Assessment of charge-transfer excitations with time-dependent, range-separated density functional theory based on long-range MP2 and multiconfigurational self-consistent field wave functions.

Charge transfer excitations can be described within Time-Dependent Density Functional Theory (TD-DFT), not only by means of the Coulomb Attenuated Method (CAM) but also with a combination of wave function theory and TD-DFT based on range separation. The latter approach enables a rigorous formulation of multi-determinantal TD-DFT schemes where excitation classes, which are absent in conventional TD-DFT spectra (like for example double excitations), can be addressed. This paper investigates the combination of both the long-range Multi-Configuration Self-Consistent Field (MCSCF) and Second Order Polarization Propagator Approximation (SOPPA) ansätze with a short-range DFT (srDFT) description. We find that the combinations of SOPPA or MCSCF with TD-DFT yield better results than could be expected from the pure wave function schemes. For the Time-Dependent MCSCF short-range DFT ansatz (TD-MC-srDFT) excitation energies calculated over a larger benchmark set of molecules with predominantly single reference character yield good agreement with their reference values, and are in general comparable to the CAM-B3LYP functional. The SOPPA-srDFT scheme is tested for a subset of molecules used for benchmarking TD-MC-srDFT and performs slightly better against the reference data for this small subset. Beyond the proof-of-principle calculations comprising the first part of this contribution, we additionally studied the low-lying singlet excited states (S1 and S2) of the retinal chromophore. The chromophore displays multireference character in the ground state and both excited states exhibit considerable double excitation character, which in turn cannot be described within standard TD-DFT, due to the adiabatic approximation. However, a TD-MC-srDFT approach can account for the multireference character, and excitation energies are obtained with accuracy comparable to CASPT2, although using a much smaller active space.

[1]  O. Franck,et al.  Generalised adiabatic connection in ensemble density-functional theory for excited states: example of the H2 molecule , 2013, 1308.4596.

[2]  K. Pernal,et al.  Calculation of electronic excited states of molecules using the Helmholtz free-energy minimum principle , 2013 .

[3]  Jógvan Magnus Haugaard Olsen,et al.  Computational screening of one- and two-photon spectrally tuned channelrhodopsin mutants. , 2013, Physical chemistry chemical physics : PCCP.

[4]  A. Savin,et al.  Electronic excitations from a linear-response range-separated hybrid scheme , 2013, 1304.1322.

[5]  Stefan Knecht,et al.  Multi-configuration time-dependent density-functional theory based on range separation. , 2012, The Journal of chemical physics.

[6]  K. Pernal.  Excitation energies from range-separated time-dependent density and density matrix functional theory. , 2012, The Journal of chemical physics.

[7]  K. Burke.  Perspective on density functional theory. , 2012, The Journal of chemical physics.

[8]  M. E. Casida,et al.  Progress in time-dependent density-functional theory. , 2011, Annual review of physical chemistry.

[9]  Emmanuel Fromager,et al.  Analysis of self-consistency effects in range-separated density-functional theory with Møller-Plesset perturbation theory. , 2011, The Journal of chemical physics.

[10]  N. Maitra,et al.  Perspectives on double-excitations in TDDFT , 2011, 1101.3379.

[11]  Á. Rubio,et al.  Assessment of dressed time-dependent density-functional theory for the low-lying valence states of 28 organic chromophores , 2010, 1101.0291.

[12]  Jacob Kongsted,et al.  Excited States in Solution through Polarizable Embedding , 2010 .

[13]  H. Ågren,et al.  Spin-flip time dependent density functional theory applied to excited states with single, double, or mixed electron excitation character. , 2010, The Journal of chemical physics.

[14]  Roi Baer,et al.  Tuned range-separated hybrids in density functional theory. , 2010, Annual review of physical chemistry.

[15]  Renzo Cimiraglia,et al.  Merging multireference perturbation and density-functional theories by means of range separation: Potential curves for Be 2 , Mg 2 , and Ca 2 , 2010 .

[16]  T. Moore,et al.  Solar fuels via artificial photosynthesis. , 2009, Accounts of chemical research.

[17]  Florent Réal,et al.  On the universality of the long-/short-range separation in multiconfigurational density-functional theory. II. Investigating f0 actinide species. , 2009, The Journal of chemical physics.

[18]  U. Ryde,et al.  Protein Influence on Electronic Spectra Modeled by Multipoles and Polarizabilities. , 2009, Journal of chemical theory and computation.

[19]  R. Baer,et al.  Reliable prediction of charge transfer excitations in molecular complexes using time-dependent density functional theory. , 2009, Journal of the American Chemical Society.

[20]  John M Herbert,et al.  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. , 2009, The Journal of chemical physics.

