DOI: 10.1063/1.3073302

Ensemble density functional theory method correctly describes bond dissociation, excited state electron transfer, and double excitations
journal, May 2015

Filatov, Michael; Huix-Rotllant, Miquel; Burghardt, Irene
The Journal of Chemical Physics, Vol. 142, Issue 18
DOI: 10.1063/1.4919773

Spin-restricted ensemble-referenced Kohn-Sham method: basic principles and application to strongly correlated ground and excited states of molecules
journal, November 2014

Filatov, Michael
Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 5, Issue 1
DOI: 10.1002/wcms.1209

The potential surfaces for the lowest singlet and triplet states of cyclobutadiene
journal, January 1978

Borden, Weston Thatcher; Davidson, Ernest R.; Hart, Paul
Journal of the American Chemical Society, Vol. 100, Issue 2
DOI: 10.1021/ja00470a006

The radical character of the acenes: A density matrix renormalization group study
text, January 2007

Hachmann, Johannes; Dorando, Jonathan J.; Aviles, Michael
arXiv
DOI: 10.48550/arxiv.0707.3120

Improved Quantum Theory of Many‐Electron Systems. V. The Spin‐Coupling Optimized GI Method
journal, August 1969

Ladner, Robert C.; Goddard, William A.
The Journal of Chemical Physics, Vol. 51, Issue 3
DOI: 10.1063/1.1672106

Recovering dynamic correlation in spin flip configuration interaction through a difference dedicated approach
journal, January 2017

Chien, Alan D.; Zimmerman, Paul M.
The Journal of Chemical Physics, Vol. 146, Issue 1
DOI: 10.1063/1.4973245

Ensemble-Density functional theory for excited states
journal, March 1990

Oliveira, L. N.; Gross, E. K. U.; Kohn, W.
International Journal of Quantum Chemistry, Vol. 38, Issue S24
DOI: 10.1002/qua.560382470

Evidence for Singlet Fission Driven by Vibronic Coherence in Crystalline Tetracene
journal, March 2017

Morrison, Adrian F.; Herbert, John M.
The Journal of Physical Chemistry Letters, Vol. 8, Issue 7
DOI: 10.1021/acs.jpclett.7b00230

One - determinantal pure state versus ensemble Kohn-Sham solutions in the case of strong electron correlation: CH 2 and C 2
journal, September 1998

Schipper, P. R. T.; Gritsenko, O. V.; Baerends, E. J.
Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 99, Issue 5
DOI: 10.1007/s002140050343

Correlation‐consistent configuration interaction: Accurate bond dissociation energies from simple wave functions
journal, March 1988

Carter, Emily A.; Goddard, William A.
The Journal of Chemical Physics, Vol. 88, Issue 5
DOI: 10.1063/1.453957

On the exact formulation of multi-configuration density-functional theory: electron density versus orbitals occupation
text, January 2014

Fromager, Emmanuel
arXiv
DOI: 10.48550/arxiv.1409.2326

Is GVB-CI superior to CASSCF?
journal, July 1999

Cullen, John
Journal of Computational Chemistry, Vol. 20, Issue 10
DOI: 10.1002/(sici)1096-987x(19990730)20:10<999::aid-jcc2>3.0.co;2-a

On the exact formulation of multi-configuration density-functional theory: electron density versus orbitals occupation
journal, August 2014

Fromager, Emmanuel
Molecular Physics, Vol. 113, Issue 5
DOI: 10.1080/00268976.2014.993342

The Theory of Complex Spectra
journal, November 1929

Slater, J. C.
Physical Review, Vol. 34, Issue 10
DOI: 10.1103/physrev.34.1293

First-Principles Quantum Dynamics of Singlet Fission: Coherent versus Thermally Activated Mechanisms Governed by Molecular $π$ Stacking
journal, August 2015

Tamura, Hiroyuki; Huix-Rotllant, Miquel; Burghardt, Irene
Physical Review Letters, Vol. 115, Issue 10
DOI: 10.1103/physrevlett.115.107401

Photogeneration of Octacene and Nonacene
journal, April 2010

Tönshoff, Christina; Bettinger, Holger F.
Angewandte Chemie International Edition, Vol. 49, Issue 24
DOI: 10.1002/anie.200906355

Using the GVB Ansatz to develop ensemble DFT method for describing multiple strongly correlated electron pairs
journal, January 2016

Filatov, Michael; Martínez, Todd J.; Kim, Kwang S.
Phys. Chem. Chem. Phys., Vol. 18, Issue 31
DOI: 10.1039/c6cp00236f

