Adapting algebraic diagrammatic construction schemes for the polarization propagator to problems with multi-reference electronic ground states exploiting the spin-flip ansatz.

For the investigation of molecular systems with electronic ground states exhibiting multi-reference character, a spin-flip (SF) version of the algebraic diagrammatic construction (ADC) scheme for the polarization propagator up to third order perturbation theory (SF-ADC(3)) is derived via the intermediate state representation and implemented into our existing ADC computer program adcman. The accuracy of these new SF-ADC(n) approaches is tested on typical situations, in which the ground state acquires multi-reference character, like bond breaking of H2 and HF, the torsional motion of ethylene, and the excited states of rectangular and square-planar cyclobutadiene. Overall, the results of SF-ADC(n) reveal an accurate description of these systems in comparison with standard multi-reference methods. Thus, the spin-flip versions of ADC are easy-to-use methods for the calculation of "few-reference" systems, which possess a stable single-reference triplet ground state.

[1]  Francesco A. Evangelista,et al.  Multireference Driven Similarity Renormalization Group: A Second-Order Perturbative Analysis. , 2015, Journal of chemical theory and computation.

[2]  Andreas Dreuw,et al.  The third-order algebraic diagrammatic construction method (ADC(3)) for the polarization propagator for closed-shell molecules: efficient implementation and benchmarking. , 2014, The Journal of chemical physics.

[3]  A. Dreuw,et al.  Investigating excited electronic states using the algebraic diagrammatic construction (ADC) approach of the polarisation propagator , 2014 .

[4]  M. Pernpointner.  The relativistic polarization propagator for the calculation of electronic excitations in heavy systems. , 2014, The Journal of chemical physics.

[5]  Jürgen Gauss,et al.  State‐specific multireference coupled‐cluster theory , 2013 .

[6]  Thomas Müller,et al.  The Multiradical Character of One- and Two-Dimensional Graphene Nanoribbons , 2013, Angewandte Chemie.

[7]  A. Savin,et al.  A multiconfigurational hybrid density-functional theory. , 2012, The Journal of chemical physics.

[8]  Yihan Shao,et al.  General formulation of spin-flip time-dependent density functional theory using non-collinear kernels: theory, implementation, and benchmarks. , 2012, The Journal of chemical physics.

[9]  H. Lischka,et al.  Multiconfiguration self-consistent field and multireference configuration interaction methods and applications. , 2012, Chemical reviews.

[10]  Jeppe Olsen,et al.  The CASSCF method: A perspective and commentary , 2011 .

[11]  Dieter Cremer,et al.  Møller–Plesset perturbation theory: from small molecule methods to methods for thousands of atoms , 2011 .

[12]  Francesco A Evangelista,et al.  An orbital-invariant internally contracted multireference coupled cluster approach. , 2011, The Journal of chemical physics.

[13]  Y. Kitagawa,et al.  A broken-symmetry study on the automerization of cyclobutadiene. Comparison with UNO- and DNO-MRCC methods , 2010 .

[14]  Walter Thiel,et al.  Benchmark of Electronically Excited States for Semiempirical Methods: MNDO, AM1, PM3, OM1, OM2, OM3, INDO/S, and INDO/S2. , 2010, Journal of chemical theory and computation.

[15]  Sanghamitra Das,et al.  Full implementation and benchmark studies of Mukherjee's state-specific multireference coupled-cluster ansatz. , 2010, The Journal of chemical physics.

[16]  Josef Paldus,et al.  Accounting for the exact degeneracy and quasidegeneracy in the automerization of cyclobutadiene via multireference coupled-cluster methods. , 2009, The Journal of chemical physics.

[17]  J. Schirmer,et al.  Review of biorthogonal coupled cluster representations for electronic excitation , 2009, 0906.5513.

[18]  Isaiah Shavitt,et al.  New implementation of the graphical unitary group approach for multireference direct configuration interaction calculations , 2009 .

[19]  M. Hanrath,et al.  Multi-reference coupled-cluster study of the potential energy surface of the hydrogen fluoride dissociation including excited states , 2009 .

[20]  Anna I Krylov,et al.  Double spin-flip approach within equation-of-motion coupled cluster and configuration interaction formalisms: Theory, implementation, and examples. , 2009, The Journal of chemical physics.

[21]  Andreas Dreuw,et al.  Unrestricted algebraic diagrammatic construction scheme of second order for the calculation of excited states of medium-sized and large molecules. , 2009, The Journal of chemical physics.

[22]  Anna I Krylov,et al.  A noniterative perturbative triples correction for the spin-flipping and spin-conserving equation-of-motion coupled-cluster methods with single and double substitutions. , 2008, The Journal of chemical physics.

[23]  Kiran Bhaskaran-Nair,et al.  Multireference state-specific Mukherjee's coupled cluster method with noniterative triexcitations. , 2008, The Journal of chemical physics.

[24]  David Casanova,et al.  The spin-flip extended single excitation configuration interaction method. , 2008, The Journal of chemical physics.

[25]  M. Frisch,et al.  CASSCF calculations for photoinduced processes in large molecules: Choosing when to use the RASSCF, ONIOM and MMVB approximations , 2007 .

[26]  T. Takada,et al.  CASCI-DFT study of the phenalenyl radical system , 2007 .

[27]  M. Barbatti,et al.  The nonadiabatic deactivation paths of pyrrole. , 2006, The Journal of chemical physics.

