A modern solvation theory: quantum chemistry and statistical chemistry

Abstract

This perspective highlights recent developments in the field of statistical mechanics for molecular liquids, i.e. the integral equation (IE) theory, especially focusing on hybrid approaches incorporating quantum chemistry and IE theory. The electronic structure of solvated molecules is characterized, followed by recent developments and applications. The latter includes for some specific systems: evaluation of acidity, basicity, pH and pKa, chemical equilibrium and molecular structure, chemical reactions, ionization and electron transfer reactions, as well as excited states and their free energy.

Communication: Constructing an implicit quantum mechanical/molecular mechanics solvent model by coarse-graining explicit solvent

“…[1][2][3][4][5] Integral equation theories such as the reference interaction site model (RISM) also provide a useful means of obtaining information about the statistical structure and properties of the solvent. 6 Alternatively, one can pre-compute the response of the solute to the solvent and use that in place of QM calculations during the a) Present address: Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA. b) gregory.beran@ucr.edu solvent sampling.…”

Effects of bridge functions on radial distribution functions of liquid water

“…This analytical approach often gives fair results on par with those by extensive Monte Carlo or molecular dynamics (MD) simulations, and combined with the reference interaction site model (RISM) method (Chandler and Andersen, 1972;Hansen and McDonald, 2006; Hirata and Rossky, 1981), can comprehensively describe the equilibrium properties of molecular liquids such as liquid water (Pettitt and Rossky, 1982), which plays essential roles in a variety of biochemical processes. Recent developments in the methods, algorithms and benchmarks (Lombardero et al, 1999;Lue and Blankschtein, 1995;Reddy et al, 2003;Richardi et al, 1999;Sato, 2013;Sumi and Sekino, 2006) indicate that the RISM-based integral equation approach can provide an alternative route for theoretical analyses on water and related aqueous systems with comparable reliability to more expensive, computer simulation approaches. However, it has also been observed (Lombardero et al, 1999;Lue and Blankschtein, 1995;Reddy et al, 2003;Richardi et al, 1999;Sato, 2013;Sumi and Sekino, 2006) that the descriptions of intermolecular correlations of water become less accurate at room temperature in comparison with at higher temperatures.…”

“…Recent developments in the methods, algorithms and benchmarks (Lombardero et al, 1999;Lue and Blankschtein, 1995;Reddy et al, 2003;Richardi et al, 1999;Sato, 2013;Sumi and Sekino, 2006) indicate that the RISM-based integral equation approach can provide an alternative route for theoretical analyses on water and related aqueous systems with comparable reliability to more expensive, computer simulation approaches. However, it has also been observed (Lombardero et al, 1999;Lue and Blankschtein, 1995;Reddy et al, 2003;Richardi et al, 1999;Sato, 2013;Sumi and Sekino, 2006) that the descriptions of intermolecular correlations of water become less accurate at room temperature in comparison with at higher temperatures.…”

A molecular level study of selective cation capture by a host–guest mechanism for 25,26,27,28-tetramethoxycalix[4]arene in MClO4solution (M = Na, K)

“…[22] In the past nearly two decades, RISM-SCF [23] and RISM-SCF-SEDD [21] have been successfully applied to a wide range of chemical phenomena in the solution phase. [24] In particular, the recently modified version of RISM-SCF-SEDD enables us to treat multi-component solvent system. The method realises the computations of DielsAlder reaction [25] and SN2 reaction [26] in roomtemperature ionic liquids and the prediction of pK a in HCl aqueous solution [27] using highly sophisticated quantum chemical methods with modest computational demands.…”