Probe Beam Dichroism and Birefringence in Stumulated Raman Scattering of Biologically Relevant Polyatomic Molecules

TL;DR

This paper provides a theoretical framework for analyzing dichroism and birefringence effects in stimulated Raman scattering of polyatomic molecules, enabling better interpretation of polarization signals in experiments.

Contribution

The authors derived general expressions for polarization changes in SRS, accounting for arbitrary beam directions and polarizations, and demonstrated how to separate dichroism and birefringence effects experimentally.

Findings

Expressions valid for any propagation direction and polarization

Simultaneous observation of dichroism and birefringence under certain conditions

Experimental separation of effects using polarization analysis

Abstract

The dichroism and birefringence effects in stumulated Raman scattering (SRS) in polyatomic molecules were studied theoretically. General expressions have been derived describing the change of the intensity and polarization of the probe pulse after transmission through a solution of arbitrary polyatomic molecules for any initial polarization of each of the laser pulses. The expressions were written in terms of spherical tensor operators that allowed for separation of the both beams polarization matrices and the material part containing three scalar values of nonlinear optical susceptibility where that rank K is limited to the values K=0,1,2. The expressions are valid for arbitrary directions of propagation of both pump and Stokes light beams and arbitrary polarizations of both beams. The expressions contain contributions from linear dichroism and birefringence in the molecular excited states. It was shown that, under certain conditions, both effects can be observed simultaneously. The geometry of almost collinear propagation of the pump and Stokes pulse beams through the molecular sample was considered, and it was shown that the contributions from linear dichroism and birefringence to the signal can be completely separated in the experiment by means of an appropriate choice of a probe beam polarization analyzer placed in front of the photodetector. The expressions obtained were used to describe the signals obtained using the polarization-modulation technique developed recently by the authors (Gorbunova et al, Phys. Chem. Chem. Phys. 2020, Vol. 22, 18155-18168). It was shown that the modulated dichroism and birefringence signals could be observed in quadrature to the second harmonic of the modulated reference signal.