Evolution of vibrational bands upon gradual protonation/deprotonation of arsinic acid H2As(O)OH in media of different polarity

Abstract

This computational work is devoted to the investigation (MP2/def2-TZVP) of the geometry and IR parameters of arsinic acid H₂AsOOH and its hydrogen-bonded complexes under vacuum and in media with different polarity. The medium effects were accounted for in two ways: (1) implicitly, using the IEFPCM model, varying the dielectric permittivity (ε) and (2) explicitly, by considering hydrogen-bonded complexes of H₂As(O)OH with various hydrogen bond donors (41 complexes) or acceptors (38 complexes), imitating a gradual transition to the As(OH)₂⁺ or AsO₂⁻ moiety, respectively. It was shown that the transition from vacuum to a medium with ε > 1 causes the As(O)OH fragment to lose its flatness. The solvent polar medium introduces significant changes in the geometry and IR spectral parameters of hydrogen-bonded complexes too: as the polarity of a medium increases, weak hydrogen bonds become weaker, and strong and medium hydrogen bonds become stronger; in the case of a complex with two hydrogen bonds cooperativity effects are observed. In almost all cases the driving force of these changes appears to be preferential solvation of charge-separated structures. In the limiting case of complete deprotonation (or conversely complete protonation) the vibrational frequencies of ν_AsO and ν_As–O turn into ν_As–O(asym) and ν_As–O(sym), respectively. In the intermediate cases the distance between ν_AsO and ν_As–O is sensitive to both implicit solvation and explicit solvation and the systematic changes of this distance can be used for estimation of the degree of proton transfer within the hydrogen bond.