The concept of acidity (the reaction in which a proton is transferred from a proton donor to the solvent, and is characterized by a pKa value) is ubiquitous in many areas of biology and chemistry, and the concept of hydricity (the analogous reaction in which a hydride ion is transferred from a hydride donor to the solvent) has been pioneered by DuBois and coworkers in the context of bio-inspired reductive chemistry. Here we describe recent work towards the calculation of accurate pKa values and thermodynamic hydricities, a goal that has remained elusive despite considerable previous effort. Our approach in both cases is to use partial information that can be calculated accurately to calibrate quantities that cannot be calculate as accurately, and apply appropriate corrections to the straightforwardly calculated pKa or hydricity.This research was carried out at Brookhaven National Laboratory under contract DE-AC02-98CH10886 with the U.S. Department of Energy and supported by its Division of Chemical Sciences, Geosciences, & Biosciences, Office of Basic Energy Sciences.

Towards the calculation of accurate acidities and hydricities in water and acetonitrile

245th National Meeting (2013)

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