A fast doubly hybrid density functional method close to chemical accuracy using a local opposite spin ansatz

We develop and validate the XYGJ-OS functional, based on the adiabatic connection formalism and Görling-Levy perturbation theory to second order and using the opposite-spin (OS) ansatz combined with locality of electron correlation. XYGJ-OS with local implementation scales as N3 with an overall accuracy of 1.28 kcal/mol for thermochemistry, bond dissociation energies, reaction barrier heights, and nonbonded interactions, comparable to that of 1.06 kcal/mol for the accurate coupled-cluster based G3 method (scales as N7) and much better than many popular density functional theory methods: B3LYP (4.98), PBE0 (4.36), and PBE (12.10).

[1]  S. Grimme,et al.  A thorough benchmark of density functional methods for general main group thermochemistry, kinetics, and noncovalent interactions. , 2011, Physical chemistry chemical physics : PCCP.

[2]  Igor Ying Zhang,et al.  Doubly hybrid density functional for accurate description of thermochemistry, thermochemical kinetics and nonbonded interactions , 2011 .

[3]  A. Savin,et al.  Double-hybrid density-functional theory made rigorous. , 2010, The Journal of chemical physics.

[4]  Laurent Nahon,et al.  Synchrotron vacuum ultraviolet radiation studies of the D-1 Pi(u) state of H-2 (Correction of vol 133, 144317, 2010) , 2011 .

[5]  Igor Ying Zhang,et al.  Basis set dependence of the doubly hybrid XYG3 functional. , 2010, The Journal of chemical physics.

[6]  Igor Ying Zhang,et al.  XYG3s: Speedup of the XYG3 fifth-rung density functional with scaling-all-correlation method. , 2010, The Journal of chemical physics.

[7]  Igor Ying Zhang,et al.  Extending the reliability and applicability of B3LYP. , 2010, Chemical communications.

[8]  Igor Ying Zhang,et al.  Trends in R-X Bond Dissociation Energies (R(•) = Me, Et, i-Pr, t-Bu, X(•) = H, Me, Cl, OH). , 2010, Journal of chemical theory and computation.

[9]  S. Grimme,et al.  A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. , 2010, The Journal of chemical physics.

[10]  Stefan Grimme,et al.  A General Database for Main Group Thermochemistry, Kinetics, and Noncovalent Interactions - Assessment of Common and Reparameterized (meta-)GGA Density Functionals. , 2010, Journal of chemical theory and computation.

[11]  M. Head‐Gordon,et al.  Long-range corrected double-hybrid density functionals. , 2009, The Journal of chemical physics.

[12]  J C Sancho-García,et al.  Assessment of double-hybrid energy functionals for pi-conjugated systems. , 2009, The Journal of chemical physics.

[13]  Stefan Grimme,et al.  Optimization and basis-set dependence of a restricted-open-shell form of B2-PLYP double-hybrid density functional theory. , 2009, The journal of physical chemistry. A.

[14]  W. Goddard,et al.  Doubly hybrid density functional for accurate descriptions of nonbond interactions, thermochemistry, and thermochemical kinetics , 2009, Proceedings of the National Academy of Sciences.

[15]  George C Schatz,et al.  Highly accurate first-principles benchmark data sets for the parametrization and validation of density functional and other approximate methods. Derivation of a robust, generally applicable, double-hybrid functional for thermochemistry and thermochemical kinetics. , 2008, The journal of physical chemistry. A.

[16]  Martin Head-Gordon,et al.  Semiempirical double-hybrid density functional with improved description of long-range correlation. , 2008, The journal of physical chemistry. A.

[17]  D. Truhlar,et al.  The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals , 2008 .

[18]  Donald G Truhlar,et al.  Density functionals with broad applicability in chemistry. , 2008, Accounts of chemical research.

[19]  Dong H. Zhang,et al.  A transition state wave packet study of the H+CH4 reaction. , 2007, The Journal of chemical physics.