[21]  Keiji Morokuma,et al.  Mechanism of spectral tuning going from retinal in vacuo to bovine rhodopsin and its mutants: multireference ab initio quantum mechanics/molecular mechanics studies. , 2008, The journal of physical chemistry. B.

[22]  Walter Thiel,et al.  Benchmarks for electronically excited states: time-dependent density functional theory and density functional theory based multireference configuration interaction. , 2008, The Journal of chemical physics.

[23]  C. Marian,et al.  Performance of the Density Functional Theory/Multireference Configuration Interaction Method on Electronic Excitation of Extended π-Systems. , 2008, Journal of chemical theory and computation.

[24]  Emmanuel Fromager,et al.  Self-consistent many-body perturbation theory in range-separated density-functional theory : A one-electron reduced-density-matrix-based formulation , 2008 .

[25]  R. Baer,et al.  A density functional theory for symmetric radical cations from bonding to dissociation. , 2008, The journal of physical chemistry. A.

[26]  Walter Thiel,et al.  Benchmarks for electronically excited states: CASPT2, CC2, CCSD, and CC3. , 2008, The Journal of chemical physics.

[27]  Trygve Helgaker,et al.  Excitation energies in density functional theory: an evaluation and a diagnostic test. , 2008, The Journal of chemical physics.

[28]  Julien Toulouse,et al.  On the universality of the long-/short-range separation in multiconfigurational density-functional theory. , 2007, The Journal of chemical physics.

[29]  R. Baer,et al.  A well-tempered density functional theory of electrons in molecules. , 2007, Physical chemistry chemical physics : PCCP.

[30]  G. Scuseria,et al.  Assessment of a long-range corrected hybrid functional. , 2006, The Journal of chemical physics.

[31]  R. Cingolani,et al.  Optical properties of N-succinimidyl bithiophene and the effects of the binding to biomolecules: comparison between coupled-cluster and time-dependent density functional theory calculations and experiments. , 2006, The journal of physical chemistry. B.

[32]  Julien Preat,et al.  An ab initio study of the absorption spectra of indirubin, isoindigo, and related derivatives. , 2006, The journal of physical chemistry. A.

[33]  Xuefei Xu,et al.  Computational characterization of low-lying states and intramolecular charge transfers in N-phenylpyrrole and the planar-rigidized fluorazene. , 2006, The journal of physical chemistry. A.

[34]  L. H. Andersen,et al.  S1 and S2 excited States of gas-phase Schiff-base retinal chromophores. , 2006, Physical review letters.

[35]  H. Werner,et al.  A short-range gradient-corrected density functional in long-range coupled-cluster calculations for rare gas dimers. , 2005, Physical chemistry chemical physics : PCCP.

[36]  Stefan Haacke,et al.  Absorption of schiff-base retinal chromophores in vacuo. , 2005, Journal of the American Chemical Society.

[37]  Marco Garavelli,et al.  Structure, spectroscopy, and spectral tuning of the gas-phase retinal chromophore: the beta-ionone "handle" and alkyl group effect. , 2005, The journal of physical chemistry. A.

[38]  Andreas Savin,et al.  van der Waals forces in density functional theory: Perturbational long-range electron-interaction corrections , 2005, cond-mat/0505062.

[39]  Tom Ziegler,et al.  The performance of time-dependent density functional theory based on a noncollinear exchange-correlation potential in the calculations of excitation energies. , 2005, The Journal of chemical physics.

[40]  Tom Ziegler,et al.  Time-dependent density functional theory based on a noncollinear formulation of the exchange-correlation potential. , 2004, The Journal of chemical physics.

[41]  A. Savin,et al.  Long-range/short-range separation of the electron-electron interaction in density functional theory , 2004, physics/0410062.

[42]  E. Baerends,et al.  Vibronic coupling and double excitations in linear response time-dependent density functional calculations: dipole-allowed states of N2. , 2004, The Journal of chemical physics.

[43]  N. Handy,et al.  A new hybrid exchange–correlation functional using the Coulomb-attenuating method (CAM-B3LYP) , 2004 .

[44]  K. Burke,et al.  Adiabatic connection for near degenerate excited states , 2004 .

[45]  Fan Zhang,et al.  A dressed TDDFT treatment of the 21Ag states of butadiene and hexatriene , 2004 .

[46]  E. Gross,et al.  Time-dependent density functional theory. , 2004, Annual review of physical chemistry.

[47]  Kieron Burke,et al.  Double excitations within time-dependent density functional theory linear response. , 2004, The Journal of chemical physics.

[48]  M. Head‐Gordon,et al.  Failure of time-dependent density functional theory for long-range charge-transfer excited states: the zincbacteriochlorin-bacteriochlorin and bacteriochlorophyll-spheroidene complexes. , 2004, Journal of the American Chemical Society.

