| S. A. L. Jones and P. D. Pacey, J. Phys. Chem. 96 (1992) 1764-1767. |
| V. S. Melissas and D. G. Truhlar, J. Chem. Phys. 99 (1993) 1013-1027. |
In their paper of 1992, Jones and Pacey explained their temperature dependence of rate constants by conventional transition state theory for the following reaction:
1). They used modified Arrhenius equation. What is the exact expression?
2). They assumed that OH stretch partition functions for the reactant and product are the same. Is this a good assumption?
3). Why did they use the geometric mean of the four lowest-frequency?
4). They thought that the tunneling contribution is minor. How did they arrive at such conclusion?
5). Plot Table X of Melissas and Truhlar paper. Does your plot support Jones and Pacey's claim on vibrations?
6). In general, the DG potential energy surface may possess a dip or shoulder close to the transition state of the reaction, as you see in Figure 2 of Melissas and Truhlar paper. Why?
7). Melissas and Truhlar say that tunneling is important. What is tunneling?
8). Jones and Pacey has their activation energy to be little over 4 kcal/mol and Melissas and Truhlar obtained about 2 kcal/mol. The difference of two kcal/mol is rather small number. Is it significant? Explain in terms of reaction kinetics.