The surface energy of a bounded electron gas
journal, August 1974

Harris, J.; Jones, R. O.
Journal of Physics F: Metal Physics, Vol. 4, Issue 8
DOI: 10.1088/0305-4608/4/8/013

The Theory of Complex Spectra
journal, October 1930

Condon, E. U.
Physical Review, Vol. 36, Issue 7
DOI: 10.1103/physrev.36.1121

Forces in Molecules
journal, August 1939

Feynman, R. P.
Physical Review, Vol. 56, Issue 4
DOI: 10.1103/physrev.56.340

Quintet multiexciton dynamics in singlet fission
journal, October 2016

Tayebjee, Murad J. Y.; Sanders, Samuel N.; Kumarasamy, Elango
Nature Physics, Vol. 13, Issue 2
DOI: 10.1038/nphys3909

Density functionals for coulomb systems
journal, September 1983

Lieb, Elliott H.
International Journal of Quantum Chemistry, Vol. 24, Issue 3
DOI: 10.1002/qua.560240302

Generalized valence bond description of bonding in low-lying states of molecules
journal, November 1973

Goddard, William A.; Dunning, Thom H.; Hunt, William J.
Accounts of Chemical Research, Vol. 6, Issue 11
DOI: 10.1021/ar50071a002

Generalised adiabatic connection in ensemble density-functional theory for excited states: example of the H ₂ molecule
journal, November 2013

Franck, Odile; Fromager, Emmanuel
Molecular Physics, Vol. 112, Issue 12
DOI: 10.1080/00268976.2013.858191

Excitation energies from time-dependent density-functional formalism for small systems
journal, March 2002

Aryasetiawan, F.; Gunnarsson, O.; Rubio, A.
Europhysics Letters (EPL), Vol. 57, Issue 5
DOI: 10.1209/epl/i2002-00517-6

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

Szalay, Péter G.; Müller, Thomas; Gidofalvi, Gergely
Chemical Reviews, Vol. 112, Issue 1
DOI: 10.1021/cr200137a

A one‐to‐one mapping between one‐particle densities and some n ‐particle ensembles
journal, November 1980

Valone, Steven M.
The Journal of Chemical Physics, Vol. 73, Issue 9
DOI: 10.1063/1.440656

Aufbau derived from a unified treatment of occupation numbers in Hartree–Fock, Kohn–Sham, and natural orbital theories with the Karush–Kuhn–Tucker conditions for the inequality constraints ni≤1 and ni≥0
journal, May 2010

Giesbertz, K. J. H.; Baerends, E. J.
The Journal of Chemical Physics, Vol. 132, Issue 19
DOI: 10.1063/1.3426319

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

Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988

Becke, A. D.
Physical Review A, Vol. 38, Issue 6
DOI: 10.1103/physreva.38.3098

Second‐order perturbation theory with a complete active space self‐consistent field reference function
journal, January 1992

Andersson, Kerstin; Malmqvist, Per‐Åke; Roos, Björn O.
The Journal of Chemical Physics, Vol. 96, Issue 2
DOI: 10.1063/1.462209

Hohenberg-Kohn theorem and non-V-representable densities
journal, August 1983

Englisch, H.; Englisch, R.
Physica A: Statistical Mechanics and its Applications, Vol. 121, Issue 1-2
DOI: 10.1016/0378-4371(83)90254-6

Self-consistent implementation of ensemble density functional theory method for multiple strongly correlated electron pairs
journal, December 2016

Filatov, Michael; Liu, Fang; Kim, Kwang S.
The Journal of Chemical Physics, Vol. 145, Issue 24
DOI: 10.1063/1.4972174

Benchmark calculations of chemical reactions in density functional theory: Comparison of the accurate Kohn–Sham solution with generalized gradient approximations for the H2+H and H2+H2 reactions
journal, September 1999

Schipper, P. R. T.; Gritsenko, O. V.; Baerends, E. J.
The Journal of Chemical Physics, Vol. 111, Issue 9
DOI: 10.1063/1.479707

Heptacene: Characterization in Solution, in the Solid State, and in Films
journal, March 2017

Einholz, Ralf; Fang, Treliant; Berger, Robert
Journal of the American Chemical Society, Vol. 139, Issue 12
DOI: 10.1021/jacs.6b13212

Quantum-Chemical Studies on Excitation Energy Transfer Processes in BODIPY-Based Donor–Acceptor Systems
journal, August 2015

Spiegel, J. Dominik; Kleinschmidt, Martin; Larbig, Alexander
Journal of Chemical Theory and Computation, Vol. 11, Issue 9
DOI: 10.1021/acs.jctc.5b00501

