Collective excitations in liquid dimethyl sulfoxide (DMSO): FIR spectrum, low frequency vibrational density of states, and ultrafast dipolar solvation dynamics

Valuable dynamical and structural information about neat liquid DMSO at ambient conditions can be obtained through a study of low frequency vibrations in the far infrared (FIR), that is, terahertz regime. For DMSO, collective excitations as well as single molecule stretches and bends have been measured by different kinds of experiments such as OHD-RIKES and terahertz spectroscopy. In the present work, we investigate the intermolecular vibrational spectrum of DMSO through three different computational techniques namely (i) the far-infrared spectrum obtained through the Fourier transform of total dipole moment auto-time correlation function, (ii) from the Fourier transform of the translational and angular velocity time autocorrelation functions, and (iii) a quenched normal mode analysis of the parent liquid at 300 K. The three spectra, although exhibit differences among each other, reveal similar features which are in good, semi-quantitative, agreement with experimental results. The study of participation ratio of the density of states obtained from the normal mode analysis shows that the broad spectrum around 100 cm−1 involves collective oscillations of 300-400 molecules. Dipolar solvation dynamics exhibit ultrafast energy relaxation with an initial time constant around 157 fs which can be attributed to the coupling to the collective excitations. We compare the properties of DMSO with those of water vis-a-vis the existence of the low frequency collective modes. Last, we find that the collective excitation spectrum exhibits strong temperature dependence.