Equations of the random-phase approximation (RPA) for high-spin open-shell molecules are derived using the time-dependent variational principle and a unitary exponential representation of the high-spin determinantal wave function parametrized with a nonredundant set of variational parameters. The restricted open-shell RPA theory is applied to derive expressions for the polarization propagator, and for the dispersion energy of high-spin open-shell complexes. It is also used to define the intramonomer correlation expansions of the RPA dispersion energy using various Møller–Plesset-type partitionings of the Hamiltonian. A close relation between the present treatment and the multipole expansion approach of Hettema and Wormer [H. Hettema and P. E. S. Wormer, J. Chem. Phys. 93, 3389 (1990)] is established and discussed. Numerical results for various high-spin open-shell–closed-shell and open-shell–open-shell complexes are presented. Comparison of the dispersion energy computed in the random phase approximation with highly correlated results from the full configuration interaction or coupled-cluster singles, doubles, and approximate triples calculations shows that the random phase approximation accounts for the major part of the intramonomer correlation effects in the dispersion energy. For open-shell–closed-shell complexes the convergence of the intramonomer correlation expansion through the second order is very good, while for the more difficult case of open-shell–open-shell complexes is much less satisfactory, and full RPA calculations are necessary to get reliable results.
Skip Nav Destination
Article navigation
22 November 2003
Research Article|
November 22 2003
Dispersion interaction of high-spin open-shell complexes in the random phase approximation
Piotr S. Żuchowski;
Piotr S. Żuchowski
Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland
Search for other works by this author on:
Béatrice Bussery-Honvault;
Béatrice Bussery-Honvault
Laboratoire PALMS, UMR 6627 du CNRS, Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France
Search for other works by this author on:
Robert Moszynski;
Robert Moszynski
Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland
Search for other works by this author on:
Bogumil Jeziorski
Bogumil Jeziorski
Department of Chemistry, University of Warsaw, Pasteura 1, 02-093 Warsaw, Poland
Search for other works by this author on:
J. Chem. Phys. 119, 10497–10511 (2003)
Article history
Received:
July 14 2003
Accepted:
August 28 2003
Citation
Piotr S. Żuchowski, Béatrice Bussery-Honvault, Robert Moszynski, Bogumil Jeziorski; Dispersion interaction of high-spin open-shell complexes in the random phase approximation. J. Chem. Phys. 22 November 2003; 119 (20): 10497–10511. https://doi.org/10.1063/1.1620496
Download citation file:
Pay-Per-View Access
$40.00
Sign In
You could not be signed in. Please check your credentials and make sure you have an active account and try again.
Citing articles via
DeePMD-kit v2: A software package for deep potential models
Jinzhe Zeng, Duo Zhang, et al.
CREST—A program for the exploration of low-energy molecular chemical space
Philipp Pracht, Stefan Grimme, et al.
Rubber wear: Experiment and theory
B. N. J. Persson, R. Xu, et al.
Related Content
On the convergence of Z-averaged perturbation theory
J. Chem. Phys. (February 2008)
An empirical extrapolation scheme for efficient treatment of induced dipoles
J. Chem. Phys. (October 2016)
Grid-free density functional calculations on periodic systems
J. Chem. Phys. (September 2007)
The subtleties of explicitly correlated Z-averaged perturbation theory: Choosing an R12 method for high-spin open-shell molecules
J. Chem. Phys. (December 2009)
Rules of pair electron correlation in MF(M=H, Li, Na)
J. Chem. Phys. (November 2001)