The prediction of biochemical acid dissociation constants using first principles quantum chemical simulations

H-Transfer steps of the Wacker process: A DFT study

“…The PCM model calculates the molecular free energy in solution as the sum over three terms: [9,31,32] …”

Modern methods for estimation of ionization constants of organic compounds in solution

“…The conductor-like screening solvation model (COSMO) [50,60,75,77,81,83,84,94,[100][101] formerly considered a medium to be a semiconductor with ε = ∞; however, in up-do-date modifications surface density of screened surface charge σ(s) is calculated from the unscreened surface charge density σ*(s) using an ε function:…”

“…In the calculations performed in [50,62,75,85,101,103] variation of geometric parameters upon solvation was taken into account, whereas other pK a predictions [44, 45, 51, 57-61, 65, 75, 84, 99-102] were made using geometric parameters optimized for unsolvated species. Geometry optimization of substituted carboxylic acids in solution increases the accuracy of calculation quite significantly [79].…”

“…This is also confirmed by the data of [82], according to which the accuracy of calculation of pK a values for all compounds increases approximately twofold in going to COSMO. By contrast, the use of solute geometry optimized for solution ensures no appreciable gain in accuracy [101].…”

10.1007/s11178-008-1006-y

“…Methods for determination of ΔG s with account taken of solvent molecules in the explicit form were used only in [61,64,71]. The most recent modification of this approach is conductor-like polarizable continuum model (CPCM) [41] which was used to calculate pK a values in [50][51][52][53][54][55][56][57][58]. The most recent modification of this approach is conductor-like polarizable continuum model (CPCM) [41] which was used to calculate pK a values in [50][51][52][53][54][55][56][57][58].…”