Abstract
Gradient extremals define stream beds connecting stationary points on molecular potential energy surfaces. Using this concept we have developed an algorithm to determine transition states. We initiate walks at equilibrium geometries and follow the gradient extremals until a stationary point is reached. As an illustration we have investigated the mechanism for exchange of protons on carbon in methylenimine (H2C=NH) using a multi-reference self-consistent-field wave function.
Similar content being viewed by others
References
See Jørgensen P, Simons J (1986) Geometrical derivatives of energy surfaces and molecular properties. Reidel, Dordrecht
McIver Jr JW, Komornicki A, (1972) J Am Chem Soc 94:2625
Komornicki A, Ishida K, Morokuma K, Ditchfield R, Conrad M (1977) Chem Phys Lett 45:595
Dupuis M, Spangler D, Wendolowski J (1980) Program QG01, Software Catalog Program
Binkley JS, DeFrees MJ, Krishnan R, Whiteside RA, Schlegel BS, Fluder EM, Pople JA (1983) GAUSSIAN 82, Carnegie-Mellon University, Pittsburgh
Brandemark U, Siegbahn PEM, (1984) Theor Chim Acta 66:217
Head JD, Zerner MC (1985) Chem Phys Lett 122:264
Comeau DC, Zellmer RJ, Shavitt I (1986) In: Jørgensen P, Simons J (eds) Geometrical derivatives of energy surfaces and molecular properties.
Cerjan CJ, Miller WH, (1981) J Chem Phys 75:2800
Simons J, Jørgensen P, Taylor H, Ozment J (1983) J Phys Chem 87:2745
Nguyen DT, Case DA (1985) J Phys Chem 89:4020
Banerjee A, Adams N, Simons J, Shepard R (1985) J Phys Chem 89:52
Jensen HJAa, Jørgensen P, Helgaker T (1986) J Chem Phys 85:3917
Hoffman DK, Nord RS, Ruedenberg K (1986) Theor Chim Acta 69:265
Pancir J (1975) Collect Czech Chem Commun 40:1112
Basilevsky MV, Shamov AG (1981) Chem Phys 60:347
Fletcher R (1980) Practical methods of optimization, vol 1. Wiley, New York
Lehn JM, Munsch B (1968) Theor Chim Acta 12:91
Pople JA, Raghavachari K, Frisch MJ, Binkley JS, Schleyer PvR (1983) J Am Chem Soc 105:6389
Jensen HJAa, Jørgensen P, Helgaker T (1987) J Am Chem Soc 109:2895
Tatewaki H (1985) J Comput Chem 6:237
Dunning Jr ThH (1970) J Chem Phys 53:2823
Huzinaga S (1965) J Chem Phys 42:1293
Jensen HJAa, Ågren H (1984) Chem Phys Lett 110:140 Jensen HJAa, Ågren H (1986) Chem Phys 104:229
Helgaker TU, Almlöf J, Jensen HJAa, Jørgensen P (1986) J Chem Phys 84:6266
Helgaker TU, Jensen HJAa, Jørgensen P (1986) J Chem Phys 84:6280
Botschwina P (1974) Chem Phys Lett 29:580
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Jørgensen, P., Jensen, H.J.A. & Helgaker, T. A gradient extremal walking algorithm. Theoret. Chim. Acta 73, 55–65 (1988). https://doi.org/10.1007/BF00526650
Received:
Revised:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF00526650