Abstract
The MINIMAX/MINIMI concept for the location of transition states and/or stable intermediates of chemical reactions is introduced, based on the synchronous transit method. According to this strategy, minimization of quadratic synchronous transit path maxima or minima is achieved by constrained exhaustive optimization of internal coordinates. The method and its efficiency are demonstrated for two-dimensional model surfaces as well as for thermally allowed electrocyclic interconversions of cyclopropyl-/allyl-cation and cyclobutene-/butadiene (gauche) within the framework of MNDO-SCF calculations. Thus, in both cases a direct comparison with the exact solution determined by minimization of the scalar gradient norm and cross reference to the original work of Halgren and Lipscomb [3] is possible.
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Halgren, T. A., Kleier, D. A., Hall Jr., J. H., Brown, L. D., Lipscomb, W. N.: J. Am. Soc.100 (21), 6595 (1978)
Dewar, M. J. S., Ford, G. P.: J. Am. Chem. Soc.101(19), 5558 (1979)
Halgren, T. A., Pepperberg, I. M., Lipscomb, W. N.: J. Chem. Soc.97(5), 1248 (1975);
Halgren, T. A., Lipscomb, W. N.: Chem. Phys. Letters49(2), 225 (1977)
Mueller, K., Brown, L. D.: Theor. Chim. Acta (Berl.)53, 75 (1979)
Mueller, K.: Angew. Chem.92, 1 (1980)
Thiel, W.: J. Am. Chem. Soc.103, 1420 (1981)
Ehrenson, S.: J. Am. Chem. Soc.96, 3778 (1974)
Tee, O. S.: J. Am. Chem. Soc.91, 7144 (1969).
PC = DR/(DR + DP) = const. =p transforms with Eq. (1) to\((x + p^2 \cdot R/(1 - 2p))^2 + y^2 = ((1 - p) \cdot p \cdot R/(1 - 2 \cdot p))^2 \) whereX R =Y R =Y P = 0,X P =R
See 2a, 3b [Loc. cit. Ref. [4] and [5] [lit. loc. cit.]
Ishida, K., Morokuma, K., Kormornicki, A.: J. Chem. Phys.66(5), 2153 (1977)
As in [3b], C-H bond lengths were excluded from optimization. These quantities do not remain constant but vary linearly/parabolically along the transit paths
Dewar, M. J. S., McKee, M. L., Rzepa, H. S.: J. Am. Chem. Soc.100, 3607 (1978)
Dewar, M. J. S., Thiel, W.: Theor. Chim. Acta (Berl.)46, 89 (1977)
Dewar, M. J. S., Thiel, W.: J. Am. Chem. Soc.99, 4907 (1977)
Dewar, M. J. S., McKee, M. L.: J. Am. Chem. Soc.100, 7499 (1978)
McIver, Jr., J. W., Kormornicki, A.: J. Am. Chem. Soc.94, 2625 (1972)
Jensen, A., Kunz, H.: to be published
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Jensen, A. Location of transition states and stable intermediates by MINIMAX/MINIMI optimization of synchronous transit pathways. Theoret. Chim. Acta 63, 269–290 (1983). https://doi.org/10.1007/BF01151605
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DOI: https://doi.org/10.1007/BF01151605