GVB-RP: A reliable MCSCF wave function for large systems
journal, January 1999

Faglioni, Francesco; Goddard, William A.
International Journal of Quantum Chemistry, Vol. 73, Issue 1
DOI: 10.1002/(sici)1097-461x(1999)73:1<1::aid-qua1>3.0.co;2-0

Correlation energy of an inhomogeneous electron gas: A coordinate‐space model
journal, January 1988

Becke, A. D.
The Journal of Chemical Physics, Vol. 88, Issue 2
DOI: 10.1063/1.454274

Density-functional theory for ensembles of fractionally occupied states. II. Application to the He atom
journal, April 1988

Oliveira, L. N.; Gross, E. K. U.; Kohn, W.
Physical Review A, Vol. 37, Issue 8
DOI: 10.1103/physreva.37.2821

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
text, January 1988

Robert, Parr,; Chengteh, Lee,; Weitao, Yang,
The University of North Carolina at Chapel Hill University Libraries
DOI: 10.17615/zrp0-ry04

Assessment of Density Functional Methods for Obtaining Geometries at Conical Intersections in Organic Molecules
journal, September 2013

Filatov, Michael
Journal of Chemical Theory and Computation, Vol. 9, Issue 10
DOI: 10.1021/ct400598b

Static density - density correlation function for interacting ground states with ensemble v -representable number densities
journal, January 1998

Farid, Behnam
Journal of Physics: Condensed Matter, Vol. 10, Issue 1
DOI: 10.1088/0953-8984/10/1/001

The Multiradical Character of One- and Two-Dimensional Graphene Nanoribbons
journal, January 2013

Plasser, Felix; Pašalić, Hasan; Gerzabek, Martin H.
Angewandte Chemie International Edition, Vol. 52, Issue 9
DOI: 10.1002/anie.201207671

Quantum Chemistry on Graphical Processing Units. 3. Analytical Energy Gradients, Geometry Optimization, and First Principles Molecular Dynamics
journal, August 2009

Ufimtsev, Ivan S.; Martinez, Todd J.
Journal of Chemical Theory and Computation, Vol. 5, Issue 10
DOI: 10.1021/ct9003004

Can a square or effectively square singlet be the ground state of cyclobutadiene
journal, October 1975

Borden, Weston T.
Journal of the American Chemical Society, Vol. 97, Issue 21
DOI: 10.1021/ja00854a002

Fission of Entangled Spins: An Electronic Structure Perspective
journal, November 2013

Feng, Xintian; Luzanov, Anatoliy V.; Krylov, Anna I.
The Journal of Physical Chemistry Letters, Vol. 4, Issue 22
DOI: 10.1021/jz402122m

Assessment of Density Functional Theory for Describing the Correlation Effects on the Ground and Excited State Potential Energy Surfaces of a Retinal Chromophore Model
journal, August 2013

Huix-Rotllant, Miquel; Filatov, Michael; Gozem, Samer
Journal of Chemical Theory and Computation, Vol. 9, Issue 9
DOI: 10.1021/ct4003465

Benchmarks of electronically excited states: Basis set effects on CASPT2 results
journal, November 2010

Silva-Junior, Mario R.; Schreiber, Marko; Sauer, Stephan P. A.
The Journal of Chemical Physics, Vol. 133, Issue 17
DOI: 10.1063/1.3499598

Exact Density Functionals for Ground-State Energies. I. General Results
journal, June 1984

Englisch, H.; Englisch, R.
physica status solidi (b), Vol. 123, Issue 2
DOI: 10.1002/pssb.2221230238

Restricted Ensemble-Referenced Kohn−Sham versus Broken Symmetry Approaches in Density Functional Theory: Magnetic Coupling in Cu Binuclear Complexes
journal, March 2007

Moreira, Ibério de P. R.; Costa, Ramon; Filatov, Michael
Journal of Chemical Theory and Computation, Vol. 3, Issue 3
DOI: 10.1021/ct7000057

Inhomogeneous Electron Gas
journal, March 1973

Rajagopal, A. K.; Callaway, J.
Physical Review B, Vol. 7, Issue 5
DOI: 10.1103/physrevb.7.1912

General SCF operator satisfying correct variational condition
journal, August 1973

Hirao, K.; Nakatsuji, H.
The Journal of Chemical Physics, Vol. 59, Issue 3
DOI: 10.1063/1.1680203

Exact Density Functionals for Ground-State Energies II. Details and Remarks
journal, July 1984

Englisch, H.; Englisch, R.
physica status solidi (b), Vol. 124, Issue 1
DOI: 10.1002/pssb.2221240140

