Low-lying excited states by constrained DFT

Ramos, Pablo; Pavanello, Michele

doi:10.1063/1.5018615

Title: Low-lying excited states by constrained DFT

Journal Article · 10 April 2018 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/1.5018615 · OSTI ID:1540161

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Rutgers Univ., Newark, NJ (United States). Dept. of Chemistry

Exploiting the machinery of Constrained Density Functional Theory (CDFT), we propose a variational method for calculating low-lying excited states of molecular systems. We dub this method eXcited CDFT (XCDFT). Excited states are obtained by self-consistently constraining a user-defined population of electrons, N_c, in the virtual space of a reference set of occupied orbitals. By imposing this population to be N_c = 1.0, we computed the first excited state of 15 molecules from a test set. Our results show that XCDFT achieves an accuracy in the predicted excitation energy only slightly worse than linear-response time-dependent DFT (TDDFT), but without incurring into problems of variational collapse typical of the more commonly adopted ΔSCF method. In addition, we selected a few challenging processes to test the limits of applicability of XCDFT. We find that in contrast to TDDFT, XCDFT is capable of reproducing energy surfaces featuring conical intersections (azobenzene and H3) with correct topology and correct overall energetics also away from the intersection. Venturing to condensed-phase systems, XCDFT reproduces the TDDFT solvatochromic shift of benzaldehyde when it is embedded by a cluster of water molecules. Finally, we find XCDFT to be a competitive method among single-reference methods for computations of excited states in terms of time to solution, rate of convergence, and accuracy of the result.

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Research Organization:: Rutgers Univ., Piscataway, NJ (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: SC0018343

OSTI ID:: 1540161

Alternate ID(s):: OSTI ID: 1432581

Journal Information:: Journal of Chemical Physics, Vol. 148, Issue 14; ISSN 0021-9606

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

Country of Publication:: United States

Language:: English

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Cited by: 35 works

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References (61)

