Selection rules and line-strength factors for multiphoton transitions in gas phase molecular spectroscopy |
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Authors: | Stephen E Bialkowski William A Guillory |
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Institution: | Department of Chemistry and Chemical Engineering, Michigan Technological University, Houghton, Michigan 49931, USA;Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, USA |
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Abstract: | Multiphoton transitions are discussed in terms applicable to experimental spectroscopy. A simple tensor operator for the equations governing multiphoton transitions in molecules is obtained. Selection rules for these processes are derived by symmetry considerations and procedures for calculation of rotational line-strength factors are given. For the general transition, the rovibronic n-photon selection rules can be determined by the symmetry product of a n-photon operator with the rovibronic wavefunctions. The line-strength factors are found by considering the integral over rotations of the nth rank tensor operators. The line-strength evaluations do not depend on exact knowledge of the vibronic overlap, to within a constant factor. |
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