[28]  Shawn T. Brown,et al.  Advances in methods and algorithms in a modern quantum chemistry program package. , 2006, Physical chemistry chemical physics : PCCP.

[29]  M. Engelhard,et al.  First steps of retinal photoisomerization in proteorhodopsin. , 2006, Biophysical journal.

[30]  Anna I Krylov,et al.  Spin-flip equation-of-motion coupled-cluster electronic structure method for a description of excited states, bond breaking, diradicals, and triradicals. , 2006, Accounts of chemical research.

[31]  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.

[32]  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.

[33]  J. Paier,et al.  Photochemistry of ethylene: a multireference configuration interaction investigation of the excited-state energy surfaces. , 2004, The Journal of chemical physics.

[34]  B. Roos,et al.  A modified definition of the zeroth-order Hamiltonian in multiconfigurational perturbation theory (CASPT2) , 2004 .

[35]  A. Trofimov,et al.  Intermediate state representation approach to physical properties of electronically excited molecules. , 2004, The Journal of chemical physics.

[36]  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.

[37]  Robert P. Krawczyk,et al.  Photoinduced dynamics of the valence states of ethene: A six-dimensional potential-energy surface of three electronic states with several conical intersections , 2003 .

[38]  Anna I. Krylov,et al.  A spin-complete version of the spin-flip approach to bond breaking: What is the impact of obtaining spin eigenfunctions? , 2003 .

[39]  Anna I. Krylov,et al.  Perturbative corrections to the equation-of-motion spin–flip self-consistent field model: Application to bond-breaking and equilibrium properties of diradicals , 2002 .

[40]  Anna I. Krylov,et al.  Spin-flip configuration interaction: an electronic structure model that is both variational and size-consistent , 2001 .

[41]  Anna I. Krylov,et al.  Size-consistent wave functions for bond-breaking: the equation-of-motion spin-flip model , 2001 .

[42]  P. Knowles,et al.  Spin-orbit matrix elements for internally contracted multireference configuration interaction wavefunctions , 2000 .

[43]  Anna I. Krylov,et al.  Spin-contamination of coupled-cluster wave functions , 2000 .

[44]  Todd J. Martínez,et al.  Photodynamics of ethylene: ab initio studies of conical intersections , 2000 .

[45]  Walter Thiel,et al.  Orthogonalization corrections for semiempirical methods , 2000 .

[46]  Luis Serrano-Andrés,et al.  The multi-state CASPT2 method , 1998 .

[47]  P. Anfinrud,et al.  Chemical dynamics in proteins: the photoisomerization of retinal in bacteriorhodopsin. , 1998, Science.

[48]  P. Anfinrud,et al.  The photoisomerization of retinal in bacteriorhodospin: experimental evidence for a three-state model. , 1996, Proceedings of the National Academy of Sciences of the United States of America.

[49]  Rodney J. Bartlett,et al.  Approximately extensive modifications of the multireference configuration interaction method: A theoretical and practical analysis , 1995 .

[50]  Jochen Schirmer,et al.  An efficient polarization propagator approach to valence electron excitation spectra , 1995 .

[51]  Rodney J. Bartlett,et al.  A multireference coupled‐cluster study of the ground state and lowest excited states of cyclobutadiene , 1994 .

[52]  H. Koch,et al.  Calculation of size‐intensive transition moments from the coupled cluster singles and doubles linear response function , 1994 .

[53]  Schirmer,et al.  Closed-form intermediate representations of many-body propagators and resolvent matrices. , 1991, Physical review. A, Atomic, molecular, and optical physics.

[54]  Alistair P. Rendell,et al.  The restricted active space self-consistent-field method, implemented with a split graph unitary group approach , 1990 .

[55]  G. Kumar,et al.  Photochemistry of azobenzene-containing polymers , 1989 .

[56]  J. Schirmer,et al.  On Green’s function calculations of the static self‐energy part, the ground state energy and expectation values , 1989 .

[57]  György G. Ferenczy,et al.  Semiempirical AM1 electrostatic potentials and AM1 electrostatic potential derived charges: A comparison with ab initio values , 1989 .

[58]  P. Knowles,et al.  An efficient internally contracted multiconfiguration–reference configuration interaction method , 1988 .

[59]  Eamonn F. Healy,et al.  Development and use of quantum mechanical molecular models. 76. AM1: a new general purpose quantum mechanical molecular model , 1985 .

[60]  B. K. Carpenter.  Heavy-atom tunneling as the dominant pathway in a solution-phase reaction? Bond shift in antiaromatic annulenes , 1983 .

[61]  Jochen Schirmer,et al.  Beyond the random-phase approximation: A new approximation scheme for the polarization propagator , 1982 .

[62]  B. K. Carpenter,et al.  Limits on the activation parameters for automerization of cyclobutadiene-1,2-d2 , 1982 .

[63]  Andreas Dreuw,et al.  The algebraic diagrammatic construction scheme for the polarization propagator for the calculation of excited states , 2015 .

[64]  Frank Neese,et al.  The ORCA program system , 2012 .

[65]  Rodney J. Bartlett,et al.  Coupled‐cluster theory and its equation‐of‐motion extensions , 2012 .

[66]  Christof Hättig,et al.  Structure Optimizations for Excited States with Correlated Second-Order Methods: CC2 and ADC(2) , 2005 .

[67]  Michael W. Schmidt,et al.  The construction and interpretation of MCSCF wavefunctions. , 1998, Annual review of physical chemistry.