ABSTRACT
I. Introduction ...................................................................................................................... 580
II. Previous Reviews ............................................................................................................. 583
III. Validation Against Accurate Quantum Mechanical Dynamics ...................................... 583
IV. Theory .............................................................................................................................. 584
A. Gas Phase ................................................................................................................. 584
B. Reactions in the Solid State and at Solid Surfaces ................................................. 590
C. Reaction in Liquids .................................................................................................. 591
1. Solute-Solvent Separation................................................................................ 591
2. Reaction Coordinates and Nonequilibrium Solvation ...................................... 592
3. VTST/MT Methods for Condensed-Phase Reactions ...................................... 594
a. Implicit Bath................................................................................................ 594
b. Reduced-Dimensionality Bath .................................................................... 595
c. Explicit Bath................................................................................................ 596
D. Reactions in Enzymes.............................................................................................. 599
V. Applications to KIEs........................................................................................................ 600
A. Gas Phase ................................................................................................................. 600
B. KIEs in Liquid Phase ............................................................................................... 603
C. Enzymes ................................................................................................................... 603
VI. Software............................................................................................................................ 605
VII. Concluding Remarks........................................................................................................ 605
Acknowledgments ........................................................................................................................ 606
Glossary ........................................................................................................................................ 606
References..................................................................................................................................... 607
The theory of absolute reaction rates, or transition-state-theory, forms the basis of
almost all of our discussions of isotope effects in chemical reactions.
