Elsevier

Chemical Physics Letters

Volume 150, Issue 6, 23 September 1988, Pages 406-415
Chemical Physics Letters

An efficient closed-shell singles and doubles coupled-cluster method

https://doi.org/10.1016/0009-2614(88)80427-5Get rights and content

Abstract

A reformulated set of equations for the closed-shell singles and doubles coupled-cluster (CCSD) method is presented. A computational cost of 12nv4n02+7nv3n03+1nv2n04 for the n6 steps is obtained, where nv is the number of virtual molecular orbitals included in the CCSD procedure, n0 is the number of doubly occupied molecular orbitals and n=n0+nv. Test calculations for the cis and trans isomers of FNNF and planar and pyramidal CH3 are presented. Equilibrium structures determined with large Gaussian basis sets at the second-order Møller-Plesset (MP2) perturbation level of theory are reported and used for the other electron correlation methods. With the largest one-particle basis set (144 contracted Gaussian functions), the equilibrium geometries of cis- and trans-FNNF agree with experiment. Based on analyses of planar and pyramidal CH3 wavefunctions and the calculated inversion barrier, it is suggested that the molecular anion may not exist in a planar configuration but that autodetachment of an electron occurs before the transition state is reached. Comparisons of our new CCSD procedure demonstrate that coupled-cluster methods are not significantly more expensive than similar electron correlation techniques.

References (55)

  • A.C. Scheiner et al.

    J. Chem. Phys.

    (1987)
  • G.E. Scuseria et al.

    Chem. Phys. Letters

    (1986)
  • C.E. Dykstra et al.

    Chem. Phys. Letters

    (1988)
  • G.W. Trucks et al.

    Chem. Phys. Letters

    (1988)
  • W.D. Laidig et al.

    Chem. Phys. Letters

    (1984)
  • M. Hoffmann et al.

    J. Chem. Phys.

    (1988)
  • G.E. Scuseria et al.

    Intern. J. Quantum Chem. Symp.

    (1987)
  • S. Huzinaga

    J. Chem. Phys.

    (1965)
  • W.J. Hehre et al.
    (1986)
  • E.D. Simandiras

    Ph.D. Thesis, Cambridge

    (1988)
  • F. Driessler et al.

    Theoret. Chim. Acta

    (1973)
  • R.J. Bartlett

    Ann. Rev. Phys. Chem.

    (1981)
  • J. Paldus
  • R.J. Bartlett et al.
  • J. Číẑek

    J. Chem. Phys.

    (1966)
    J. Číẑek

    Advan. Chem. Phys.

    (1969)
  • J. Noga et al.

    J. Chem. Phys.

    (1987)
  • G.E. Scuseria et al.

    Chem. Phys. Letters

    (1988)
  • G. Fitzgerald et al.

    Chem. Phys. Letters

    (1985)
  • U. Kaldor

    J. Chem. Phys.

    (1987)
  • B. Jeziorski et al.

    J. Chem. Phys.

    (1988)
  • R.J. Bartlett et al.

    Intern. J. Quantum Chem.

    (1978)
  • T.J. Lee et al.

    Chem. Phys. Letters

    (1987)
  • S.J. Cole et al.

    J. Chem. Phys.

    (1987)
  • G.E. Scuseria et al.

    J. Chem. Phys.

    (1987)
  • P. Pulay et al.

    J. Chem. Phys.

    (1984)
  • P. Carsky et al.

    J. Chem. Phys.

    (1987)
  • T.J. Lee and J.E. Rice, to be...
  • Cited by (0)

    1

    NATO/NSF Postdoctoral Fellow.

    2

    Research Fellow at Newnham College, Cambridge.

    View full text