Numerical multiconfiguration self-consistent field study of the total (electronic and nuclear) parallel polarizability and hyperpolarizability for the OH, OH+, OH−

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Abstract
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.