Influence of different dielectric continuum solvent models on the accuracy of pKa Values (CROSBI ID 576500)
Prilog sa skupa u zborniku | sažetak izlaganja sa skupa | međunarodna recenzija
Podaci o odgovornosti
Glasovac, Zoran ; Eckert-Maksić, Mirjana ; Maksić, Zvonimir B.
engleski
Influence of different dielectric continuum solvent models on the accuracy of pKa Values
The most common computational approach for calculation of pKa values is based on the thermodynamical cycle. Within this approach, solvation energies (DeltaG_sol) can be calculated by various methods, of which dielectric continuum solvent models (DCSM) are particularly interesting because of their low demands for computer resources. However, in a series of papers Klamt and coworkers pointed to a systematic discrepancy between calculated and experimental pKa's, where parameters a and b significantly differ from the ideal values of 1 and [G°sol(H+) + DeltaG°^→*], respectively. To overcome this problem, we have employed linear correlation between experimental pKa's and the „reduced basicities“ (DeltaG'_a, sol) in acetonitrile. In continuation of this work, quest for the simplest, but yet the most adequate, DCSM for the calculation of pKa values of different nitrogen bases was conducted. Herein detailed analysis of quality of different DCS models applied will be presented. For this purpose, performance of several variants of PCM solvation models will be compared with that of COSMO, SMX and SS(V)PE approaches. Quality of each method will be discussed in terms of deviation of the regression parameters a and b (slope and intercept, respectively) from the ideal values. In addition, possibility of G°_sol(H^+) calculations from the intercept b will be presented. The latter is particularly important for the solvents for which no experimental data for G°_sol(H^+) is available in literature.
pKa calculations; dielectric continuum solvent models
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Podaci o prilogu
125-x.
2011.
objavljeno
Podaci o matičnoj publikaciji
The 13th European Symposium on Organic Reactivity - Book of Abstracts
Burk, Peeter
Tartu:
Podaci o skupu
The 13th European Symposium on Organic Reactivity
poster
11.09.2011-16.09.2011
Tartu, Estonija