High Pressure Vibrational Spectra of Molecules via Molecular Dynamics Simulations

Pressure has a profound effect on intermolecular interactions and thus vibrational frequencies of molecular species in the condensed phase. Although a significant amount of experimental data on pressure dependences of vibrational frequencies has been obtained by now using high-pressure Raman and infra-red spectroscopy, theoretical studies of these effects are limited to a few recent publications utilizing a newly developed quantum mechanical technique based on specially adapted self-consistent reaction field model.¹ In this work, we apply an alternative approach, based on the use of constant pressure molecular dynamics simulations, to compute high-pressure vibrational spectra for a number of simple molecular systems.
[1] See M. Pagliai, R. Cammi, G. Cardini, V.Schettino, J. Phys. Chem. A, 2016, 120, 5136 and references therein.