[20]  Xin Xu,et al.  The X1 method for accurate and efficient prediction of heats of formation. , 2007, The Journal of chemical physics.

[21]  T. Takatani,et al.  Performance of spin-component-scaled Møller-Plesset theory (SCS-MP2) for potential energy curves of noncovalent interactions. , 2007, Physical chemistry chemical physics : PCCP.

[22]  Yihan Shao,et al.  Fast evaluation of scaled opposite spin second‐order Møller–Plesset correlation energies using auxiliary basis expansions and exploiting sparsity , 2007, J. Comput. Chem..

[23]  S. Grimme,et al.  Double-hybrid density functionals with long-range dispersion corrections: higher accuracy and extended applicability. , 2007, Physical chemistry chemical physics : PCCP.

[24]  Weitao Yang,et al.  Many-electron self-interaction error in approximate density functionals. , 2006, The Journal of chemical physics.

[25]  D. Truhlar,et al.  A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions. , 2006, The Journal of chemical physics.

[26]  S. Grimme,et al.  Towards chemical accuracy for the thermodynamics of large molecules: new hybrid density functionals including non-local correlation effects. , 2006, Physical chemistry chemical physics : PCCP.

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

[28]  Jirí Cerný,et al.  Benchmark database of accurate (MP2 and CCSD(T) complete basis set limit) interaction energies of small model complexes, DNA base pairs, and amino acid pairs. , 2006, Physical chemistry chemical physics : PCCP.

[29]  Weitao Yang,et al.  Self-interaction-free exchange-correlation functional for thermochemistry and kinetics. , 2006, The Journal of chemical physics.

[30]  Filipp Furche,et al.  The performance of semilocal and hybrid density functionals in 3d transition-metal chemistry. , 2006, The Journal of chemical physics.

[31]  S. Grimme Semiempirical hybrid density functional with perturbative second-order correlation. , 2006, The Journal of chemical physics.

[32]  Weitao Yang,et al.  Orbital-dependent correlation energy in density-functional theory based on a second-order perturbation approach: success and failure. , 2005, The Journal of chemical physics.

[33]  Leo Radom,et al.  Trends in R-X bond dissociation energies (R = Me, Et, i-Pr, t-Bu; X = H, CH3, OCH3, OH, F): a surprising shortcoming of density functional theory. , 2005, The journal of physical chemistry. A.

[34]  Per Linse,et al.  Monte Carlo simulations of oppositely charged macroions in solution. , 2005, The Journal of chemical physics.

[35]  Donald G Truhlar,et al.  Design of density functionals that are broadly accurate for thermochemistry, thermochemical kinetics, and nonbonded interactions. , 2005, The journal of physical chemistry. A.

[36]  Martin Head-Gordon,et al.  Auxiliary basis expansions for large-scale electronic structure calculations. , 2005, Proceedings of the National Academy of Sciences of the United States of America.

[37]  Donald G Truhlar,et al.  Benchmark database of barrier heights for heavy atom transfer, nucleophilic substitution, association, and unimolecular reactions and its use to test theoretical methods. , 2005, The journal of physical chemistry. A.

[38]  Martin Head-Gordon,et al.  Scaled opposite-spin second order Møller-Plesset correlation energy: an economical electronic structure method. , 2004, The Journal of chemical physics.

[39]  Donald G. Truhlar,et al.  Doubly Hybrid Meta DFT: New Multi-Coefficient Correlation and Density Functional Methods for Thermochemistry and Thermochemical Kinetics , 2004 .

[40]  Xin Xu,et al.  From The Cover: The X3LYP extended density functional for accurate descriptions of nonbond interactions, spin states, and thermochemical properties. , 2004, Proceedings of the National Academy of Sciences of the United States of America.

[41]  G. Scuseria,et al.  Climbing the density functional ladder: nonempirical meta-generalized gradient approximation designed for molecules and solids. , 2003, Physical review letters.

[42]  S. Grimme Improved second-order Møller–Plesset perturbation theory by separate scaling of parallel- and antiparallel-spin pair correlation energies , 2003 .