Exact ensemble density functional theory for excited states in a model system: Investigating the weight dependence of the correlation energy
journal, January 2017

Deur, Killian; Mazouin, Laurent; Fromager, Emmanuel
Physical Review B, Vol. 95, Issue 3
DOI: 10.1103/physrevb.95.035120

Fluorescence of Naphthacene Vapor
journal, October 1963

Williams, R.; Goldsmith, G. J.
The Journal of Chemical Physics, Vol. 39, Issue 8
DOI: 10.1063/1.1734574

Nature of ground and electronic excited states of higher acenes
journal, August 2016

Yang, Yang; Davidson, Ernest R.; Yang, Weitao
Proceedings of the National Academy of Sciences, Vol. 113, Issue 35
DOI: 10.1073/pnas.1606021113

Quantum Chemistry on Graphical Processing Units. 2. Direct Self-Consistent-Field Implementation
journal, March 2009

Ufimtsev, Ivan S.; Martinez, Todd J.
Journal of Chemical Theory and Computation, Vol. 5, Issue 4
DOI: 10.1021/ct800526s

Double spin-flip approach within equation-of-motion coupled cluster and configuration interaction formalisms: Theory, implementation, and examples
journal, January 2009

Casanova, David; Slipchenko, Lyudmila V.; Krylov, Anna I.
The Journal of Chemical Physics, Vol. 130, Issue 4
DOI: 10.1063/1.3066652

Shape of Multireference, Equation-of-Motion Coupled-Cluster, and Density Functional Theory Potential Energy Surfaces at a Conical Intersection
journal, June 2014

Gozem, Samer; Melaccio, Federico; Valentini, Alessio
Journal of Chemical Theory and Computation, Vol. 10, Issue 8
DOI: 10.1021/ct500154k

Singlet Fission
journal, April 2021

Tykwinski, Rik R.; Guldi, Dirk M.
ChemPhotoChem, Vol. 5, Issue 5
DOI: 10.1002/cptc.202100053

Works referencing / citing this record:

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text, January 2018

Deur, Killian; Mazouin, Laurent; Senjean, Bruno
arXiv
DOI: 10.48550/arxiv.1803.00291

Ground and excited energy levels can be extracted exactly from a single ensemble density-functional theory calculation
journal, March 2019

Deur, Killian; Fromager, Emmanuel
The Journal of Chemical Physics, Vol. 150, Issue 9
DOI: 10.1063/1.5084312

Eliminating spin-contamination of spin-flip time dependent density functional theory within linear response formalism by the use of zeroth-order mixed-reference (MR) reduced density matrix
journal, September 2018

Lee, Seunghoon; Filatov, Michael; Lee, Sangyoub
The Journal of Chemical Physics, Vol. 149, Issue 10
DOI: 10.1063/1.5044202

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text, January 2018

Deur, Killian; Fromager, Emmanuel
arXiv
DOI: 10.48550/arxiv.1812.02461

Synergistic Approach of Ultrafast Spectroscopy and Molecular Simulations in the Characterization of Intramolecular Charge Transfer in Push-Pull Molecules
journal, January 2020

Patrizi, Barbara; Cozza, Concetta; Pietropaolo, Adriana
Molecules, Vol. 25, Issue 2
DOI: 10.3390/molecules25020430

Efficient implementations of analytic energy gradient for mixed-reference spin-flip time-dependent density functional theory (MRSF-TDDFT)
journal, May 2019

Lee, Seunghoon; Kim, Emma Eunji; Nakata, Hiroya
The Journal of Chemical Physics, Vol. 150, Issue 18
DOI: 10.1063/1.5086895

Exploring weight-dependent density-functional approximations for ensembles in the Hubbard dimer
journal, July 2018

Deur, Killian; Mazouin, Laurent; Senjean, Bruno
The European Physical Journal B, Vol. 91, Issue 7
DOI: 10.1140/epjb/e2018-90124-7

Synergistic Approach of Ultrafast Spectroscopy and Molecular Simulations in the Characterization of Intramolecular Charge Transfer in Push-Pull Molecules
journal, January 2020

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DOI: 10.3390/molecules25020430

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https://doi.org/10.1063/1.4919773
Analytical derivatives of the individual state energies in ensemble density functional theory method. I. General formalism

Journal Article Filatov, Michael ; Liu, Fang ; Martínez, Todd J. - Journal of Chemical Physics

