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

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-depen...

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Bibliographic Details
Published in:The Journal of chemical physics 2014-07, Vol.141 (3), p.034504-034504
Main Authors: Ford, J S, Andrews, D L
Format: Article
Language:English
Subjects:
ABSORPTION
Chromophores
EFFICIENCY
INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY
INTERACTIONS
Laser beams
LASERS
MOLECULES
Photon absorption
PHOTONS
POLARIZATION
QUANTUM ELECTRODYNAMICS
Quantum theory
RAYLEIGH SCATTERING
REFRACTIVE INDEX
Refractivity
Scalars
SOLUTIONS
SOLVENTS
TIME DEPENDENCE
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Summary: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.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.4887539