Modeling Molecules Under Pressure with Gaussian Potentials

Abstract

<div> <div> <div> <p>The computational modeling of molecules under high pressure is a growing research area that augments experimental high-pressure chemistry. Here, a new electronic structure method for modeling atoms and molecules under pressure, the <i>Gaussians On Sur</i><i>ace Tesserae Simulate HYdrostatic Pressure</i> (GOSTSHYP) approach, is introduced. In this method, a set of Gaussian potentials is distributed evenly on the van der Waals surface of the investigated chemical system, leading to a compression of the electron density and the atomic scaffold. Since no parameters other than the pressure need to be specified, GOSTSHYP allows straightforward geometry optimizations and <i>ab initio</i> Molecular Dynamics simulations of chemical systems under pressure for non-expert users. Calculated energies, bond lengths and dipole moments under pressure fall within the range of established computational methods for high-pressure chemistry. A Diels-Alder reaction and the cyclotrimerization of acetylene showcase the ability of GOSTSHYP to model pressure-induced chemical reactions. The connection to mechanochemistry is pointed out. </p> </div> </div> </div>