Journal of Chemical Physics
Feedback | Help | Exit
The Journal of Chemical Physics
Search:
   
 
 
 
Previous Article
Nearside–farside analysis of differential cross sections: Ar + N2 rotationally inelastic scattering using associated Legendre functions of the first and second kinds
We have carried out the first nearside–farside (NF) analysis of angular scattering for molecular collisions in which the partial wave series for the scattering amplitude is expanded in a basis se...
Next Article
A stochastic technique for solving the Lorentz–Boltzmann equation for hard spheres: Application to the kinetics of gas absorption
The Lorentz–Boltzmann equation for tagged particle motion in a hard sphere fluid may be interpreted as describing the motion of a particle propagating via a series of binary uncorrelated collisio...

Transition states for chemical reactions I. Geometry and classical barrier height

J. Chem. Phys. 108, 5704 (1998); doi:10.1063/1.476317

Issue Date: 8 April 1998

You are not logged in to this journal. Log in

David K. Malick and G. A. Petersson
Hall-Atwater Laboratories of Chemistry, Wesleyan University, Middletown, Connecticut 06459

John A. Montgomery, Jr.
Lorentzian, Inc., 140 Washington Ave., North Haven, Connecticut 06473
A new computational procedure for the characterization of transition states for chemical reactions is proposed and tested. Previous calculations have frequently employed a single point high-level energy calculation at a transition state geometry obtained with a less expensive computational method, Energy[Method(1)]//Geom[Method(2)]. If we instead search the "inexpensive" intrinsic reaction coordinate (IRC) for the maximum of Energy[Method(1)] along this reaction path, the resulting "IRCMax method", Max{Energy[Method(1)]}//IRC{Geom[Method(2)]}, reduces errors in transition state geometries by a factor of 4 to 5, and reduces errors in classical barrier heights by as much as a factor of 10. When applied to the CBS-4, G2(MP2), G2, CBS-Q, and CBS-QCI/APNO model chemistries, the IRCMax method reduces to the standard model for the reactants and products, and gives rms errors in the classical barrier heights for ten atom exchange reactions of 1.3, 1.2, 1.0, 0.6, and 0.3 kcal/mol, respectively. ©1998 American Institute of Physics.
History: Received 3 September 1997; accepted 25 November 1997
Permalink: http://link.aip.org/link/?JCPSA6/108/5704/1
BUY THIS ARTICLE   (US$24)
Download PDF (158 kB) View Cart

KEYWORDS and PACS

Keywords
PACS
  • 82.30.-b
    Physical chemistry Specific chemical reactions; reaction mechanisms
  • 33.15.Bh
    Molecular properties and interactions with photons Properties of molecules and molecular ions General molecular conformation and symmetry; stereochemistry
  • 31.90.+s
    Electronic structure of atoms, molecules and their ions: theory Other topics in the theory of the electronic structure of atoms, molecules, and their ions
  • YEAR: 1998

RELATED DATABASES


To view database links for this article,
you need to log in.
To view database links for this article,
you need to log in.

