Journal of Chemical Physics
Feedback | Help | Exit
The Journal of Chemical Physics
   
 
 
 
Previous Article
Electronic structure aspects of the spin-forbidden reaction CH3(X 2A<sub>2</sub><sup>[double-prime]</sup>)+N(4S)-->HCN(X 1Sigma+)+H2(X 1Sigma<sub>g</sub><sup>+</sup>)
Second order configuration interaction wave functions based on molecular orbitals determined from a state-averaged multiconfigurational self-consistent field procedure are used to investigate the inte...
Next Article
Exchange and correlation energy in density functional theory: Comparison of accurate density functional theory quantities with traditional Hartree–Fock based ones and generalized gradient approximations for the molecules Li2, N2, F2
The density functional definition of exchange and correlation differs from the traditional one. In order to calculate the density functional theory (DFT), quantities accurately, molecular Kohn–Sh...

The MaxFlux algorithm for calculating variationally optimized reaction paths for conformational transitions in many body systems at finite temperature

J. Chem. Phys. 107, 5000 (1997); doi:10.1063/1.474863

Issue Date: 1 October 1997

You are not logged in to this journal. Log in

Shuanghong Huo and John E. Straub
Department of Chemistry, Boston University, Boston, Massachusetts 02215
An algorithm for the calculation of reaction paths between known reactant and product states in systems of low or high dimension is described. The optimal reaction path is defined as the path of maximum flux for a diffusive dynamics assuming isotropic friction. The resulting reaction path is temperature dependent and independent of the magnitude of the friction. Comparison is made with a number of algorithms designed for the calculation of minimum-energy reaction paths. Applications to two model potentials and an extended atom model of a dipeptide are presented. The applications demonstrate the ability of the algorithm to isolate a temperature-dependent optimal reaction path for a high dimensional molecular system. ©1997 American Institute of Physics.
History: Received 29 April 1997; accepted 26 June 1997
Permalink: http://link.aip.org/link/?JCPSA6/107/5000/1
BUY THIS ARTICLE   (US$28)
Download PDF (199 kB) View Cart

KEYWORDS and PACS

Keywords
PACS
  • 82.30.Qt
    Physical Chemistry Specific chemical reactions; reaction mechanisms Isomerization and rearrangement
  • 82.20.Wt
    Physical Chemistry Chemical kinetics Computational modeling; simulation
  • YEAR: 1996-97

PUBLICATION DATA

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

REFERENCES (28)
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. J. Cerjan and W. H. Miller, J. Chem. Phys. 75, 2800 (1981);
    2. R. S. Berry, H. L. Davis, and T. L. Beck, Chem. Phys. Lett. 147, 13 (1988);
    D. T. Nguyen and D. A. Case, J. Phys. Chem. 89, 4020 (1985);
    T. Lazaridis, D. J. Tobias, C. L. Brooks III, and M. E. Paulaitis, J. Chem. Phys. 95, 7612 (1991).
  2. K. Müller and L. D. Brown, Theor. Chim. Acta (Berlin) 53, 75 (1979).
  3. K. Müller, Angew. Chem. Int. Ed. Engl. 19, 1 (1980).
  4. S. Fischer and M. Karplus, Chem. Phys. Lett. 96, 5272 (1992);
    5. J. E. Sinclair and R. Fletcher, J. Phys. C: Solid State Phys. 7, 864 (1974).
  5. A. Ulitsky and D. Shalloway, J. Chem. Phys. 106, 10099 (1997).
  6. R. Elber and M. Karplus, Chem. Phys. Lett. 139, 375 (1987).
  7. L. R. Pratt, J. Chem. Phys. 85, 5045 (1986).
  8. R. Czerminski and R. Elber, Int. J. Quantum Chem. 24, 167 (1990).
  9. R. Czerminski and R. Elber, J. Chem. Phys. 92, 5580 (1990).
  10. A. Ulitsky and R. Elber, J. Chem. Phys. 92, 1510 (1990).
  11. G. Mills, H. Jónsson, and G. K. Schenter, Surf. Sci. 324, 305 (1995);
    12. O. S. Smart, Chem. Phys. Lett. 222, 503 (1994).
  12. R. Elber, in Recent Developments in Theoretical Studies of Proteins, edited by R. Elber (World Scientific, Singapore, 1996).
  13. P. G. Wolynes, in Complex Systems, SFI Studies in the Sciences of Complexity, edited by D. L. Stein, (Addison-Wesley Longman, 1989).
  14. L. Onsager and S. Machlup, Phys. Rev. 91, 1505, 1512 (1953).
  15. R. Olender and R. Elber, J. Chem. Phys. 105, 9299 (1996).
  16. R. E. Gillian and K. R. Wilson, J. Chem. Phys. 97, 1757 (1992).
  17. J. E. Straub, B. J. Berne, and B. Roux, J. Chem. Phys. 93, 6804 (1990);
    18. C. L. Brooks III and S. A. Adelman, J. Chem. Phys. 77, 4845 (1982).
  18. D. G. Truhlar and B. C. Garrett, Acc. Chem. Res. 13, 440 (1980).
  19. C. W. Gardiner, Handbook of Stochastic Methods (Springer, New York, 1983).
  20. B. J. Berne, M. Borkovec, and J. E. Straub, J. Phys. Chem. 92, 3711 (1988).
  21. A. M. Berezhkovskii, L. M. Berezhkovskii, and V. Yu. Zitzerman, Chem. Phys. 130, 55 (1989).
  22. R. S. Larson, Physica A 137, 295 (1986).
  23. M. Berkowitz, J. D. Morgan, J. A. McCammon, and S. H. Northrup, J. Chem. Phys. 79, 5563 (1983).
  24. A more general definition of the path of least resistance was presented for the case of isotropic, spatially dependent friction gamma(r) (Ref. 23). It was defined as the path which minimizes the line integral [script R] = [integral]<sub>[bold r][sub R]</sub><sup>[bold r][sub P]</sup>e<sup>beta [script W]([bold r])</sup>dl(r). The effective potential [script W](r) = U(r)+kBT ln[gamma(r)/gamma(rR)], where gamma(rR) is the friction at an arbitrarily chosen reference point. For the case of spatially independent friction gamma considered in this work [script W](r) = U(r). In general, it is best to optimize [script R] rather than [script P]. However, while methods exist for the calculation of spatially dependent diffusion tensors (Refs. 17 and 28) the calculation of the friction along all coordinates in a multidimensional space remains computationally forbidding.
  25. P. Amara and J. E. Straub, J. Phys. Chem. 99, 14 840 (1995).
  26. K. Fukui, S. Kato, and H. Fujimoto, J. Am. Chem. Soc. 97, 1 (1975).
  27. B. R. Brooks, R. Bruccoleri, B. Olafson, D. States, S. Swaninathan, and M. Karplus, J. Comput. Chem. 4, 187 (1983).
  28. J. E. Straub, M. Borkovec, and B. J. Berne, J. Phys. Chem. 91, 4995 (1987).

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