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Issue 17, 2013
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A 3D-RISM-SCF method with dual solvent boxes for a highly polarized system: application to 1,6-anhydrosugar formation reaction of phenyl α- and β-d-glucosides under basic conditions

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Abstract

One of the difficulties in application of the usual reference interaction site model self-consistent field (RISM-SCF) method to a highly polarized and bulky system arises from the approximate evaluation of electrostatic potential (ESP) with pure point charges. To improve this ESP evaluation, the ESP near a solute is directly calculated with a solute electronic wavefunction, that distant from a solute is approximately calculated with solute point charges, and they are connected with a switching function. To evaluate the fine solvation structure near the solute by incorporating the long-range solute–solvent Coulombic interaction with low computational cost, we introduced the dual solvent box protocol; one small box with the fine spacing is employed for the first and the second solvation shells and the other large box with the normal spacing is employed for long-range solute–solvent interaction. The levoglucosan formation from phenyl α- and β-D-glucosides under basic conditions is successfully inspected by this 3D-RISM-SCF method at the MP2 and SCS-MP2 levels, though the 1D-RISM-SCF could not be applied to this reaction due to the presence of highly polarized and bulky species. This 3D-RISM-SCF calculation reproduces the experimentally reported higher reactivity of the β-anomer. The 3D-RISM-SCF-calculated activation free energy for the β-anomer is closer to the experimental value than the PCM-calculated one. Interestingly, the solvation effect increases the difference in reactivity between these two anomers. The reason is successfully elucidated with 3D-RISM-SCF-calculated microscopic solvation structure and decomposition analysis of solute–solvent interaction.

Graphical abstract: A 3D-RISM-SCF method with dual solvent boxes for a highly polarized system: application to 1,6-anhydrosugar formation reaction of phenyl α- and β-d-glucosides under basic conditions

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Publication details

The article was received on 02 Nov 2012, accepted on 25 Feb 2013 and first published on 01 Mar 2013


Article type: Paper
DOI: 10.1039/C3CP43892A
Phys. Chem. Chem. Phys., 2013,15, 6368-6381

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    A 3D-RISM-SCF method with dual solvent boxes for a highly polarized system: application to 1,6-anhydrosugar formation reaction of phenyl α- and β-D-glucosides under basic conditions

    S. Aono, T. Hosoya and S. Sakaki, Phys. Chem. Chem. Phys., 2013, 15, 6368
    DOI: 10.1039/C3CP43892A

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