A polarizability driven ab initio molecular dynamics approach to stimulating Raman activity: Application to C20

Abstract

We describe a novel variant of the driven molecular dynamics (DMD) method derived for probing Raman active vibrations. The method is an extension of the conventional μ-DMD formulation for simulating IR activity by means of coupling an oscillating electric field to the molecule’s dipole moment, μ, and inducing absorption of energy via tuning the field to a resonant frequency. Presently, we modify the above prescription to invoke Raman activity by coupling two electric fields, i.e. a ‘Pump’ photon of frequency ωP and a Stokes photon of frequency ωS to the molecule’s polarizability tensor, α, with the difference in the frequencies ω = ωP – ωS corresponding to the Stokes Raman shift. If ω is close to a Raman active vibrational frequency, energy absorption ensues. Varying ω allows identifying and assigning all Raman active vibrational modes, including anharmonic corrections, by means of trajectory analysis. We show that only one element of the full polarizability tensor, and its nuclear derivative, is needed for an α-DMD trajectory, making this method well suited for ab initio dynamics implementation. Numerical results using first-principles calculations are presented and discussed for the vibrational fundamentals, combination bands, overtones of H2O, CH4, and the C20 fullerene.