The state-averaged (SA) spin restricted ensemble referenced Kohn-Sham (REKS) method and its state interaction (SI) extension, SI-SA-REKS, enable one to describe correctly the shape of the ground and excited potential energy surfaces of molecules undergoing bond breaking/bond formation reactions including features such as conical intersections crucial for theoretical modeling of non-adiabatic reactions. Until recently, application of the SA-REKS and SI-SA-REKS methods to modeling the dynamics of such reactions was obstructed due to the lack of the analytical energy derivatives. Here, the analytical derivatives of the individual SA-REKS and SI-SA-REKS energies are derived. The final analytic gradient expressions are formulated entirelymore »« less
Cited by 46
https://doi.org/10.1063/1.4994542

Full Text Available
Analytical derivatives of the individual state energies in ensemble density functional theory. II. Implementation on graphical processing units (GPUs)

Journal Article Liu, Fang ; Filatov, Michael ; Martínez, Todd J. - Journal of Chemical Physics

Conical intersections control excited state reactivity, and thus, elucidating and predicting their geometric and energetic characteristics are crucial for understanding photochemistry. Locating these intersections requires accurate and efficient electronic structure methods. Unfortunately, the most accurate methods (e.g., multireference perturbation theories such as XMS-CASPT2) are computationally challenging for large molecules. The state-interaction state-averaged restricted ensemble referenced Kohn–Sham (SI-SA-REKS) method is a computationally efficient alternative. The application of SI-SA-REKS to photochemistry was previously hampered by a lack of analytical nuclear gradients and nonadiabatic coupling matrix elements. We have recently derived analytical energy derivatives for the SI-SA-REKS method and implemented the method effectivelymore »« less
https://doi.org/10.1063/5.0041389

Full Text Available
Self-consistent implementation of ensemble density functional theory method for multiple strongly correlated electron pairs

Journal Article Filatov, Michael ; Liu, Fang ; Kim, Kwang S. ; ... - Journal of Chemical Physics

Here, the spin-restricted ensemble-referenced Kohn-Sham (REKS) method is based on an ensemble representation of the density and is capable of correctly describing the non-dynamic electron correlation stemming from (near-)degeneracy of several electronic configurations. The existing REKS methodology describes systems with two electrons in two fractionally occupied orbitals. In this work, the REKS methodology is extended to treat systems with four fractionally occupied orbitals accommodating four electrons and self-consistent implementation of the REKS(4,4) method with simultaneous optimization of the orbitals and their fractional occupation numbers is reported. The new method is applied to a number of molecular systems where simultaneous dissociationmore »« less
Cited by 18
https://doi.org/10.1063/1.4972174

Full Text Available
Description of electron transfer in the ground and excited states of organic donor–acceptor systems by single-reference and multi-reference density functional methods

Journal Article Filatov, Michael - Journal of Chemical Physics

Electron transfer in the ground and excited states of a model donor–acceptor (D–A) system is investigated using the single-reference and multi-reference density functional theory (DFT) methods. To analyze the results of the calculations, a simple two-site multi-reference model was derived that predicts a stepwise electron transfer in the S{sub 0} state and a wave-like dependence of the S{sub 1} electron transfer on the external stimulus. The standard single-reference Kohn-Sham (KS) DFT approach and the time-dependent DFT (TDDFT) method failed to describe the correct dependence of the S{sub 0} and S{sub 1} electron transfer on the external electric field applied alongmore »« less
https://doi.org/10.1063/1.4896455

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Title: Description of ground and excited electronic states by ensemble density functional method with extended active space

Abstract

Citation Formats

A spin-restricted ensemble-referenced Kohn–Sham method and its application to diradicaloid situations journal, May 1999

Graphical Processing Units for Quantum Chemistry journal, November 2008

Generating Efficient Quantum Chemistry Codes for Novel Architectures journal, November 2012

Rayleigh-Ritz variational principle for ensembles of fractionally occupied states journal, April 1988

Quantifying charge resonance and multiexciton character in coupled chromophores by charge and spin cumulant analysis journal, June 2015

Density-functional theory for ensembles of fractionally occupied states. I. Basic formalism journal, April 1988

Automated Code Engine for Graphical Processing Units: Application to the Effective Core Potential Integrals and Gradients journal, December 2015

Quantum Chemistry on Graphical Processing Units. 1. Strategies for Two-Electron Integral Evaluation journal, January 2008

Electronic coupling in the excited electronic state of stacked DNA base homodimers journal, January 2007

The Theory of Complex Spectra journal, April 1932

A perspective on the CASPT2 method journal, April 2011

Assessment of density functional theory based ΔSCF (self-consistent field) and linear response methods for longest wavelength excited states of extended π-conjugated molecular systems journal, July 2014

