Theory of electro-optical effects in two-photon spectroscopy

Andrews, David L., Blake, Nick P. and Hopkins, Kevin P. (1988) Theory of electro-optical effects in two-photon spectroscopy. The Journal of Chemical Physics, 88 (10). pp. 6022-6029. ISSN 0021-9606

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This paper develops the general theory of electro‐optical effects in two‐photon molecular spectroscopy. Two distinct mechanisms can play a role in these nonlinear interactions with an external static electric field. One relates specifically to polar fluids and is associated with the partial molecular alignment produced by the applied field. The resultant anisotropy produces a relaxation of symmetry restrictions on the allowed two‐photon transitions. The other mechanism directly involves a nonlinear electro‐optical channel and is associated with quite distinct selection rules. Both mechanisms induce changes in line intensities and can under suitable polarization conditions enable certain transitions to be ‘‘switched into’’ the spectra. Generalized rate equations are derived using standard quantum electrodynamical procedures. The results, which are applicable to any required laser beam configuration, are cast in terms of irreducible Cartesian tensors. This facilitates the elucidation of the selection rules appropriate for molecules of any given symmetry. A comprehensive tabulation of the transformation properties of the relevant molecular tensors under the operations of the common molecular point groups is also presented, paving the way for the subsequent application of the results specifically to two‐photon absorption and Raman scattering processes.

Item Type: Article
Faculty \ School: Faculty of Science > School of Chemistry
UEA Research Groups: Faculty of Science > Research Groups > Physical and Analytical Chemistry (former - to 2017)
Faculty of Science > Research Groups > Chemistry of Light and Energy
Faculty of Science > Research Groups > Centre for Photonics and Quantum Science
Depositing User: Pure Connector
Date Deposited: 18 Jan 2016 17:08
Last Modified: 09 Feb 2023 13:42
DOI: 10.1063/1.454494


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