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Information‐theoretic analysis of rotational distributions from quantal and quasiclassical computations of reactive and nonreactive scattering
Author(s) -
Bernstein R. B.
Publication year - 2009
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.560100829
Subject(s) - moment (physics) , rotational partition function , computation , rotational energy , relaxation (psychology) , scattering , excitation , exponential function , statistical physics , classical mechanics , physics , chemistry , angular momentum , rotational transition , quantum mechanics , mathematics , mathematical analysis , algorithm , psychology , social psychology
An information‐theoretic approach to the analysis of rotational excitation cross sections was developed by Levine, Bernstein, Johnson, Procaccia, and coworkers and applied to state‐to‐state cross sections available from numerical computations of reactive and nonreactive scattering (for example, by Wyatt and Kuppermann and their coworkers and by Pack and Pattengill and others). The rotational surprisals are approximately linear in the energy transferred, thereby accounting for the so‐called “exponential gap law” for rotational relaxation discovered experimentally by Polanyi, Woodall, and Ding. For the “linear surprisal” case the unique relation between the surprisal parameter θ R and the first moment of the rotational energy distribution provides a link between the pattern of the rotational state distribution and those features of the potential surface which govern the average energy transfer.