A new mixing of Hartree–Fock and local density‐functional theories journal, January 1993

A combination of Kohn–Sham density functional theory and multi-reference configuration interaction methods journal, October 1999

Excitation Energies from Spin-Restricted Ensemble-Referenced Kohn−Sham Method: A State-Average Approach † journal, December 2008

A theoretical study of the structure of cyclobutadiene journal, March 1977

Classification of Spectra of Cata‐Condensed Hydrocarbons journal, May 1949

Progress in Time-Dependent Density-Functional Theory text, January 2011

The radical character of the acenes: A density matrix renormalization group study journal, October 2007

Synthesis, Stability, and Photochemistry of Pentacene, Hexacene, and Heptacene: A Matrix Isolation Study journal, October 2009

Progress in Time-Dependent Density-Functional Theory journal, May 2012

Singlet Fission journal, November 2010

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

Ensemble density functional theory method correctly describes bond dissociation, excited state electron transfer, and double excitations journal, May 2015

Spin-restricted ensemble-referenced Kohn-Sham method: basic principles and application to strongly correlated ground and excited states of molecules journal, November 2014

The potential surfaces for the lowest singlet and triplet states of cyclobutadiene journal, January 1978

The radical character of the acenes: A density matrix renormalization group study text, January 2007

Improved Quantum Theory of Many‐Electron Systems. V. The Spin‐Coupling Optimized GI Method journal, August 1969

Recovering dynamic correlation in spin flip configuration interaction through a difference dedicated approach journal, January 2017

Ensemble-Density functional theory for excited states journal, March 1990

Evidence for Singlet Fission Driven by Vibronic Coherence in Crystalline Tetracene journal, March 2017

One - determinantal pure state versus ensemble Kohn-Sham solutions in the case of strong electron correlation: CH 2 and C 2 journal, September 1998

Correlation‐consistent configuration interaction: Accurate bond dissociation energies from simple wave functions journal, March 1988

On the exact formulation of multi-configuration density-functional theory: electron density versus orbitals occupation text, January 2014

Is GVB-CI superior to CASSCF? journal, July 1999

On the exact formulation of multi-configuration density-functional theory: electron density versus orbitals occupation journal, August 2014

The Theory of Complex Spectra journal, November 1929

First-Principles Quantum Dynamics of Singlet Fission: Coherent versus Thermally Activated Mechanisms Governed by Molecular π Stacking journal, August 2015

Photogeneration of Octacene and Nonacene journal, April 2010

Using the GVB Ansatz to develop ensemble DFT method for describing multiple strongly correlated electron pairs journal, January 2016

The surface energy of a bounded electron gas journal, August 1974

The Theory of Complex Spectra journal, October 1930

Forces in Molecules journal, August 1939

Quintet multiexciton dynamics in singlet fission journal, October 2016

Density functionals for coulomb systems journal, September 1983

Generalized valence bond description of bonding in low-lying states of molecules journal, November 1973

Generalised adiabatic connection in ensemble density-functional theory for excited states: example of the H 2 molecule journal, November 2013

Excitation energies from time-dependent density-functional formalism for small systems journal, March 2002

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

A one‐to‐one mapping between one‐particle densities and some n ‐particle ensembles journal, November 1980

Aufbau derived from a unified treatment of occupation numbers in Hartree–Fock, Kohn–Sham, and natural orbital theories with the Karush–Kuhn–Tucker conditions for the inequality constraints ni≤1 and ni≥0 journal, May 2010

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

Density-functional exchange-energy approximation with correct asymptotic behavior journal, September 1988

Second‐order perturbation theory with a complete active space self‐consistent field reference function journal, January 1992

Hohenberg-Kohn theorem and non-V-representable densities journal, August 1983

Self-consistent implementation of ensemble density functional theory method for multiple strongly correlated electron pairs journal, December 2016

Benchmark calculations of chemical reactions in density functional theory: Comparison of the accurate Kohn–Sham solution with generalized gradient approximations for the H2+H and H2+H2 reactions journal, September 1999

Heptacene: Characterization in Solution, in the Solid State, and in Films journal, March 2017

Quantum-Chemical Studies on Excitation Energy Transfer Processes in BODIPY-Based Donor–Acceptor Systems journal, August 2015

GVB-RP: A reliable MCSCF wave function for large systems journal, January 1999

Correlation energy of an inhomogeneous electron gas: A coordinate‐space model journal, January 1988

Density-functional theory for ensembles of fractionally occupied states. II. Application to the He atom journal, April 1988

