Use of exchange maximization to generate starting vectors for self-consistent field calculations on metal cluster/adsorbate systems

• Published in: Journal of computational chemistry Vol. 23; no. 10; pp. 943 - 949
• Main Authors: Buenker, R. J., Whitten, J. L., Izgorodina, E. I., Liebermann, H.-P., Kokh, D. B.
• Format: Journal Article
• Language: English
• Published: New York Wiley Subscription Services, Inc., A Wiley Company 30.07.2002
• Subjects: metal cluster/adsorbate systems; self-consistent field calculations; starting vectors
• ISSN: 0192-8651; 1096-987X
• DOI: 10.1002/jcc.10094

Localized molecular orbitals (LMOs) derived from exchange maximization with respect to all atom‐centered basis functions in the basis set are shown to generate a good starting electronic field for self‐consistent field calculations on extended systems such as metal clusters, for which well‐defined chemical bonds are not present. Examples studied are a cluster of 20 Ni atoms and the Pt97CO, Ag43/H3CNON, Ag91/H2CO, and vinylidene/Ni metal cluster plus adsorbate systems. It is also shown that improved starting vectors can be obtained by remixing a subset of the LMOs with the largest exchange eigenvalues through diagonalization of the Fock matrix computed with a null electronic field. Employing only a subset of the exchange‐maximized LMOs in the first iterations, and then gradually expanding the space in which the diagonalizations are carried out in succeeding cycles, is shown to be an effective means of guiding the SCF procedure to the converged full‐basis solution. © 2002 Wiley Periodicals, Inc. J Comput Chem 23: 943–949, 2002