The second derivative of the electronic energy with respect to the compression scaling factor in the XP-PCM model: Theory and applications to compression response functions of atoms

Abstract

We present the analytical theory for the second derivative of the electronic energy with respect to the scaling factor of the compression cavity within the eXtreme pressure polarizable continuum model (XP-PCM) for the study of compressed atomic and molecular systems. The theory has been exploited to study compression response functions describing how the atomic/molecular properties are effected by an external pressure. The response functions considered include the atomic compressibility and the pressure coefficients of the ionization energy (IE) and electron affinity (EA). The theory has been validated by numerical application to compressed neon, argon, and krypton atoms.

Keywords: analytical derivatives of electronic energy; atomic compressibility; atoms under pressure; electron affinity; extreme-pressure polarizable continuum model; ionization energy.