Transition State Reaction Rate Theory
Cf. Research Interests:

In plain words: Transition State Theory (TST) was first developed in the 1930's by Henry Eyring and Eugene Wigner and proved to be a remarkable simplification for calculating chemical reaction rates. Because of it, one could truly think of a chemical reaction as being determined by a bottleneck region or structure (called the transition state or activated complex). The effort of such a calculation then shifts to describing a static structure rather than a moving one. Truly a great simplification. However, TST is approximate as soon as you allow the reaction to occur in a solvent. (That is almost every interesting reaction!) In collaboration with Turgay Uzer, we are exploring a new development of TST that may allow us to obtain exact results even in complex solvents.

Moving Non-Recrossing Transition State

Detailed summary in construction

Relevant references are:

  • W. H. Miller, R. Hernandez, N. C. Handy, D. Jayatilaka and A. Willetts; "Ab initio calculation of anharmonic constants for a transition state, with application to semiclassical transition state tunneling probabilities," Chem. Phys. Lett. 172, 62 (1990). (doi:10.1016/0009-2614(90)87217-F)
  • M. J. Cohen, N. C. Handy, R. Hernandez and W. H. Miller; "Cumulative reaction probabilities for H + H2 → H2 + H from a knowledge of the anharmonic force field," Chem. Phys. Lett. 192, 407 (1992). (doi:10.1016/0009-2614(92)85491-R)
  • R. Hernandez and W. H. Miller, "Semiclassical transition state theory - a new perspective," Chem. Phys. Lett. 214, 129 (1993). (HTML, doi:10.1016/0009-2614(93)90071-8)
  • R. Hernandez; "A combined use of perturbation theory and diagonalization: application to bound energy levels and semiclassical rate theory," J. Chem. Phys. 101, 9534 (1994). (HTML, doi:10.1063/1.467985)
  • R. Hernandez and E. Pollak; "Reduced-dimensional semiclassical reaction rate theory for dissipative systems," unpublished notes.
  • T. Bartsch, R. Hernandez, and T. Uzer; "The transition state in a noisy environment," Phys. Rev. Lett. 95, 058301 (2005). (cond-mat/0506231, doi:10.1103/PhysRevLett.95.058301)
  • T. Bartsch, T.Uzer and R. Hernandez; "Stochastic transition states: Reaction geometry amidst noise," J. Chem. Phys. 123, 204102 (2005). (cond-mat/0509425, doi:10.1063/1.2109827)
  • T. Bartsch, T. Uzer, J. M. Moix and R. Hernandez; "Identifying reactive trajectories using a moving transition state," J. Chem. Phys. 124, 244310 (2006). (cond-mat/0604640, doi:10.1063/1.2206587)