Essentials of Computational Chemistry

546 15 ADIABATIC REACTION DYNAMICS
small a rate constant, the pre-exponential is predicted to be too large, which returns the rate
constant to a reasonable value, and vice versa. In spite of such compensating errors, in the
case of acetone the final error in the rate is almost a factor of 20. At lower temperatures,
this error would increase dramatically.
Nevertheless, the agreement that is obtained – which is probably the best one should
expect given the small size of the basis set used in the CCSD(T) calculations
and the possible problems associated with biradical character in the methyl vinyl
ether pathway – suggests that the theoretically predicted TS structures are accurate
representations of the actual transition states. This establishes the concerted nature of three
of the rearrangements and the stepwise nature of the fourth.
Bibliography and Suggested Additional Reading
Chuang, Y.-Y., Cramer, C. J., and Truhlar, D. G. 1998. ‘The Interface of Electronic Structure and
Dynamics for Reactions in Solution’, Int. J. Quantum Chem., 70, 887.
Chuang, Y.-Y., Radhakrishnan, M. L., Fast, P. L., Cramer, C. J., and Truhlar, D. G. 1999. ‘Direct
Dynamics for Free Radical Kinetics in Solution: Solvent Effect on the Rate Constant for the Reaction
of Methanol with Atomic Hydrogen’, J. Phys. Chem. A, 103, 4893.
Espenson, J. H. 1995. Chemical Kinetics and Reaction Mechanisms, 2nd Edn., McGraw-Hill: New
York.
Garrett, B. C. and Truhlar, D. G. 1979. ‘Semiclassical Tunneling Calculations’, J. Phys. Chem., 83,
2921.
Hynes, J. T. 1996. ‘Crossing the Transition State in Solution’, in Solvent Effects and Chemical Reactivity,
Tapia,O.andBertrán, J. Eds., Kluwer: Dordrecht, 231.
Jensen, F. 1999. Introduction to Computational Chemistry, Wiley: Chichester.
Jensen, F. and Norrby, P.-O. 2003. ‘Transition States from Empirical Force Fields’, Theor. Chem. Acc.,
109, 1.
Johnston, H. S. 1966. Gas Phase Reaction Rate Theory, Ronald Press: New York.
Lowry, T. H. and Richardson, K. S. 1981. Mechanism and Theory in Organic Chemistry, 2nd Edn.,
Harper & Row: New York.
Steinfeld, J. I., Francisco, J. S., and Hase, W. L. 1999. Chemical Kinetics and Dynamics, 2nd Edn.,
Prentice Hall: Upper Saddle River, NJ.
Truhlar, D. G., Garrett, B. C., and Klippenstein, S. J. 1996. ‘Current Status of Transition-state Theory’,
J. Phys. Chem., 100, 12771.
Tucker, S. C. and Truhlar, D. G. 1989. ‘Dynamical Formulation of Transition State Theory: Variational
Transition States and Semiclassical Tunneling’, in New Theoretical Concepts for Understanding
Organic Reactions, Bertrán, J. and Czismadia, I. G., Eds., Kluwer: Berlin, 291.
Worth, G. A. and Robb, M. A. 2002. ‘Applying Direct Molecular Dynamics to Non-adiabatic Systems’,
Adv. Chem. Phys., 124, 355.
References
Allison, T. C. and Truhlar, D. G. 1998. In: Modern Methods, for Multidimensional Dynamics Computations
in Chemistry, Thompson, D. L., Ed., World Scientific: Singapore, 618.
Bell, R. P. 1959. Trans. Faraday Soc., 55, 1.
Dubnikova F. and Lifshitz, A. 2000. J. Phys. Chem. A, 104, 4489.
Eckart, C. 1930. Phys. Rev., 35, 1303.