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

REFERENCES (37)
View in Separate Window/Tab
For access to fully linked references, you need to log in. For access to fully linked references, you need to Log in.
  1. C. Peng and H. B. Schlegel, Isr. J. Chem. 33, 449 (1993).
  2. N. C. Handy and H. F. Schaefer, III, J. Chem. Phys. 81, 5031 (1984).
  3. J. A. Pople, R. Krishnan, H. B. Schlegel, and J. S. Binkley, Int. J. Quant. Chem. Symp. 13, 325 (1979).
  4. H. B. Schlegel, J. Comput. Chem. 3, 214 (1982).
  5. M. Head-Gordon and T. Head-Gordon, Chem. Phys. Lett. 220, 122 (1994).
  6. M. J. Frisch, M. Head-Gordon, and J. A. Pople, Chem. Phys. Lett. 166, 275 (1990).
  7. M. J. Frisch, M. Head-Gordon, and J. A. Pople, Chem. Phys. Lett. 166, 281 (1990).
  8. W. J. Hehre, L. Radom, P. v. R. Schleyer, and J. A. Pople, Ab Initio Molecular Orbital Theory (Wiley, New York, 1986).
  9. J. A. Pople and R. K. Nesbet, J. Chem. Phys. 22, 571 (1954).
  10. C. C. J. Roothan, Rev. Mod. Phys. 23, 69 (1951).
  11. J. A. Pople, M. Head-Gordon, D. J. Fox, K. Raghavachari, and L. A. Curtiss, J. Chem. Phys. 90, 5622 (1989).
  12. L. A. Curtiss, C. Jones, G. W. Trucks, K. Raghavachari, and J. A. Pople, J. Chem. Phys. 93, 2537 (1990).
  13. L. A. Curtiss, K. Raghavachari, G. W. Trucks, and J. A. Pople, J. Chem. Phys. 94, 7221 (1991).
  14. L. A. Curtiss, K. Raghavachari, and J. A. Pople, J. Chem. Phys. 98, 1293 (1993).
  15. J. A. Montgomery, Jr., J. W. Ochterski, and G. A. Petersson, J. Chem. Phys. 101, 5900 (1994).
  16. J. W. Ochterski, G. A. Petersson, and J. A. Montgomery, Jr., J. Chem. Phys. 104, 2598 (1996).
  17. GAUSSIAN94, Revision B.3, M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. Keith, G. A. Petersson, J. A. Montgomery, Jr., K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Gomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. P. Stewart, M. Head-Gordon, C. Gonzalez, and J. A. Pople (Gaussian, Inc., Pittsburgh, PA, 1995).
  18. C. Møller and M. S. Plesset, Phys. Rev. 46, 618 (1934).
  19. R. Ditchfield, W. J. Hehre, and J. A. Pople, J. Chem. Phys. 54, 724 (1971).
  20. W. J. Hehre, R. Ditchfield, and J. A. Pople, J. Chem. Phys. 56, 2257 (1972).
  21. J. S. Binkley, J. A. Pople, and W. J. Hehre, J. Am. Chem. Soc. 102, 939 (1980).
  22. M. S. Gordon, J. S. Binkley, J. A. Pople, W. J. Pietro, and W. J. Hehre, J. Am. Chem. Soc. 104, 2797 (1982).
  23. D. G. Truhlar and A. Kuppermann, J. Am. Chem. Soc. 93, 1840 (1971).
  24. K. Fukui, Acc. Chem. Res. 14, 363 (1981).
  25. C. Gonzalez, and H. B. Schlegel, J. Phys. Chem. 90, 2154 (1989).
  26. R. T. Skodje, D. G. Truhlar, and B. C. Garrett, J. Chem. Phys. 77, 5955 (1982).
  27. J. W. Ochterski, G. A. Petersson, and K. B. Wiberg, J. Am. Chem. Soc. 117, 11299 (1995).
  28. D. L. Diedrich and J. B. Anderson, Science 258, 786 (1992).
  29. K. P. Huber, and G. Herzberg, Constants of Diatomic Molecules (Van Nostrand Reinhold, New York, 1979).
  30. D. L. Gray and A. G. Robiette, Mol. Phys. 37, 1901 (1979).
  31. E. Hirota, J. Mol. Spectrosc. 77, 213 (1979).
  32. G. Herzberg, Electronic Spectra and Electronic Structure of Polyatomic Molecules (Van Nostrand, Princeton, New Jersey, 1966), Vol. III.
  33. M. W. Chase, C. A. Davies, J. R. Downey, D. J. Frurip, R. A. McDonald, and A. N. Syverud, J. Phys. Chem. Ref. Data 14, Suppl. 1 (1985).
  34. P. Ho and C. F. Melius, J. Phys. Chem. 94, 5120 (1990).
  35. M. D. Allendorf and C. F. Melius, J. Phys. Chem. 97, 72 (1993).
  36. G. E. Scuseria, J. Chem. Phys. 95, 7426 (1991).
  37. P. J. Knowles, P. Stark, and H. Werner, Chem. Phys. Lett. 185, 555 (1991).

CITING ARTICLES
For access to citing articles, you need to log in.
For access to citing articles, you need to Log in.


Copyright © American Institute of Physics