Self-Consistent Field Calculations of Excited States Using the Maximum Overlap Method (MOM) ^† Gilbert, Andrew T. B.; Besley, Nicholas A.; Gill, Peter M. W. The Journal of Physical Chemistry A, Vol. 112, Issue 50 https://doi.org/10.1021/jp801738f	journal	December 2008
Excited-state potential-energy surfaces of metal-adsorbed organic molecules from linear expansion Δ-self-consistent field density-functional theory (ΔSCF-DFT) Maurer, Reinhard J.; Reuter, Karsten The Journal of Chemical Physics, Vol. 139, Issue 1 https://doi.org/10.1063/1.4812398	journal	July 2013
The implementation of a self-consistent constricted variational density functional theory for the description of excited states Ziegler, Tom; Krykunov, Mykhaylo; Cullen, John The Journal of Chemical Physics, Vol. 136, Issue 12 https://doi.org/10.1063/1.3696967	journal	March 2012
Density Functional Physicality in Electronic Coupling Estimation: Benchmarks and Error Analysis Kim, Hyungjun; Goodson, Theodore; Zimmerman, Paul M. The Journal of Physical Chemistry Letters, Vol. 8, Issue 14 https://doi.org/10.1021/acs.jpclett.7b01434	journal	July 2017
Current Status of the AMOEBA Polarizable Force Field Ponder, Jay W.; Wu, Chuanjie; Ren, Pengyu The Journal of Physical Chemistry B, Vol. 114, Issue 8 https://doi.org/10.1021/jp910674d	journal	March 2010
The ORCA program system: The ORCA program system Neese, Frank Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 1 https://doi.org/10.1002/wcms.81	journal	June 2011
Singlet fission in pentacene through multi-exciton quantum states Zimmerman, Paul M.; Zhang, Zhiyong; Musgrave, Charles B. Nature Chemistry, Vol. 2, Issue 8 https://doi.org/10.1038/nchem.694	journal	June 2010
Photochemistry of benzaldehyde Berger, Michael.; Goldblatt, Irwin L.; Steel, Colin. Journal of the American Chemical Society, Vol. 95, Issue 6 https://doi.org/10.1021/ja00787a004	journal	March 1973
Isomerization Through Conical Intersections Levine, Benjamin G.; Martínez, Todd J. Annual Review of Physical Chemistry, Vol. 58, Issue 1 https://doi.org/10.1146/annurev.physchem.57.032905.104612	journal	May 2007
Efficient Real-Time Time-Dependent Density Functional Theory Method and its Application to a Collision of an Ion with a 2D Material Wang, Zhi; Li, Shu-Shen; Wang, Lin-Wang Physical Review Letters, Vol. 114, Issue 6 https://doi.org/10.1103/physrevlett.114.063004	journal	February 2015
Double excitations within time-dependent density functional theory linear response Maitra, Neepa T.; Zhang, Fan; Cave, Robert J. The Journal of Chemical Physics, Vol. 120, Issue 13 https://doi.org/10.1063/1.1651060	journal	April 2004
An accurate and linear-scaling method for calculating charge-transfer excitation energies and diabatic couplings Pavanello, Michele; Van Voorhis, Troy; Visscher, Lucas The Journal of Chemical Physics, Vol. 138, Issue 5 https://doi.org/10.1063/1.4789418	journal	February 2013
Modeling environment effects on spectroscopies through QM/classical models Mennucci, Benedetta Physical Chemistry Chemical Physics, Vol. 15, Issue 18 https://doi.org/10.1039/c3cp44417a	journal	January 2013
Constrained subsystem density functional theory Ramos, Pablo; Pavanello, Michele Physical Chemistry Chemical Physics, Vol. 18, Issue 31 https://doi.org/10.1039/c6cp00528d	journal	January 2016
Atomistic Study of the Long-Lived Quantum Coherences in the Fenna-Matthews-Olson Complex Shim, Sangwoo; Rebentrost, Patrick; Valleau, Stéphanie Biophysical Journal, Vol. 102, Issue 3 https://doi.org/10.1016/j.bpj.2011.12.021	journal	February 2012
Design Strategies To Improve the Sensitivity of Photoactive Metal Carbonyl Complexes (photoCORMs) to Visible Light and Their Potential as CO-Donors to Biological Targets Chakraborty, Indranil; Carrington, Samantha J.; Mascharak, Pradip K. Accounts of Chemical Research, Vol. 47, Issue 8 https://doi.org/10.1021/ar500172f	journal	July 2014
Benchmarks for electronically excited states: CASPT2, CC2, CCSD, and CC3 Schreiber, Marko; Silva-Junior, Mario R.; Sauer, Stephan P. A. The Journal of Chemical Physics, Vol. 128, Issue 13 https://doi.org/10.1063/1.2889385	journal	April 2008
Communication: CDFT-CI couplings can be unreliable when there is fractional charge transfer Mavros, Michael G.; Van Voorhis, Troy The Journal of Chemical Physics, Vol. 143, Issue 23 https://doi.org/10.1063/1.4938103	journal	December 2015
Perspective: Fundamental aspects of time-dependent density functional theory Maitra, Neepa T. The Journal of Chemical Physics, Vol. 144, Issue 22 https://doi.org/10.1063/1.4953039	journal	June 2016
The formulation of a constricted variational density functional theory for double excitations Seidu, Issaka; Krykunov, Mykhaylo; Ziegler, Tom Molecular Physics, Vol. 112, Issue 5-6 https://doi.org/10.1080/00268976.2013.852261	journal	October 2013
Time-Dependent Density Functional Response Theory for Molecules Casida, Mark E. Recent Advances in Density Functional Methods https://doi.org/10.1142/9789812830586_0005	book	November 1995
