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Compensation of London Dispersion in the Gas Phase and in Aprotic Solvents
Author(s) -
Pollice Robert,
Fleckenstein Felix,
Shenderovich Ilya,
Chen Peter
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201905436
Subject(s) - london dispersion force , dispersion (optics) , dimer , compensation (psychology) , gas phase , solvent , chemical physics , polar , molecule , chemistry , phase (matter) , computational chemistry , van der waals force , physics , optics , organic chemistry , quantum mechanics , psychology , psychoanalysis
The importance of London dispersion for structure and stability of molecules with less than about 200 atoms has been established in recent years but the quantitative understanding is still largely based on computations because of a persistent lack of suitable experimental data. We herein report a comprehensive computational and experimental study of the compensation of London dispersion in proton‐bound dimer dissociations showing that total compensation is largely invariant in both polar and nonpolar aprotic solvents spanning a wide range of bulk polarizabilities. Additionally, we find that compensation by solvent (which is about 40–80 %) largely dominates over compensation in the gas phase (which is about 0–40 %) for typical experimental temperatures.