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site of this enzyme. It is hard to imagine a more striking vindication of our assumption that enzymes function by reducing the energies of transition states. The mysterious ways of nature are truly beautiful

[70].

9.SUMMARY

Pair natural orbital extrapolations to the complete basis set limit provide the foundation for a sequence of cost-effective CBS models. The current models: CBS-QCI/APNO, CBS-QB3, and CBS-4M, are applicable to species with 5, 10, and 20 non-hydrogen atoms, and are reliable to ca. 0.5, 1.0, and 2.0 kcal/mol respectively. These methods are applicable to transition states for chemical reactions with the IRCMax procedure. The ZC-VTST CBS-QCI/APNO model is capable of quantitative predictions of absolute rate constants. A double extrapolation promises a new generation of significantly more accurate and reliable models that will no longer require empirical corrections. The isomerasecatalyzed conversion of to provided a case study for the extension of such high-accuracy methods to enzyme kinetics. The impact that high-accuracy computational quantum chemistry is currently having on combustion chemistry will soon be extended to biology. This is an exciting time for computational science.

ACKNOWLEDGEMENTS

The author is grateful to the U. S. Department of Energy and Gaussian, Inc. for the continuing support of this research and recognizes the very important contributions of his many collaborators including: Marc R. Nyden, Mohammad A. Al-Laham, Joseph W. Ochterski, John A. Montgomery, Jr., David K. Malick, Michael J. Frisch, and Rex F. Pratt.

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