Polarizabilities and hyperpolarizabilities<fnoteref idrefs="fn1" presence="notmissing"></fnoteref><footnote id="fn1">In memoriam of David M. Bishop.</footnote>

Abstract

This chapter presents and discusses recent achievements towards determining and interpreting polarizabilities and hyperpolarizabilities of atoms, molecules, clusters, supramolecular assemblies, polymers, and aggregates. It evidences both the strong activities in the field and their dual character. Indeed, on the one hand, the polarizabilities and even more the hyperpolarizabilities are difficult quantities to predict, so that they are ideal targets when elaborating new calculation methods. This comes from the fact that many aspects need to be addressed in their evaluation: vibrational versus electronic contributions, frequency dispersion including resonance, electron correlation and relativistic effects, impact of the surroundings. On the other hand, linear and nonlinear responses are evaluated in a strategy of designing new systems with remarkable electric, magnetic, and optical properties. In this second motivation for calculating the polarizabilities and hyperpolarizabilities, the emphasis is also put on the interpretation and the deduction of structure-property relationships while these investigations are parts of multidisciplinary approaches including synthetic and experimental characterizations.