A simple practical procedure is proposed for the transformation of a complete-active-space self-consistent-field (CAS-SCF) wave function to Hehler-London valence bond space via the construction of an effective (Heisenberg) Hamiltonian. With such a procedure, the computed Heitler-London parameters Q and Kij can be used for a posteriori rationalization of the bonding effects in molecular structures. In particular, the diabatization of the adiabatic potential surface, first proposed by Evans can now be accomplished in a rigorous way. The technique is applied to some previously computed transition structures for cycloaddition reactions. © 1988 American Institute of Physics.
Bernardi, F., Olivucci, M., Mcdouall, J.J.W., Robb, M.A. (1988). Parametrization of a Heitler–London valence bond Hamiltonian from complete-active-space self-consistent-field computations: An application to chemical reactivity. THE JOURNAL OF CHEMICAL PHYSICS, 89(10), 6365-6375 [10.1063/1.455404].
Parametrization of a Heitler–London valence bond Hamiltonian from complete-active-space self-consistent-field computations: An application to chemical reactivity
Olivucci, M.;
1988-01-01
Abstract
A simple practical procedure is proposed for the transformation of a complete-active-space self-consistent-field (CAS-SCF) wave function to Hehler-London valence bond space via the construction of an effective (Heisenberg) Hamiltonian. With such a procedure, the computed Heitler-London parameters Q and Kij can be used for a posteriori rationalization of the bonding effects in molecular structures. In particular, the diabatization of the adiabatic potential surface, first proposed by Evans can now be accomplished in a rigorous way. The technique is applied to some previously computed transition structures for cycloaddition reactions. © 1988 American Institute of Physics.
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https://hdl.handle.net/11365/32927
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