An Accurate and Linear Scaling Method to Calculate Charge-Transfer Excitation Energies and Diabatic Couplings Pavanello, Michele; Van Voorhis, Troy; Visscher, Lucas arXiv https://doi.org/10.48550/arxiv.1211.4880	text	January 2012
On the rotation-inversion controversy on photoisomerization of azobenzenes. Experimental proof of inversion Rau, Hermann; Lueddecke, Erik Journal of the American Chemical Society, Vol. 104, Issue 6 https://doi.org/10.1021/ja00370a028	journal	March 1982
Excitons in Solids from Time-Dependent Density-Functional Theory: Assessing the Tamm-Dancoff Approximation Byun, Young-Moo; Ullrich, Carsten Computation, Vol. 5, Issue 4 https://doi.org/10.3390/computation5010009	journal	January 2017
Communication: Conical intersections using constrained density functional theory–configuration interaction Kaduk, Benjamin; Van Voorhis, Troy The Journal of Chemical Physics, Vol. 133, Issue 6 https://doi.org/10.1063/1.3470106	journal	August 2010
Constrained Density Functional Theory Kaduk, Benjamin; Kowalczyk, Tim; Van Voorhis, Troy Chemical Reviews, Vol. 112, Issue 1 https://doi.org/10.1021/cr200148b	journal	November 2011
Perspectives on double-excitations in TDDFT Elliott, Peter; Goldson, Sharma; Canahui, Chris Chemical Physics, Vol. 391, Issue 1 https://doi.org/10.1016/j.chemphys.2011.03.020	journal	November 2011
On the Mechanism of the cis−trans Isomerization in the Lowest Electronic States of Azobenzene: S ₀ , S ₁ , and T ₁ Cembran, Alessandro; Bernardi, Fernando; Garavelli, Marco Journal of the American Chemical Society, Vol. 126, Issue 10 https://doi.org/10.1021/ja038327y	journal	March 2004
Performance of Frozen Density Embedding for Modeling Hole Transfer Reactions Ramos, Pablo; Papadakis, Markos; Pavanello, Michele The Journal of Physical Chemistry B, Vol. 119, Issue 24 https://doi.org/10.1021/jp511275e	journal	December 2014
DFT/TDDFT investigation on the UV-vis absorption and fluorescence properties of alizarin dye Amat, Anna; Miliani, Costanza; Romani, Aldo Physical Chemistry Chemical Physics, Vol. 17, Issue 9 https://doi.org/10.1039/c4cp04728a	journal	January 2015
The Different Photoisomerization Efficiency of Azobenzene in the Lowest nπ* and ππ* Singlets: The Role of a Phantom State Conti, Irene; Garavelli, Marco; Orlandi, Giorgio Journal of the American Chemical Society, Vol. 130, Issue 15 https://doi.org/10.1021/ja710275e	journal	April 2008
Improved non-valence virtual orbitals for CI calculations Caballol, Rosa; Malrieu, Jean-Paul Chemical Physics, Vol. 140, Issue 1 https://doi.org/10.1016/0301-0104(90)89043-p	journal	January 1990
Conical intersections and double excitations in time-dependent density functional theory Levine, Benjamin G.; Ko, Chaehyuk; Quenneville, Jason Molecular Physics, Vol. 104, Issue 5-7 https://doi.org/10.1080/00268970500417762	journal	March 2006
Orthogonality Constrained Density Functional Theory for Electronic Excited States Evangelista, Francesco A.; Shushkov, Philip; Tully, John C. The Journal of Physical Chemistry A, Vol. 117, Issue 32 https://doi.org/10.1021/jp401323d	journal	May 2013
Single-Reference ab Initio Methods for the Calculation of Excited States of Large Molecules Dreuw, Andreas; Head-Gordon, Martin Chemical Reviews, Vol. 105, Issue 11 https://doi.org/10.1021/cr0505627	journal	November 2005
Accelerated Molecular Dynamics Simulations with the AMOEBA Polarizable Force Field on Graphics Processing Units Lindert, Steffen; Bucher, Denis; Eastman, Peter Journal of Chemical Theory and Computation, Vol. 9, Issue 11 https://doi.org/10.1021/ct400514p	journal	October 2013
Application of the local self-consistent-field method to core-ionized and core-excited molecules, polymers, and proteins: True orthogonality between ground and excited states Ferré, Nicolas; Assfeld, Xavier The Journal of Chemical Physics, Vol. 117, Issue 9 https://doi.org/10.1063/1.1496462	journal	September 2002
Electronic excitations in a dielectric continuum solvent with quantum Monte Carlo: Acrolein in water Floris, Franca Maria; Filippi, Claudia; Amovilli, Claudio The Journal of Chemical Physics, Vol. 140, Issue 3 https://doi.org/10.1063/1.4861429	journal	January 2014
Assessment of the ΔSCF density functional theory approach for electronic excitations in organic dyes Kowalczyk, Tim; Yost, Shane R.; Voorhis, Troy Van The Journal of Chemical Physics, Vol. 134, Issue 5 https://doi.org/10.1063/1.3530801	journal	February 2011
Delta Self-Consistent Field as a method to obtain potential energy surfaces of excited molecules on surfaces Gavnholt, Jeppe; Olsen, Thomas; Engelund, Mads arXiv https://doi.org/10.48550/arxiv.0807.3242	text	January 2008
Benchmarks for electronically excited states: Time-dependent density functional theory and density functional theory based multireference configuration interaction Silva-Junior, Mario R.; Schreiber, Marko; Sauer, Stephan P. A. The Journal of Chemical Physics, Vol. 129, Issue 10 https://doi.org/10.1063/1.2973541	journal	September 2008
