One- and two-photon absorption in solution: The effects of a passive auxiliary beam

Ford, Jack and Andrews, David (2014) One- and two-photon absorption in solution: The effects of a passive auxiliary beam. The Journal of Chemical Physics, 141 (3). ISSN 0021-9606

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The efficiencies of one- and two-photon absorption by chromophores in solution may be significantly modified by a sufficiently intense beam of off-resonant light. A molecular analysis based on quantum electrodynamics (QED) fully accounts for this phenomenon of laser-modified absorption. A time-dependent perturbation-theory treatment describes the process in terms of stimulated forward Rayleigh-scattering of the auxiliary beam occurring simultaneously with the absorption interaction(s). Our formulation accommodates media modifications to the basic character of light-matter interactions, taking into account the refractive and dispersive properties of a solution-phase environment. This introduces the bulk refractive index of the solvent directly into the QED framework. The measurable electronic response of molecules freely rotating in solution is defined by an average of all orientations. We explicitly derive fixed-orientation and rotationally averaged calculations for the Fermi-rule rate of laser-modified one- and two-photon absorption. For a given beam polarization geometry, the solution-phase molecular response is expressible as a set of natural invariant scalars. These results reveal details of the dependence on the beam polarisations and on the rotationally averaged molecular response: we illustrate the breadth of variation available via geometric manipulation of beam polarization, and raise new possibilities for quantum weak measurements of laser states.

Item Type: Article
Additional Information: Copyright 2014 AIP Publishing. This article may be downloaded for personal use only. Any other use requires prior permission of the author and AIP Publishing.
Faculty \ School: Faculty of Science > School of Chemistry
Depositing User: Pure Connector
Date Deposited: 02 Feb 2016 13:03
Last Modified: 09 Feb 2023 13:40
DOI: 10.1063/1.4887539

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