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Spectroscopic properties of OCS and OCCl+ by Møller–Plesset perturbation theory and configuration interaction
Ab initio calculations have been carried out on the stretching potential energy surfaces of OCS and the isoelectronic positive ion OCCl+. The methods used included fourth order Møller–Ple...
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The virial theorem has been used to derive sum rules for dipole- and mixed-dipole–quadrupole nuclear electric shieldings and corresponding geometrical derivatives of dipole and quadrupole moment...

Analytic evaluation of energy gradients for the singles and doubles coupled cluster method including perturbative triple excitations: Theory and applications to FOOF and Cr2

J. Chem. Phys. 94, 442 (1991); doi:10.1063/1.460359

Issue Date: 1 January 1991

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Gustavo E. Scuseria
Department of Chemistry and Rice Quantum Institute, Rice University, Houston, Texas 77251-1892
The analytic energy gradient for the singles and doubles coupled cluster method including a perturbative correction due to triple excitations [CCSD(T)] is formulated and computationally implemented. Encouraged by the recent success in reproducing the experimental equilibrium structure and vibrational frequencies of ozone, the new CCSD(T) gradient method is tested with two other ``difficult'' quantum chemistry problems: FOOF and Cr2. With the largest basis set employed in this work [triple zeta plus two sets of polarization functions (TZ2Pf)] at the CCSD(T) level of theory, the predictions for the O–O and O–F bond lengths in FOOF are 1.218 and 1.589 Å, respectively. These figures are in good agreement with the experimental values 1.216 and 1.575 Å. Based on CCSD calculations with even larger basis sets, it is concluded that the error of 0.014 Å in the O–F bond length at the TZ2Pf/CCSD(T) level of theory is due to the remaining basis set deficiency. On the other hand, the CCSD(T) prediction for the equilibrium bond length of Cr2 (1.604 Å), obtained with a large (10s8p3d2f1g) basis set capable of achieving the Hartree–Fock limit, is still 0.075 Å shorter than experiment, clearly indicating the importance of higher than connected triple excitations in a single-reference treatment of this particular problem. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 28 June 1990; accepted 21 September 1990
Permalink: http://link.aip.org/link/?JCPSA6/94/442/1
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KEYWORDS and PACS

Keywords
PACS
  • 34.20.Mq
    Atomic and molecular collision processes and interactions Interatomic and intermolecular potentials and forces, potential energy surfaces for collisions Potential energy surfaces for collisions
  • 31.20.Gm
    Electronic structure of atoms and molecules: theory Specific calculations and results Other accurate, or nearly ab initio calculations (MNDO method, SAMO method, etc.)
  • YEAR: 1990-91

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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