Bond Lengths and Dipole Moments of Diatomic Molecules under Isotropic Pressure with the XP-PCM and GOSTSHYP Models.

Abstract

While high-pressure chemistry has a well-established history, methods to simulate pressure at the single-molecule level have been somewhat lacking. The current work aims at comparing two static models (XP-PCM and GOSTSHYP) to apply isotropic pressure to single molecules, focusing on the equilibrium bond length and electric dipole moment of diatomic molecules. Numerical challenges arising in the potential energy surface using the XP-PCM method were examined, and a pragmatic approach was followed to mitigate these. The definition of the cavity was scrutinized, and two approaches to retrieve the isotropic character that could potentially be lost when using the standard methodology were suggested. Subsequently, equilibrium bond lengths under pressure were evaluated, showing reasonable agreement between GOSTSHYP and XP-PCM, but some discrepancies persist. A Taylor series analysis introduced elsewhere was then applied to rationalize the observed trends in terms of the bond surface. Finally, the dipole moment was shown to be highly sensitive to the cavity definition, and qualitative agreement necessitates the use of our adapted procedure.