Using Conformational Sampling to Model Spectral and Structural Changes of Molecules at Elevated Pressures

Conformational sampling is nowadays a standard routine
in computational
chemistry. Within this work, we present a method to perform conformational
sampling for systems exposed to elevated pressures within the CREST
program, allowing us to model pressure-induced changes of molecular
ensembles and structural parameters. For this purpose, we extend the
molecular Hamiltonian with the PV (pressure times volume) term, using
the solvent-accessible volume. The volume computation is performed
within the new standalone library libpvol. A first application
shows good agreement with experimental data and provides a reasonable
explanation for severe pressure-induced structural and spectroscopic
changes of the molecules dichloroethane and tetra(4-methoxyphenyl)ethylene.