Rotation-torsion spectra of HSOH, involving the vibrational ground state and the fundamental torsional state, have been simulated at T = 300 K. The simulations are carried out with the variational computer program TROVE in conjunction with recently reported ab initio potential energy and electric dipole moment surfaces. HSOH is a near-prolate-symmetric top at equilibrium and the simulated spectra are of perpendicular-band-type with strong R-branch and Q-branch transitions. Recently, an anomalous (b-type-transition)/(c-type-transition) intensity ratio in the vibrational-ground-state (r)Q(K(a))-branches of HSOH has been experimentally observed. Our calculations reproduce correctly the anomaly and show that it originates in the large-amplitude torsional motion of HSOH. We analyze our theoretical results in order to explain the effect and to provide unambiguous (b/c)-type-transition assignments.
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http://dx.doi.org/10.1039/c002803g | DOI Listing |
Phys Chem Chem Phys
August 2010
Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz 1, D-45470 Mülheim an der Ruhr, Germany.
Rotation-torsion spectra of HSOH, involving the vibrational ground state and the fundamental torsional state, have been simulated at T = 300 K. The simulations are carried out with the variational computer program TROVE in conjunction with recently reported ab initio potential energy and electric dipole moment surfaces. HSOH is a near-prolate-symmetric top at equilibrium and the simulated spectra are of perpendicular-band-type with strong R-branch and Q-branch transitions.
View Article and Find Full Text PDFPhys Chem Chem Phys
May 2005
Molecular- and Biophysics Group, Institute for Molecules and Materials, Radboud University Nijmegen, P.O. Box 9010, NL-6500 GL Nijmegen, The Netherlands.
The laser induced fluorescence spectra of several torsional transitions of the S1 <-- S0 electronic transition were recorded for the hydroxy deuterated o- and m-cresols. Both cis and trans rotamers were observed in a high resolution molecular beam experiment. The spectra were analyzed using a genetic algorithm assisted automatic assignment.
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