title: Torsional electric dipole moment functions calculated for HOOH and ClOOCl.
abstract: The periodic torsional, electric dipole moment (EDM) functions μ(φ) = ∑m = 0pmcos (m + 1∕2)φ, of the atmospherically significant molecules HOOH and ClOOCl, have been derived from calculations at the CCSD(T) (coupled-cluster singles and doubles model, plus a noniterative triples correction) level of electronic-structure theory with augmented, correlation-consistent basis sets extrapolated to the approximate complete basis set limit. The μ(φ) of HOOH, defined by {pm} = {3.0979, -0.0301, -0.0058} D, is used to calculate squared transition EDMs that compare well with those previously derived using the experimental torsional line intensities. The μ(φ) of ClOOCl, defined by μ(φ) = {1.1935, 0.1163, 0.1341, -0.0040, -0.0099} D, requires a longer Fourier expansion because, in the range of dihedral angles from the cis (φ = 0) to the trans (φ = π) transition structures, three inflection points are found for ClOOCl, but only one for HOOH. The permanent EDM calculated for HOOH, 1.754 D, is in close agreement with the value deduced from experiment. Compared to HOOH, the permanent EDM vector calculated for ClOOCl is directed analogously, but has a significantly smaller magnitude, 0.700 D.
authors.affiliation: Department of Chemistry, University of California, Irvine, California 92697, USA. mark.mcgrath@uci.edu
authors.forename: Mark P
authors.initials: MP
authors.lastname: McGrath