A simple computational scheme for obtaining localized bonding schemes and their weights from a CASSCF wave function.

Abstract

We devise and apply a simple computational scheme for obtaining localized bonding schemes and their weights from a CASSCF wave function. These bonding schemes are close to resonance structures drawn by chemists. Firstly, a CASSCF wave function is computed. Secondly, the CASSCF computation is repeated but now the delocalized complete active space MOs are substituted by Weinhold's localized natural atomic orbitals. In this way the original CASSCF wave function is represented by a sequence of Slater determinants composed of localized natural atomic orbitals. Thus, a standard CASSCF wave function can be reinterpreted in terms of a local picture. To test the method we obtain localized bonding schemes and their weights for the ground and the pi-pi* excited state of ethylene. Moreover, bonding schemes and their weights are derived for the ground, the 1(1)B(u), and the 2(1)Ag pi-pi* excited states of trans-butadiene. The large weight bonding schemes are shown to be a qualitative indicator for the known photochemistry of butadiene. The remarkable stability of the Arduengo carbene is discussed by obtaining bonding schemes that indicate a stabilizing delocalization of the pi electrons. We illustrate that the large weight bonding schemes are in line with the observed reactivity of the Arduengo carbene.