[43]  L. Curtiss,et al.  Gaussian-3X (G3X) theory : use of improved geometries, zero-point energies, and Hartree-Fock basis sets. , 2001 .

[44]  L. Curtiss,et al.  Assessment of Gaussian-3 and density functional theories for a larger experimental test set , 2000 .

[45]  L. Curtiss,et al.  Gaussian-3 (G3) theory for molecules containing first and second-row atoms , 1998 .

[46]  Holger Patzelt,et al.  RI-MP2: optimized auxiliary basis sets and demonstration of efficiency , 1998 .

[47]  Krishnan Raghavachari,et al.  Assessment of Gaussian-2 and density functional theories for the computation of ionization potentials and electron affinities , 1998 .

[48]  Vincenzo Barone,et al.  Exchange functionals with improved long-range behavior and adiabatic connection methods without adjustable parameters: The mPW and mPW1PW models , 1998 .

[49]  Burke,et al.  Generalized Gradient Approximation Made Simple. , 1996, Physical review letters.

[50]  Kohn,et al.  Density functional and density matrix method scaling linearly with the number of atoms. , 1996, Physical review letters.

[51]  A. Becke Density-functional thermochemistry. , 1996 .

[52]  M. Frisch,et al.  Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields , 1994 .

[53]  Görling,et al.  Exact Kohn-Sham scheme based on perturbation theory. , 1994, Physical review. A, Atomic, molecular, and optical physics.

[54]  Martin W. Feyereisen,et al.  Use of approximate integrals in ab initio theory. An application in MP2 energy calculations , 1993 .

[55]  Görling,et al.  Correlation-energy functional and its high-density limit obtained from a coupling-constant perturbation expansion. , 1993, Physical review. B, Condensed matter.

[56]  A. Becke Density-functional thermochemistry. III. The role of exact exchange , 1993 .

[57]  A. Becke A New Mixing of Hartree-Fock and Local Density-Functional Theories , 1993 .

[58]  Wang,et al.  Accurate and simple analytic representation of the electron-gas correlation energy. , 1992, Physical review. B, Condensed matter.

[59]  Axel D. Becke,et al.  Density-functional thermochemistry. I. The effect of the exchange-only gradient correction , 1992 .

[60]  Jan Almlöf,et al.  Elimination of energy denominators in Møller—Plesset perturbation theory by a Laplace transform approach , 1991 .

[61]  Yang,et al.  Direct calculation of electron density in density-functional theory. , 1991, Physical review letters.

[62]  A. Becke,et al.  Density-functional exchange-energy approximation with correct asymptotic behavior. , 1988, Physical review. A, General physics.

[63]  Parr,et al.  Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density. , 1988, Physical review. B, Condensed matter.

[64]  J. Perdew,et al.  Hellmann-Feynman, virial, and scaling requisites for the exact universal density functionals. Shape of the correlation potential and diamagnetic susceptibility for atoms. , 1985, Physical review. A, General physics.

[65]  S. H. Vosko,et al.  Accurate spin-dependent electron liquid correlation energies for local spin density calculations: a critical analysis , 1980 .

[66]  M. Levy Universal variational functionals of electron densities, first-order density matrices, and natural spin-orbitals and solution of the v-representability problem. , 1979, Proceedings of the National Academy of Sciences of the United States of America.

[67]  John P. Perdew,et al.  Exchange-correlation energy of a metallic surface: Wave-vector analysis , 1977 .

[68]  B. Lundqvist,et al.  Exchange and correlation in atoms, molecules, and solids by the spin-density-functional formalism , 1976 .

[69]  W. Kohn,et al.  Self-Consistent Equations Including Exchange and Correlation Effects , 1965 .

[70]  P. Hohenberg,et al.  Inhomogeneous Electron Gas , 1964 .

[71]  P. Dirac Note on Exchange Phenomena in the Thomas Atom , 1930, Mathematical Proceedings of the Cambridge Philosophical Society.