Hilbert-space treatment of incoherent, time-resolved spectroscopy. II. Pathway description of optical multiple population-period transient spectroscopy.
This paper applies the general methods developed in the previous paper (Paper I) to the case of one-photon, dipole transitions of a molecular solute. The results generalize transient-grating spectroscopy to an arbitrarily number of dimensions. Transition and detection operators are derived, and their matrix elements are calculated in the complex-valued basis set developed in Paper I. Selection rules make it possible to analyze which incoherent pathways, and thus which correlation functions, contribute to an N-dimensional multiple population-period transient spectroscopy experiment. Irreducible-tensor methods allow the amplitudes of the contributing orientational-correlation functions to be calculated for arbitrary polarization conditions. A second-rank polarization tensor is used to describe the polarization of the pair of beams creating or detecting a grating. Several known results for one-dimensional experiments are rederived in this formalism to provide examples of its use.
Berg
Mark A
MA
Department of Chemistry and Biochemistry, University of South Carolina, Columbia, South Carolina 29208, USA. berg@chem.sc.edu