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density text, January 1988

Assessment of Density Functional Methods for Obtaining Geometries at Conical Intersections in Organic Molecules journal, September 2013

Static density - density correlation function for interacting ground states with ensemble v -representable number densities journal, January 1998

The Multiradical Character of One- and Two-Dimensional Graphene Nanoribbons journal, January 2013

Quantum Chemistry on Graphical Processing Units. 3. Analytical Energy Gradients, Geometry Optimization, and First Principles Molecular Dynamics journal, August 2009

Can a square or effectively square singlet be the ground state of cyclobutadiene journal, October 1975

Fission of Entangled Spins: An Electronic Structure Perspective journal, November 2013

Assessment of Density Functional Theory for Describing the Correlation Effects on the Ground and Excited State Potential Energy Surfaces of a Retinal Chromophore Model journal, August 2013

Benchmarks of electronically excited states: Basis set effects on CASPT2 results journal, November 2010

Exact Density Functionals for Ground-State Energies. I. General Results journal, June 1984

Restricted Ensemble-Referenced Kohn−Sham versus Broken Symmetry Approaches in Density Functional Theory: Magnetic Coupling in Cu Binuclear Complexes journal, March 2007

Inhomogeneous Electron Gas journal, March 1973

General SCF operator satisfying correct variational condition journal, August 1973

Exact Density Functionals for Ground-State Energies II. Details and Remarks journal, July 1984

Exact ensemble density functional theory for excited states in a model system: Investigating the weight dependence of the correlation energy journal, January 2017

A spin-restricted ensemble-referenced Kohn–Sham method and its application to diradicaloid situations
journal, May 1999

Graphical Processing Units for Quantum Chemistry
journal, November 2008

Generating Efficient Quantum Chemistry Codes for Novel Architectures
journal, November 2012

Rayleigh-Ritz variational principle for ensembles of fractionally occupied states
journal, April 1988

Quantifying charge resonance and multiexciton character in coupled chromophores by charge and spin cumulant analysis
journal, June 2015

Density-functional theory for ensembles of fractionally occupied states. I. Basic formalism
journal, April 1988

Automated Code Engine for Graphical Processing Units: Application to the Effective Core Potential Integrals and Gradients
journal, December 2015

Quantum Chemistry on Graphical Processing Units. 1. Strategies for Two-Electron Integral Evaluation
journal, January 2008

Electronic coupling in the excited electronic state of stacked DNA base homodimers
journal, January 2007

The Theory of Complex Spectra
journal, April 1932

A perspective on the CASPT2 method
journal, April 2011

Assessment of density functional theory based ΔSCF (self-consistent field) and linear response methods for longest wavelength excited states of extended π-conjugated molecular systems
journal, July 2014

A new mixing of Hartree–Fock and local density‐functional theories
journal, January 1993

A combination of Kohn–Sham density functional theory and multi-reference configuration interaction methods
journal, October 1999

Excitation Energies from Spin-Restricted Ensemble-Referenced Kohn−Sham Method: A State-Average Approach ^†
journal, December 2008

A theoretical study of the structure of cyclobutadiene
journal, March 1977

Classification of Spectra of Cata‐Condensed Hydrocarbons
journal, May 1949

Progress in Time-Dependent Density-Functional Theory
text, January 2011

The radical character of the acenes: A density matrix renormalization group study
journal, October 2007

Synthesis, Stability, and Photochemistry of Pentacene, Hexacene, and Heptacene: A Matrix Isolation Study
journal, October 2009

Progress in Time-Dependent Density-Functional Theory
journal, May 2012

Singlet Fission
journal, November 2010

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

Ensemble density functional theory method correctly describes bond dissociation, excited state electron transfer, and double excitations
journal, May 2015

Spin-restricted ensemble-referenced Kohn-Sham method: basic principles and application to strongly correlated ground and excited states of molecules
journal, November 2014

The potential surfaces for the lowest singlet and triplet states of cyclobutadiene
journal, January 1978

The radical character of the acenes: A density matrix renormalization group study
text, January 2007

Improved Quantum Theory of Many‐Electron Systems. V. The Spin‐Coupling Optimized GI Method
journal, August 1969

Recovering dynamic correlation in spin flip configuration interaction through a difference dedicated approach
journal, January 2017

Ensemble-Density functional theory for excited states
journal, March 1990

Evidence for Singlet Fission Driven by Vibronic Coherence in Crystalline Tetracene
journal, March 2017

One - determinantal pure state versus ensemble Kohn-Sham solutions in the case of strong electron correlation: CH 2 and C 2
journal, September 1998

