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Rotational decoupling of vibrational modes due to rotational excitation: Application to a model of the HDO stretching motions
Author(s) -
Shirts Randall B.
Publication year - 1987
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560310114
Subject(s) - decoupling (probability) , excitation , rotation around a fixed axis , intramolecular force , chemistry , quantum , kinetic energy , kinetic isotope effect , coupling (piping) , atomic physics , vibration , molecular physics , physics , classical mechanics , quantum mechanics , deuterium , materials science , control engineering , engineering , metallurgy
Rotational motion can have a significant effect on intramolecular vibrational dynamics. In this paper, we explore the recently discovered phenomenon of rotational decoupling through both quantum mechanical and classical methods. It is found in a model system for the stretching motions of HDO, that rotational motion about the c axis can decouple the stretches. This fact can be understood as a cancellation between kinetic and centrifugal coupling as illuminated using classical resonance analysis and quantum matrix element calculations. The significance of this phenomenon is discussed in infrared multiple photon absorption experiments with specific application to isotope separation in HDO.