Implementation of the locally renormalized CCSD(T) approaches for arbitrary reference function.

Several new variants of the locally-renormalized coupled-cluster (CC) approaches that account for the effect of triples (LR-CCSD(T)) have been formulated and implemented for arbitrary reference states using the TENSOR CONTRACTION ENGINE functionality, enabling the automatic generation of an efficient parallel code. Deeply rooted in the recently derived numerator-denominator-connected (NDC) expansion for the ground-state energy [K. Kowalski and P. Piecuch, J. Chem. Phys. 122, 074107 (2005)], LR-CCSD(T) approximations use, in analogy to the completely renormalized CCSD(T) (CR-CCSD(T)) approach, the three-body moments in constructing the noniterative corrections to the energies obtained in CC calculations with singles and doubles (CCSD). In contrast to the CR-CCSD(T) method, the LR-CCSD(T) approaches discussed in this paper employ local denominators, which assure the additive separability of the energies in the noninteracting system limit when the localized occupied spin-orbitals are employed in the CCSD and LR-CCSD(T) calculations. As clearly demonstrated on several challenging examples, including breaking the bonds of the F2, N2, and CN molecules, the LR-CCSD(T) approaches are capable of providing a highly accurate description of the entire potential-energy surface (PES), while maintaining the characteristic N(7) scaling of the ubiquitous CCSD(T) approach. Moreover, as illustrated numerically for the ozone molecule, the LR-CCSD(T) approaches yield highly competitive values for a number of equilibrium properties including bond lengths, angles, and harmonic frequencies.

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

[2]  Karol Kowalski,et al.  Extensive generalization of renormalized coupled-cluster methods. , 2005, The Journal of chemical physics.

[3]  Ludwik Adamowicz,et al.  Automated generation of coupled-cluster diagrams: implementation in the multireference state-specific coupled-cluster approach with the complete-active-space reference. , 2005, The Journal of chemical physics.

[4]  So Hirata,et al.  Combined coupled-cluster and many-body perturbation theories. , 2004, The Journal of chemical physics.

[5]  I. Hubač,et al.  Breaking N2 triple bond: the coupled-cluster corrected multi-reference configuration interaction description , 2004 .

[6]  Jeppe Olsen,et al.  A coupled cluster and full configuration interaction study of CN and CN , 2004 .

[7]  So Hirata,et al.  Higher-order equation-of-motion coupled-cluster methods. , 2004, The Journal of chemical physics.

[8]  Karol Kowalski,et al.  New coupled-cluster methods with singles, doubles, and noniterative triples for high accuracy calculations of excited electronic states. , 2004, The Journal of chemical physics.

[9]  S. Hirata.  Tensor Contraction Engine: Abstraction and Automated Parallel Implementation of Configuration-Interaction, Coupled-Cluster, and Many-Body Perturbation Theories , 2003 .

[10]  Michael J. McGuire,et al.  Recent advances in electronic structure theory: Method of moments of coupled-cluster equations and renormalized coupled-cluster approaches , 2002 .

[11]  Mihály Kállay,et al.  A general state-selective multireference coupled-cluster algorithm , 2002 .

[12]  Martin Head-Gordon,et al.  A perturbative correction to the quadratic coupled-cluster doubles method for higher excitations , 2002 .

[13]  P. Piecuch,et al.  A comparison of the renormalized and active-space coupled-cluster methods: Potential energy curves of BH and F2 , 2001 .

[14]  So Hirata,et al.  Erratum: “Perturbative corrections to coupled-cluster and equation-of-motion coupled-cluster energies: A determinantal analysis” [J. Chem. Phys. 114, 3919 (2001)] , 2001 .

[15]  Martin Head-Gordon,et al.  A second-order perturbative correction to the coupled-cluster singles and doubles method: CCSD(2) , 2001 .

[16]  So Hirata,et al.  Perturbative corrections to coupled-cluster and equation-of-motion coupled-cluster energies: A determinantal analysis , 2001 .

[17]  Jeppe Olsen,et al.  The initial implementation and applications of a general active space coupled cluster method , 2000 .

[18]  Jeppe Olsen,et al.  Full configuration interaction benchmarking of coupled-cluster models for the lowest singlet energy surfaces of N2 , 2000 .

[19]  Karol Kowalski,et al.  Renormalized CCSD(T) and CCSD(TQ) approaches: Dissociation of the N2 triple bond , 2000 .

[20]  Anna I. Krylov,et al.  Second order perturbation corrections to singles and doubles coupled-cluster methods: General theory and application to the valence optimized doubles model , 2000 .

[21]  J. Paldus,et al.  Reduced multireference coupled cluster method IV: open-shell systems , 2000 .

