Gas-phase acidities of tetrahedral oxyacids from ab initio electronic structure theory
Density functional calculations have been performed on several protonation states of the oxyacids of Si, P, V, As, Cr, and S. Structures and vibrational frequencies are in good agreement with experimental values where these are available. A reasonably well-defined correlation between the calculated gas-phase acidities and the measured pK{sub a} in aqueous solution has been found. The pK{sub a}/gas-phase acidity slopes are consistent with those derived from previous molecular mechanics calculations on ferric hydrolysis and the first two acidity constants for orthosilicic acid. The successive deprotonation of other H{sub n}TO{sub 4} species, for a given tetrahedral anion T are roughly consistent with this slope, but not to the extent that there is a universal correlation among all species.
- Research Organization:
- Pacific Northwest National Lab., Richland, WA (US)
- Sponsoring Organization:
- USDOE
- DOE Contract Number:
- AC06-76RL01830
- OSTI ID:
- 20034423
- Journal Information:
- Journal of Physical Chemistry A: Molecules, Spectroscopy, Kinetics, Environment, amp General Theory, Vol. 104, Issue 17; Other Information: PBD: 4 May 2000; ISSN 1089-5639
- Country of Publication:
- United States
- Language:
- English
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