[49]  Dmitrij Rappoport,et al.  Photoinduced intramolecular charge transfer in 4-(dimethyl)aminobenzonitrile--a theoretical perspective. , 2004, Journal of the American Chemical Society.

[50]  Massimo Olivucci,et al.  Probing the rhodopsin cavity with reduced retinal models at the CASPT2//CASSCF/AMBER level of theory. , 2003, Journal of the American Chemical Society.

[51]  Yun Lu,et al.  Performance assessment of density‐functional methods for study of charge‐transfer complexes , 2003, J. Comput. Chem..

[52]  K. Morokuma,et al.  Investigation of the S0S1 excitation in bacteriorhodopsin with the ONIOM(MO:MM) hybrid method , 2003 .

[53]  Anna I. Krylov,et al.  The spin–flip approach within time-dependent density functional theory: Theory and applications to diradicals , 2003 .

[54]  Trond Saue,et al.  Linear response at the 4-component relativistic level: Application to the frequency-dependent dipole polarizabilities of the coinage metal dimers , 2003 .

[55]  H. Lüthi,et al.  Assessment of time-dependent density-functional theory for the calculation of critical features in the absorption spectra of a series of aromatic donor–acceptor systems , 2002 .

[56]  Celestino Angeli,et al.  Introduction of n-electron valence states for multireference perturbation theory , 2001 .

[57]  F. Gadéa,et al.  Charge-transfer correction for improved time-dependent local density approximation excited-state potential energy curves: Analysis within the two-level model with illustration for H2 and LiH , 2000 .

[58]  L. Serrano-Andrés,et al.  Theoretical Study of the Twisted Intramolecular Charge Transfer in 1-Phenylpyrrole , 2000 .

[59]  Luis Serrano-Andrés,et al.  Does density functional theory contribute to the understanding of excited states of unsaturated organic compounds , 1999 .

[60]  S. Grimme,et al.  A COMBINATION OF KOHN-SHAM DENSITY FUNCTIONAL THEORY AND MULTI-REFERENCE CONFIGURATION INTERACTION METHODS , 1999 .

[61]  S. Grimme,et al.  Electron energy loss and DFT/SCI study of the singlet and triplet excited states of aminobenzonitriles and benzoquinuclidines: role of the amino group twist angle. , 1999 .

[62]  Markus P. Fülscher,et al.  Theoretical Study of the Electronic Spectroscopy of Peptides. III. Charge-Transfer Transitions in Polypeptides , 1998 .

[63]  Dennis R. Salahub,et al.  Molecular excitation energies to high-lying bound states from time-dependent density-functional response theory: Characterization and correction of the time-dependent local density approximation ionization threshold , 1998 .

[64]  Andreas Savin,et al.  Combining long-range configuration interaction with short-range density functionals , 1997 .

[65]  Martin J. Packer,et al.  A new implementation of the second‐order polarization propagator approximation (SOPPA): The excitation spectra of benzene and naphthalene , 1996 .

[66]  L. Serrano-Andrés,et al.  THEORETICAL STUDY OF THE INTERNAL CHARGE TRANSFER IN AMINOBENZONITRILES , 1995 .

[67]  Björn O. Roos,et al.  Second-order perturbation theory with a complete active space self-consistent field reference function , 1992 .

[68]  Kerstin Andersson,et al.  Second-order perturbation theory with a CASSCF reference function , 1990 .

[69]  R. Birge,et al.  Two‐photon double resonance spectroscopy of bacteriorhodopsin. Assignment of the electronic and dipolar properties of the low‐lying 1A*−g‐like and 1B*+u‐like π, π* states , 1990 .

[70]  T. H. Dunning.  Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen , 1989 .

[71]  J. Olsen,et al.  Linear and nonlinear response functions for an exact state and for an MCSCF state , 1985 .

[72]  P. Jørgensen,et al.  Polarization propagator methods in atomic and molecular calculations , 1984 .

[73]  E. Gross,et al.  Density-Functional Theory for Time-Dependent Systems , 1984 .

[74]  M. Graetzel,et al.  Artificial photosynthesis: water cleavage into hydrogen and oxygen by visible light , 1981 .

[75]  Jacob Kongsted,et al.  Molecular Properties through Polarizable Embedding , 2011 .

[76]  Poul Jørgensen,et al.  Response functions from Fourier component variational perturbation theory applied to a time-averaged quasienergy , 1998 .

[77]  A. Savin,et al.  On degeneracy, near-degeneracy and density functional theory , 1996 .

[78]  Jorge M. Seminario.  Recent developments and applications of modern density functional theory , 1996 .