A computational model for label-free detection of non-fluorescent biochromophores by stimulated emission.

We created a computational model to investigate the characteristics of label-free molecular detection by stimulated emission, which is the fundamental process of stimulated emission microscopy proposed and experimentally demonstrated by Min et al. In our model the molecule is considered to be a two-state quantum system with finite number of vibrational states. The laser excitations are modelled as zero order Gaussian beams. The field-molecule interaction is considered to be an electric dipole interaction. Based on these assumptions we constructed a Liouville-von Neumann master equation for the reduced density operator. The numerical solution of the master equation determines the expectation value of additional photons produced by stimulated emission. Based on this model algorithms are proposed to evaluate relative excitations. Linear dependence in concentration and quadratic dependence in space resolution were obtained at weak excitations. Time delay dependent relative excitation can be evaluated by taking into account only a single vibrational mode. However, to calculate the spectrum of relative excitation two entangled vibrational modes are necessary. An algorithm is proposed that overcomes the problem of computational complexity and enables to evaluate the spectrum on a high-end computer. High correlation between calculated and measured data of time delay and frequency dependent relative excitation, confirm the validity of the proposed model.