The variational subspace valence bond method

Journal Article · Tue Apr 07 00:00:00 EDT 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4916743· OSTI ID:22415601

Fletcher, Graham D. ^[1]

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1. Argonne National Laboratory, 9700 South Cass Ave., Lemont, Illinois 60439 (United States)

The variational subspace valence bond (VSVB) method based on overlapping orbitals is introduced. VSVB provides variational support against collapse for the optimization of overlapping linear combinations of atomic orbitals (OLCAOs) using modified orbital expansions, without recourse to orthogonalization. OLCAO have the advantage of being naturally localized, chemically intuitive (to individually model bonds and lone pairs, for example), and transferrable between different molecular systems. Such features are exploited to avoid key computational bottlenecks. Since the OLCAO can be doubly occupied, VSVB can access very large problems, and calculations on systems with several hundred atoms are presented.

• OSTI ID: 22415601
• Journal Information: Journal of Chemical Physics, Vol. 142, Issue 13; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ATOMS
CHEMICAL BONDS
LCAO METHOD
MOLECULES
OPTIMIZATION
VALENCE
VARIATIONAL METHODS