[22]  Karol Kowalski,et al.  The method of moments of coupled-cluster equations and the renormalized CCSD[T], CCSD(T), CCSD(TQ), and CCSDT(Q) approaches , 2000 .

[23]  Martin Head-Gordon,et al.  A second-order correction to singles and doubles coupled-cluster methods based on a perturbative expansion of a similarity-transformed Hamiltonian , 2000 .

[24]  S. Kucharski,et al.  Coupled-cluster methods with internal and semi-internal triply excited clusters: Vibrational spectrum of the HF molecule , 1999 .

[25]  R. Bartlett,et al.  Connected quadruples for the frequencies of O3 , 1999 .

[26]  Josef Paldus,et al.  Simultaneous handling of dynamical and nondynamical correlation via reduced multireference coupled cluster method: Geometry and harmonic force field of ozone , 1999 .

[27]  I. Grabowski,et al.  A COUPLED-CLUSTER CORRECTION TO THE MULTI-REFERENCE CONFIGURATION INTERACTION METHOD , 1999 .

[28]  J. Paldus,et al.  Reduced multireference couple cluster method. II. Application to potential energy surfaces of HF, F2, and H2O , 1998 .

[29]  R. Bartlett,et al.  COUPLED-CLUSTER CALCULATIONS OF STRUCTURE AND VIBRATIONAL FREQUENCIES OF OZONE : ARE TRIPLE EXCITATIONS ENOUGH? , 1998 .

[30]  J. Paldus,et al.  Externally corrected singles and doubles coupled cluster methods for open-shell systems. II. Applications to the low lying doublet states of OH, NH2, CH3 and CN radicals , 1998 .

[31]  J. Stanton.  Why CCSD(T) works: a different perspective , 1997 .

[32]  H. Schaefer,et al.  Molecular geometry and vibrational frequencies of ozone from compact variational wave functions explicitly including triple and quadruple substitutions , 1997 .

[33]  Josef Paldus,et al.  Reduced multireference CCSD method: An effective approach to quasidegenerate states , 1997 .

[34]  D. Yarkony,et al.  Modern Electronic Structure Theory: Part I , 1995 .

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

[36]  John F. Stanton,et al.  Perturbative treatment of the similarity transformed Hamiltonian in equation‐of‐motion coupled‐cluster approximations , 1995 .

[37]  P. Piecuch,et al.  BREAKING BONDS WITH THE STATE-SELECTIVE MULTIREFERENCE COUPLED-CLUSTER METHOD EMPLOYING THE SINGLE-REFERENCE FORMALISM , 1995 .

[38]  Ludwik Adamowicz,et al.  STATE-SELECTIVE MULTIREFERENCE COUPLED-CLUSTER THEORY EMPLOYING THE SINGLE-REFERENCE FORMALISM : IMPLEMENTATION AND APPLICATION TO THE H8 MODEL SYSTEM , 1994 .

[39]  Mark S. Gordon,et al.  General atomic and molecular electronic structure system , 1993, J. Comput. Chem..

[40]  Ludwik Adamowicz,et al.  Multireference coupled cluster method for electronic structure of molecules , 1993 .

[41]  Ludwik Adamowicz,et al.  A state-selective multireference coupled-cluster theory employing the single-reference formalism , 1993 .

[42]  R. Bartlett,et al.  The coupled‐cluster single, double, triple, and quadruple excitation method , 1992 .

[43]  N. Oliphant,et al.  Coupled‐cluster method truncated at quadruples , 1991 .

[44]  John F. Stanton,et al.  A benchmark coupled-cluster single, double, and triple excitation (CCSDT) study of the structure and harmonic vibrational frequencies of the ozone molecule☆ , 1991 .

[45]  Gustavo E. Scuseria,et al.  The vibrational frequencies of ozone , 1990 .

[46]  M. Head‐Gordon,et al.  A fifth-order perturbation comparison of electron correlation theories , 1989 .

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

[48]  Henry F. Schaefer,et al.  A new implementation of the full CCSDT model for molecular electronic structure , 1988 .

[49]  Rodney J. Bartlett,et al.  Erratum: The full CCSDT model for molecular electronic structure [J. Chem. Phys. 86, 7041 (1987)] , 1988 .

[50]  R. Bartlett,et al.  The full CCSDT model for molecular electronic structure , 1987 .

[51]  R. Bartlett,et al.  The description of N2 and F2 potential energy surfaces using multireference coupled cluster theory , 1987 .

[52]  S. J. Cole,et al.  Towards a full CCSDT model for electron correlation , 1985 .

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

[54]  T. H. Dunning.  Gaussian Basis Functions for Use in Molecular Calculations. III. Contraction of (10s6p) Atomic Basis Sets for the First‐Row Atoms , 1970 .