Vibrational contributions to the molecular polarizability and hyperpolarizabilities are calculated for OH, OH+, and OH- for an electric field directed along the bond axis. It was found that vibrational averaging of the polarizability works reasonably well for OH and OH-, but fails for OH+, giving a result 16% to low. For the hyperpolarizabilities, the vibrational averaging strongly underestimates the vibronic contribution, whose size can exceed the electronic contribution, and therefore disqualifies this procedure for evaluation of these types of higher-order molecular properties.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry