A direct ab initio dynamics study of the water-assisted tautomerization of formamide

✍ Scribed by Robert L. Bell; Deni L. Taveras; Thanh N. Truong; Jack Simons

• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 341 KB
• Volume: 63
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/(sici)1097-461x(1997)63:4<861::aid-qua7>3.0.co;2-u

✦ Synopsis

Direct ab initio dynamics calculations based on a canonical variational transition-state theory with several multidimensional semiclassical tunneling approximations were carried out to obtain rate constants for the water-assisted tautomerization of formamide. The accuracy of the density functionals, namely, B-LYP, B3-LYP, and BH&H-LYP, were examined. We found that the BH&H-LYP method yields the most accurate transition-state properties when comparing it to ab initio MP2 and QCISD results, whereas B-LYP and B3-LYP methods predict barrier heights too low. Reaction path information was calculated at both the MP2 and nonlocal hybrid BH&H-Ž . LYP levels using the 6-31G d, p basis set. At the BH&H-LYP level, we found that the zero-point energy motion lowers the barrier to tautomerization in the formamide᎐water complex by 3.6 kcalrmol. When tunneling is considered, the activation energy at the BH&H-LYP level at 300 K is 17.1 kcalrmol. This is 3.4 kcalrmol below the zero-pointcorrected barrier and 7.0 kcalrmol below the classical barrier. Excellent agreement between BH&H-LYP and MP2 rate constants further supports the use of BH&H-LYP for rate calculations of large systems.