Application of the Approximate 3D-Reference Interaction Site Model (RISM) Molecular Solvation Theory to Acetonitrile as Solvent

Abstract

The integral equation formalism based reference interaction site model (RISM) molecular solvation theory is applied to pure liquid acetonitrile and water–acetonitrile binary mixtures of different compositions. Solvate formation of d- and f-block ions by ACN is also calculated to check applicability of the RISM theory. The generalized Amber force field (GAFF) and the universal force field (UFF) parameters were found to be suitable for applications with the RISM theory for acetonitrile solvent. The presence of local microsolvated clusters for water–acetonitrile mixtures is validated in the RISM calculations.

Biomolecular Simulations with the Three-Dimensional Reference Interaction Site Model with the Kovalenko-Hirata Closure Molecular Solvation Theory

“…Non-polar solvents that are modeled using the 3D-RISM-KH theory are hydrocarbons (hexadecane, cyclohexane), haloalkane (chloroform), and alcohol (n-octanol, t-butanol) [ 41 , 47 , 101 , 102 ]. Other solvents like nitro-compounds (nitromethane, nitroethane, and nitrobenzene), acetonitrile, and dimethyl sulfoxide (DMSO) were also used in RISM-KH calculations for both liquid structure and solvation energetic studies [ 42 , 103 , 104 ]. The performance of the 3D-RISM-KH calculations is summarized in Table 1 .…”

“…This makes the RISM formalism an excellent candidate from the perspective of building materials of desired properties, as the theory provides understanding of all the underlying interactions between different constituent fragments. The RISM theory with the integral equation formalism was developed and used for solvation structure and energetics calculations, although the potential of this theory goes beyond regular solvation energy calculations and expands to molecular partitioning, physical-chemical property calculation, and molecular simulations [ 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 , 44 , 45 , 46 , 47 , 48 ]. The key feature of the RISM theory is that it can provide reasonably accurate result rapidly, a feature that made this the theory an essential part of the multiscale modeling framework ( Figure 1 ).…”

A Force Field for a Manganese-Vanadium Water Oxidation Catalyst: Redox Potentials in Solution as Showcase

“…The acetonitrile molecules and the counterions were described with GAFF [48] in the same way as in the classical MM MD simulations, see below. It was previously shown that GAFF describes this particular solvent very well [55,56]. In order to account for the electrostatic interactions between the QM nuclei and the MM point charges that enter the Hamiltonian, a cutoff of 10 Å was applied.…”

Identifying Systematic Force Field Errors Using a 3D-RISM Element Counting Correction

“…Refs. [ 7 , 8 , 9 , 10 , 11 ] These corrections have been shown to produce HFEs of similar quality to explicit solvent calculations, and have been extended to correct entropy [ 12 ] as well as other solvents [ 13 , 14 , 15 , 16 , 17 , 18 , 19 ]. While other approaches exist, such as creating new bridge functionals [ 11 ] or using hard-sphere liquids as a reference [ 20 ], most have employed corrections based on the partial molar volume (PMV).…”