Embedding wave function theory in density functional theory.

We present a framework for embedding a highly accurate coupled-cluster calculation within a larger density functional calculation. We use a perturbative buffer to help insulate the coupled-cluster region from the rest of the system. Regions are defined, not in real space, but in Hilbert space, though connection between the two can be made by spatial localization of single-particle orbitals. Relations between our embedding approach and some similar techniques are discussed. We present results for small sample systems for which we can extract essentially exact results, demonstrating that our approach seems to work quite well and is generally more reliable than some of the related approaches due to the introduction of additional interaction terms.

[1]  Jing Ma,et al.  Linear scaling local correlation approach for solving the coupled cluster equations of large systems , 2002, J. Comput. Chem..

[2]  M. Karplus,et al.  Combining ab initio and density functional theories with semiempirical methods , 2002 .

[3]  Christian Ochsenfeld,et al.  Linear and sublinear scaling formation of Hartree-Fock-type exchange matrices , 1998 .

[4]  D R Yarkony,et al.  Modern electronic structure theory , 1995 .

[5]  John F. Stanton,et al.  Applications of Post‐Hartree—Fock Methods: A Tutorial , 2007 .

[6]  T. Pakkanen,et al.  Chemisorption theory for metallic surfaces: Electron localization and the description of surface interactions , 1980 .

[7]  David E. Woon,et al.  Gaussian basis sets for use in correlated molecular calculations. IV. Calculation of static electrical response properties , 1994 .

[8]  C. David Sherrill,et al.  The Configuration Interaction Method: Advances in Highly Correlated Approaches , 1999 .

[9]  Emily A. Carter,et al.  Periodic density functional embedding theory for complete active space self-consistent field and configuration interaction calculations: Ground and excited states , 2002 .

[10]  Hans-Joachim Werner,et al.  Low-order scaling local electron correlation methods. IV. Linear scaling local coupled-cluster (LCCSD) , 2001 .

[11]  Leslie Greengard,et al.  A fast algorithm for particle simulations , 1987 .

[12]  Michael J. Frisch,et al.  A linear scaling method for Hartree–Fock exchange calculations of large molecules , 1996 .

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

[14]  Benjamin G. Janesko,et al.  Explicitly correlated divide-and-conquer-type electronic structure calculations based on two-electron reduced density matrices , 2003 .

[15]  R. Parr.  Density-functional theory of atoms and molecules , 1989 .

[16]  K. Morokuma,et al.  A NEW ONIOM IMPLEMENTATION IN GAUSSIAN98. PART I. THE CALCULATION OF ENERGIES, GRADIENTS, VIBRATIONAL FREQUENCIES AND ELECTRIC FIELD DERIVATIVES , 1999 .

[17]  John F. Stanton,et al.  On the extent of spin contamination in open‐shell coupled‐cluster wave functions , 1994 .

[18]  Rodney J. Bartlett,et al.  COUPLED-CLUSTER THEORY: AN OVERVIEW OF RECENT DEVELOPMENTS , 1995 .

[19]  Rodney J. Bartlett,et al.  Analytic energy derivatives in many‐body methods. I. First derivatives , 1989 .

[20]  Dennis R. Salahub,et al.  Kohn-Sham orbitals and orbital energies: fictitious constructs but good approximations all the same , 2002 .

[21]  Philippe Y. Ayala,et al.  Linear scaling coupled cluster and perturbation theories in the atomic orbital basis , 1999 .

[22]  P. C. Hariharan,et al.  The influence of polarization functions on molecular orbital hydrogenation energies , 1973 .

[23]  Gregory S. Tschumper,et al.  Gauging the applicability of ONIOM (MO/MO) methods to weak chemical interactions in large systems: hydrogen bonding in alcohol dimers , 2002 .

[24]  R. Bartlett.  Many-Body Perturbation Theory and Coupled Cluster Theory for Electron Correlation in Molecules , 1981 .

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

[26]  R. Bartlett,et al.  A full coupled‐cluster singles and doubles model: The inclusion of disconnected triples , 1982 .

[27]  R. Bartlett,et al.  Can simple localized bond orbitals and coupled cluster methods predict reliable molecular energies , 1985 .

[28]  K. Morokuma,et al.  On the application of the IMOMO (integrated molecular orbital + molecular orbital) method , 2000 .

[29]  S. F. Boys,et al.  Canonical Configurational Interaction Procedure , 1960 .

[30]  K. Burke,et al.  Generalized Gradient Approximation Made Simple [Phys. Rev. Lett. 77, 3865 (1996)] , 1997 .

[31]  John P. Perdew,et al.  Optimized effective potential made simple: Orbital functionals, orbital shifts, and the exact Kohn-Sham exchange potential , 2003, cond-mat/0303396.

[32]  Eric Schwegler,et al.  Linear scaling computation of the Hartree–Fock exchange matrix , 1996 .

[33]  K. Morokuma,et al.  ONIOM: A Multilayered Integrated MO + MM Method for Geometry Optimizations and Single Point Energy Predictions. A Test for Diels−Alder Reactions and Pt(P(t-Bu)3)2 + H2 Oxidative Addition , 1996 .

[34]  Klaus Ruedenberg,et al.  Localized Atomic and Molecular Orbitals , 1963 .

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

[36]  R. Dreizler,et al.  Density-Functional Theory , 1990 .

[37]  N. Govind,et al.  Electronic-structure calculations by first-principles density-based embedding of explicitly correlated systems , 1999 .

[38]  R. Bartlett.  Coupled-cluster approach to molecular structure and spectra: a step toward predictive quantum chemistry , 1989 .

[39]  Gustavo E. Scuseria,et al.  Linear Scaling Density Functional Calculations with Gaussian Orbitals , 1999 .

[40]  A. Görling,et al.  Efficient localized Hartree-Fock methods as effective exact-exchange Kohn-Sham methods for molecules , 2001 .

[41]  Weitao Yang,et al.  A density‐matrix divide‐and‐conquer approach for electronic structure calculations of large molecules , 1995 .

[42]  Paul G. Mezey,et al.  A fast intrinsic localization procedure applicable for ab initio and semiempirical linear combination of atomic orbital wave functions , 1989 .

[43]  Josef Paldus,et al.  A Critical Assessment of Coupled Cluster Method in Quantum Chemistry , 2007 .