Time-dependent surface-enhanced Raman scattering: A theoretical approach

A new procedure for computing the time-dependent Raman scattering of molecules in the proximity of plasmonic nanoparticles (NPs) is proposed, drawing inspiration from the pioneering Lee and Heller’s theory. This strategy is based on a preliminary simulation of the molecular vibronic wavefunction in the presence of a plasmonic nanostructure and an incident light pulse. Subsequently, the Raman signal is evaluated through an inverse Fourier Transform of the coefficients’ dynamics. Employing a multiscale approach, the system is treated by coupling the quantum mechanical description of the molecule with the polarizable continuum model for the NP. This method offers a unique advantage by providing insights into the time evolution of the plasmon-enhanced Raman signal, tracking the dynamics of the incident electric field. It not only provides for the total Raman signal at the process’s conclusion but also gives transient information. Importantly, the flexibility of this approach allows for the simulation of various incident electric field profiles, enabling a closer alignment with experimental setups. This adaptability ensures that the method is relevant and applicable to diverse real-world scenarios.