Pinacolone-Alcohol Gas-Phase Solvation Balances as Experimental Dispersion Benchmarks.

ABSTRACT: The influence of distant London dispersion forces on the docking preference of alcohols of different size between the two lone electron pairs of the carbonyl group in pinacolone was explored by infrared spectroscopy of the OH stretching fundamental in supersonic jet expansions of 1:1 solvate complexes. Experimentally, no pronounced tendency of the alcohol to switch from the methyl to the bulkier tert-butyl side with increasing size was found. In all cases, methyl docking dominates by at least a factor of two, whereas DFT-optimized structures suggest a very close balance for the larger alcohols, once corrected by CCSD(T) relative electronic energies. Together with inconsistencies when switching from a C4 to a C5 alcohol, this points at deficiencies of the investigated B3LYP and in particula

SUBMITTER: Zimmermann C 

PROVIDER: S-EPMC7662480 | biostudies-literature | 2020 Nov

REPOSITORIES: biostudies-literature