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>

Toward an Understanding of the Pressure Effect on the Intramolecular Vibrational Frequencies of Sulfur Hexafluoride

“…The different pressure effects in determining a more pronounced covalent or ionic character of bonds in a molecule represent an interesting point to be analyzed in more detail to rationalize the trend of vibrational frequencies with pressure not only using the XP-PCM method but other single molecule computational approaches. 6 , 64 − 69 Finally, it would be useful to extend this kind of analysis in periodic DFT calculations on molecular crystalline systems, which explicitly describe the intermolecular interactions to achieve further information on spectroscopic properties.…”

The activation efficiency of mechanophores can be modulated by adjacent polymer composition

“…In the future, we plan to apply our ndings to maximize the efficiency of ex-activation of mechanophores in polymers, [32][33][34] which can be used for the release of small molecules. Moreover, it is planned to apply quantum chemical models of pressure [35][36][37][38][39][40][41][42] to test the role of the linkers in experiments in which mechanophore activation is achieved by compression. Finally, our future studies will focus on a more realistic modeling of the polymer environment by using a multiscale model of mechanophores embedded in a polymer matrix.…”

Trapping the Transition State in a [2,3]-Sigmatropic Rearrangement by Applying Pressure

“…Several quantum chemical methods for the application of hydrostatic pressure to molecules during geometry optimizations have been reported. [22][23][24][25][26][27][28][29] We apply the eXtended Hydrostatic Compression Force Field (X-HCFF) approach [28] in this paper, since this method has been used successfully to predict structural parameters and chemical reactions in the GPa regime.…”