The improved virtual orbital-complete active space configuration interaction method, a “packageable” efficient ab initio many-body method for describing electronically excited states Potts, Davin M.; Taylor, Caroline M.; Chaudhuri, Rajat K. The Journal of Chemical Physics, Vol. 114, Issue 6 https://doi.org/10.1063/1.1337053	journal	February 2001
Assessing computationally efficient isomerization dynamics: ΔSCF density-functional theory study of azobenzene molecular switching Maurer, Reinhard J.; Reuter, Karsten The Journal of Chemical Physics, Vol. 135, Issue 22 https://doi.org/10.1063/1.3664305	journal	December 2011
Predicting Near Edge X-ray Absorption Spectra with the Spin-Free Exact-Two-Component Hamiltonian and Orthogonality Constrained Density Functional Theory Verma, Prakash; Derricotte, Wallace D.; Evangelista, Francesco A. Journal of Chemical Theory and Computation, Vol. 12, Issue 1 https://doi.org/10.1021/acs.jctc.5b00817	journal	December 2015
Electronically excited states of ethylene Wiberg, Kenneth B.; Hadad, Christopher M.; Foresman, James B. The Journal of Physical Chemistry, Vol. 96, Issue 26 https://doi.org/10.1021/j100205a032	journal	December 1992
Charge-Transfer in Time-Dependent Density Functional Theory Maitra, Neepa T. arXiv https://doi.org/10.48550/arxiv.1707.08054	text	January 2017
Chromophore-specific theoretical spectroscopy: From subsystem density functional theory to mode-specific vibrational spectroscopy Neugebauer, Johannes Physics Reports, Vol. 489, Issue 1-3 https://doi.org/10.1016/j.physrep.2009.12.001	journal	April 2010
The Photochemical Isomerization of Azobenzene ¹ Zimmerman, George; Chow, Lue-Yung; Paik, Un-Jin Journal of the American Chemical Society, Vol. 80, Issue 14 https://doi.org/10.1021/ja01547a010	journal	July 1958
Theoretical Analysis of the Electronic Spectra of Benzaldehyde Molina, Vicent; Merchán, Manuela The Journal of Physical Chemistry A, Vol. 105, Issue 15 https://doi.org/10.1021/jp004041t	journal	April 2001
Identifying the preferred interaction mode of naringin with gold nanoparticles through experimental, DFT and TDDFT techniques: insights into their sensing and biological applications Singh, Baljinder; Rani, Monika; Singh, Janpreet RSC Advances, Vol. 6, Issue 83 https://doi.org/10.1039/c6ra12076h	journal	January 2016
Ultrafast investigation of photoinduced charge transfer in aminoanthraquinone pharmaceutical product Zhang, Song; Sun, Simei; Zhou, Miaomiao Scientific Reports, Vol. 7, Issue 1 https://doi.org/10.1038/srep43419	journal	February 2017
On the required shape corrections to the local density and generalized gradient approximations to the Kohn–Sham potentials for molecular response calculations of (hyper)polarizabilities and excitation energies Grüning, Myrta; Gritsenko, Oleg V.; van Gisbergen, Stan J. A. The Journal of Chemical Physics, Vol. 116, Issue 22 https://doi.org/10.1063/1.1476007	journal	June 2002
Excited-state intramolecular proton-transfer (ESIPT)-inspired solid state emitters Padalkar, Vikas S.; Seki, Shu Chemical Society Reviews, Vol. 45, Issue 1 https://doi.org/10.1039/c5cs00543d	journal	January 2016
On the relation between time-dependent and variational density functional theory approaches for the determination of excitation energies and transition moments. Ziegler, Tom; Seth, Michael; Krykunov, Mykhaylo The Journal of Chemical Physics, Vol. 130, Issue 15 https://doi.org/10.1063/1.3114988	journal	April 2009
Discovering and understanding materials through computation Louie, Steven G.; Chan, Yang-Hao; da Jornada, Felipe H. Nature Materials, Vol. 20, Issue 6 https://doi.org/10.1038/s41563-021-01015-1	journal	May 2021
Perspectives on double-excitations in TDDFT Elliott, Peter; Goldson, Sharma; Canahui, Chris arXiv https://doi.org/10.48550/arxiv.1101.3379	text	January 2011
Mixed Quantum Mechanical/Molecular Mechanical Molecular Dynamics Simulations of Biological Systems in Ground and Electronically Excited States Brunk, Elizabeth; Rothlisberger, Ursula Chemical Reviews, Vol. 115, Issue 12 https://doi.org/10.1021/cr500628b	journal	April 2015
Valence shell electronic spectroscopy of isoprene studied by theoretical calculations and by electron scattering, photoelectron, and absolute photoabsorption measurements Martins, G.; Ferreira-Rodrigues, A. M.; Rodrigues, F. N. Physical Chemistry Chemical Physics, Vol. 11, Issue 47 https://doi.org/10.1039/b916620c	journal	January 2009
Single-Reference ab initio Methods for the Calculation of Excited States of Large Molecules Dreuw, Andreas; Head-Gordon, Martin ChemInform, Vol. 37, Issue 5 https://doi.org/10.1002/chin.200605293	journal	January 2006
VMD: Visual molecular dynamics Humphrey, William; Dalke, Andrew; Schulten, Klaus Journal of Molecular Graphics, Vol. 14, Issue 1 https://doi.org/10.1016/0263-7855(96)00018-5	journal	February 1996
Recent Advances in Density Functional Methods Chong, Delano P. Recent Advances in Computational Chemistry https://doi.org/10.1142/2914	book	November 1995

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