Correlation‐consistent configuration interaction: Accurate bond dissociation energies from simple wave functions
journal, March 1988

On the exact formulation of multi-configuration density-functional theory: electron density versus orbitals occupation
text, January 2014

Is GVB-CI superior to CASSCF?
journal, July 1999

On the exact formulation of multi-configuration density-functional theory: electron density versus orbitals occupation
journal, August 2014

The Theory of Complex Spectra
journal, November 1929

First-Principles Quantum Dynamics of Singlet Fission: Coherent versus Thermally Activated Mechanisms Governed by Molecular $π$ Stacking
journal, August 2015

Photogeneration of Octacene and Nonacene
journal, April 2010

Using the GVB Ansatz to develop ensemble DFT method for describing multiple strongly correlated electron pairs
journal, January 2016

The surface energy of a bounded electron gas
journal, August 1974

The Theory of Complex Spectra
journal, October 1930

Forces in Molecules
journal, August 1939

Quintet multiexciton dynamics in singlet fission
journal, October 2016

Density functionals for coulomb systems
journal, September 1983

Generalized valence bond description of bonding in low-lying states of molecules
journal, November 1973

Generalised adiabatic connection in ensemble density-functional theory for excited states: example of the H ₂ molecule
journal, November 2013

Excitation energies from time-dependent density-functional formalism for small systems
journal, March 2002

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

A one‐to‐one mapping between one‐particle densities and some n ‐particle ensembles
journal, November 1980

Aufbau derived from a unified treatment of occupation numbers in Hartree–Fock, Kohn–Sham, and natural orbital theories with the Karush–Kuhn–Tucker conditions for the inequality constraints ni≤1 and ni≥0
journal, May 2010

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

Density-functional exchange-energy approximation with correct asymptotic behavior
journal, September 1988

Second‐order perturbation theory with a complete active space self‐consistent field reference function
journal, January 1992

Hohenberg-Kohn theorem and non-V-representable densities
journal, August 1983

Self-consistent implementation of ensemble density functional theory method for multiple strongly correlated electron pairs
journal, December 2016

Benchmark calculations of chemical reactions in density functional theory: Comparison of the accurate Kohn–Sham solution with generalized gradient approximations for the H2+H and H2+H2 reactions
journal, September 1999

Heptacene: Characterization in Solution, in the Solid State, and in Films
journal, March 2017

Quantum-Chemical Studies on Excitation Energy Transfer Processes in BODIPY-Based Donor–Acceptor Systems
journal, August 2015

GVB-RP: A reliable MCSCF wave function for large systems
journal, January 1999

Correlation energy of an inhomogeneous electron gas: A coordinate‐space model
journal, January 1988

Density-functional theory for ensembles of fractionally occupied states. II. Application to the He atom
journal, April 1988

Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density
text, January 1988

Assessment of Density Functional Methods for Obtaining Geometries at Conical Intersections in Organic Molecules
journal, September 2013

Static density - density correlation function for interacting ground states with ensemble v -representable number densities
journal, January 1998

The Multiradical Character of One- and Two-Dimensional Graphene Nanoribbons
journal, January 2013

Quantum Chemistry on Graphical Processing Units. 3. Analytical Energy Gradients, Geometry Optimization, and First Principles Molecular Dynamics
journal, August 2009

Can a square or effectively square singlet be the ground state of cyclobutadiene
journal, October 1975

Fission of Entangled Spins: An Electronic Structure Perspective
journal, November 2013

Assessment of Density Functional Theory for Describing the Correlation Effects on the Ground and Excited State Potential Energy Surfaces of a Retinal Chromophore Model
journal, August 2013

Benchmarks of electronically excited states: Basis set effects on CASPT2 results
journal, November 2010

Exact Density Functionals for Ground-State Energies. I. General Results
journal, June 1984

Restricted Ensemble-Referenced Kohn−Sham versus Broken Symmetry Approaches in Density Functional Theory: Magnetic Coupling in Cu Binuclear Complexes
journal, March 2007

Inhomogeneous Electron Gas
journal, March 1973

General SCF operator satisfying correct variational condition
journal, August 1973

Exact Density Functionals for Ground-State Energies II. Details and Remarks
journal, July 1984

Exact ensemble density functional theory for excited states in a model system: Investigating the weight dependence of the correlation energy
journal, January 2017

Fluorescence of Naphthacene Vapor
journal, October 1963

Nature of ground and electronic excited states of higher acenes
journal, August 2016

Quantum Chemistry on Graphical Processing Units. 2. Direct Self-Consistent-Field Implementation
journal, March 2009