Mode localization in highly excited vibrational states: Fundamentals of structure in overtone and multiphoton spectra

Abstract

Fundamental classical and quantum arguments are presented that strongly indicate that the usual arguments leading to the expectation that the high vibrational states of polyatomic molecules form exclusively a uniform mode-mixed quasicontinuum are flawed. The basic dynamics shows that a uniform mode-mixed quasicontinuum exists but embedded in it can be mode-localized states characterized by extreme motion. Experimental evidence for these ideas is reviewed. © 1984.