Excitation Spectra of Nucleobases with Multiconfigurational Density Functional Theory.

Range-separated hybrid methods between wave function theory and density functional theory (DFT) can provide high-accuracy results, while correcting some of the inherent flaws of both the underlying wave function theory and DFT. We here assess the accuracy for excitation energies of the nucleobases thymine, uracil, cytosine, and adenine, using a hybrid between complete active space self-consistent field (CASSCF) and DFT methods. The method is based on range separation, thereby avoiding all double-counting of electron correlation and is denoted long-range CASSCF short-range DFT (CAS-srDFT). Using a linear response extension of CAS-srDFT, we compare the first 7-8 excited states of the nucleobases with perturbative multireference approaches as well as coupled cluster based methods. Our results show that the CAS-srDFT method can provide accurate excitation energies in good correspondence with the computationally more expensive methods.

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

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

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

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

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

[6]  Ajith Perera,et al.  Benchmark studies on the building blocks of DNA. 1. Superiority of coupled cluster methods in describing the excited states of nucleobases in the Franck-Condon region. , 2012, The journal of physical chemistry. A.

[7]  T. Dunning,et al.  Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions , 1992 .

[8]  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 .

[9]  Jacob Kongsted,et al.  Polarizable embedding with a multiconfiguration short-range density functional theory linear response method. , 2015, The Journal of chemical physics.

[10]  C. Hättig,et al.  Quantum-chemical investigation of the structures and electronic spectra of the nucleic acid bases at the coupled cluster CC2 level. , 2007, The journal of physical chemistry. A.

[11]  Jeppe Olsen,et al.  Second‐order Mo/ller–Plesset perturbation theory as a configuration and orbital generator in multiconfiguration self‐consistent field calculations , 1988 .

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

[13]  Luca Frediani,et al.  The Dalton quantum chemistry program system , 2013, Wiley interdisciplinary reviews. Computational molecular science.

[14]  J. Olsen,et al.  Erratum: Second‐order Mo/ller–Plesset perturbation theory as a configuration and orbital generator in multiconfiguration self‐consistent‐field calculations [J. Chem. Phys. 88, 3834 (1988)] , 1988 .

[15]  G. Scuseria,et al.  Hybrid functionals based on a screened Coulomb potential , 2003 .

[16]  Andreas Savin,et al.  Density functionals for the Yukawa electron-electron interaction , 1995 .

[17]  Jerzy Leszczynski,et al.  TDDFT investigation on nucleic acid bases: Comparison with experiments and standard approach , 2004, J. Comput. Chem..

[18]  L. Blancafort.  Excited-state potential energy surface for the photophysics of adenine. , 2006, Journal of the American Chemical Society.

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

[20]  B. Roos,et al.  Theoretical Study of the Electronic Spectrum of Cytosine , 1995 .

[21]  W. Domcke,et al.  Ab initio studies on the radiationless decay mechanisms of the lowest excited singlet states of 9H-adenine. , 2005, Journal of the American Chemical Society.

[22]  Shuhua Li,et al.  Ab initio study on deactivation pathways of excited 9H-guanine. , 2006, The Journal of chemical physics.

[23]  G. Fogarasi,et al.  Tautomers of cytosine and their excited electronic states: a matrix isolation spectroscopic and quantum chemical study. , 2011, Physical chemistry chemical physics : PCCP.

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

[25]  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 .

[26]  A. Savin,et al.  Combining multideterminantal wave functions with density functionals to handle near-degeneracy in atoms and molecules , 2002 .

[27]  Stefan Knecht,et al.  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. , 2013, The Journal of chemical physics.

[28]  Markus Reiher,et al.  Density matrix renormalization group with efficient dynamical electron correlation through range separation. , 2015, The Journal of chemical physics.

[29]  W. Thiel,et al.  Basis set effects on coupled cluster benchmarks of electronically excited states: CC3, CCSDR(3) and CC2 , 2010 .

[30]  A TDDFT study of the excited states of DNA bases and their assemblies. , 2006, The journal of physical chemistry. B.

[31]  L. Serrano-Andrés,et al.  A three-state model for the photophysics of adenine. , 2006, Chemistry.

[32]  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.

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

[34]  Johan Lorentzon,et al.  Theoretical Study of the Electronic Spectra of Uracil and Thymine , 1995 .

[35]  Andreas Savin,et al.  Long-range/short-range separation of the electron-electron interaction in density functional theory , 2004 .

[36]  Markus P. Fülscher,et al.  A Theoretical Study of the Electronic Spectra of Adenine and Guanine , 1997 .

[37]  C. Marian.  A new pathway for the rapid decay of electronically excited adenine. , 2005, The Journal of chemical physics.

[38]  Manuela Merchán,et al.  Ultrafast internal conversion of excited cytosine via the lowest pipi electronic singlet state. , 2003, Journal of the American Chemical Society.

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

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

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

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

[43]  S. Matsika.  Radiationless Decay of Excited States of Uracil through Conical Intersections , 2004 .

[44]  W. Thiel,et al.  Benchmarks of electronically excited states: basis set effects on CASPT2 results. , 2010, The Journal of chemical physics.

[45]  John M Herbert,et al.  Charge-transfer excited states in a pi-stacked adenine dimer, as predicted using long-range-corrected time-dependent density functional theory. , 2008, The journal of physical chemistry. B.

[46]  J. Kongsted,et al.  Polarizable embedding based on multiconfigurational methods: Current developments and the road ahead , 2014 .

[47]  K. Hirao,et al.  A long-range correction scheme for generalized-gradient-approximation exchange functionals , 2001 .

[48]  C. Crespo-Hernández,et al.  Ultrafast excited-state dynamics in nucleic acids. , 2004, Chemical reviews.

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

[50]  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.

[51]  Emmanuel Fromager,et al.  On the exact formulation of multi-configuration density-functional theory: electron density versus orbitals occupation , 2014, 1409.2326.

[52]  Rebecca K. Carlson,et al.  Multiconfiguration Pair-Density Functional Theory. , 2014, Journal of chemical theory and computation.

[53]  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.

[54]  James A. Platts,et al.  Hybrid density functional theory for π‐stacking interactions: Application to benzenes, pyridines, and DNA bases , 2006, J. Comput. Chem..