Journal of Chemical Physics
Feedback | Help | Exit
The Journal of Chemical Physics
   
 
 
 
Previous Article
Volume fraction dependence and reorganization in cluster–cluster aggregation processes
Off-lattice diffusion limited cluster aggregation simulations in two dimensions have been performed in a wide volume fraction range between 0.001 and 0.60. Starting from a system of 10 000 monomers wi...
Next Article
Influence of surface topology and electrostatic potential on water/electrode systems
We have used the classical molecular dynamics technique to simulate the ordering of a water film adsorbed on an atomic model of a tip of a scanning tunneling microscope approaching a planar metal surf...

Methods for molecular dynamics with nonadiabatic transitions

J. Chem. Phys. 102, 496 (1995); doi:10.1063/1.469428

Issue Date: 1 January 1995

You are not logged in to this journal. Log in

D. F. Coker and L. Xiao
Department of Chemistry, Boston University, 590 Commonwealth Avenue, Boston, Massachusetts 02215
We show how the dynamically nonlocal formulation of classical nuclear motion in the presence of quantal electronic transitions presented many years ago by P. Pechukas [Phys. Rev. 181, 166 (1969); 181, 174 (1969)] can be localized in time using time dependent perturbation theory to give an impulsive force which acts when trajectories hop between electronic surfaces. The action of this impulsive force is completely equivalent to adjusting the nuclear velocities in the direction of the nonadiabatic coupling vector so as to conserve energy, a procedure which is widely used in surface hopping trajectory methods [J. C. Tully, J. Chem. Phys. 93, 1061 (1990)]. This is the first time the precise connection between these two formulations of the nonadiabatic dynamics problem has been considered. We also demonstrate that the stationary phase approximation to the reduced propagator at the heart of Pechukas' theory is not unitary due to its neglect of nonstationary paths. As such mixed quantum-classical evolution schemes based on this approximation are not norm conserving and in general must fail to give the correct branching between different competing electronic states. Tully's phase coherent, fewest switches branching algorithm is guaranteed to conserve the norm. The branching between different alternatives predicted by this approach, however, may be inaccurate, due to use of the approximate local dynamics. We explore the relative merits of these different approximations using Tully's 1D two state example scattering problems for which numerically exact results are easily obtained. ©1995 American Institute of Physics.
History: Received 24 May 1994; accepted 7 September 1994
Permalink: http://link.aip.org/link/?JCPSA6/102/496/1
BUY THIS ARTICLE   (US$28)
Download PDF (322 kB) View Cart

KEYWORDS and PACS

Keywords
PACS
  • 82.20.Fd
    Physical chemistry Chemical kinetics Stochastic and trajectory models, other theories and models
  • 82.20.Db
    Physical chemistry Chemical kinetics Statistical theories (including transition state)
  • 31.70.Dk
    Electronic structure of atoms, molecules and their ions: theory Effects of atomic and molecular interactions on electronic structure Environmental and solvent effects
  • YEAR: 1995

PUBLICATION DATA

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

REFERENCES (39)
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. J. C. Tully, J. Chem. Phys. 93, 1061 (1990).
  2. B. Space and D. F. Coker, J. Chem. Phys. 94, 1976 (1990).
  3. B. Space and D. F. Coker, J. Chem. Phys. 96, 652 (1992).
  4. D. F. Coker, in Computer Simulation in Chemical Physics, edited by M. P. Allen and D. J. Tildesley (Kluwer Academic, Dordrecht, 1993), pp. 315–377.
  5. F. Webster, P. J. Rossky, and R. A. Friesner, Comp. Phys. Comm. 63, 494 (1991).
  6. F. J. Webster, J. Schnitker, M. S. Friedrichs, R. A. Friesner, and P. J. Rossky, Phys. Rev. Lett. 66, 3172 (1991).
  7. F. J. Webster, E. T. Tang, P. J. Rossky, and R. A. Friesner, J. Chem. Phys. 100, 4835 (1994).
  8. P. J. Kuntz, J. Chem. Phys. 95, 141 (1991).
  9. P. J. Kuntz and J. J. Hogreve, J. Chem. Phys. 95, 156 (1991).
  10. I. H. Gersonde and H. Gabriel, J. Chem. Phys. 98, 2094 (1993).
  11. S. Sawada and H. Metiu, J. Chem. Phys. 84, 227 (1986).
  12. W. H. Miller, in Advances in Chemical Physics, Vol. XXV, edited by I. Prigogine and S. A. Rice (Wiley, New York, 1974).
  13. P. Pechukas, Phys. Rev. 181, 166 (1969).
  14. P. Pechukas, Phys. Rev. 181, 174 (1969).
  15. E. E. Nikitin, Theory of Elementary Atomic and Molecular Processes in Gases (Clarendon, Oxford, 1974).
  16. M. S. Child, in Semiclassical Methods in Molecular Scattering and Spectroscopy, edited by D. Reidel (Kluwer Academic, Dordrecht, 1980).
  17. A. P. Penner and R. Wallace, Phys. Rev. A 7, 1007 (1973).
  18. A. P. Penner and R. Wallace, Phys. Rev. A 9, 1136 (1974).
  19. G. D. Billing, Chem. Phys. 9, 359 (1975).
  20. J. C. Tully and R. K. Preston, J. Chem. Phys. 55, 217 (1971).
  21. J. C. Tully, in Dynamics on Molecular Collisions, Part B, edited by W. H. Miller (Plenum, New York, 1976).
  22. W. H. Miller and F. F. George, J. Chem. Phys. 56, 5637 (1972).
  23. J. R. Stine and J. T. Muckerman, J. Phys. Chem. 91, 459 (1987).
  24. J. R. Stine and J. T. Muckerman, J. Chem. Phys. 65, 3975 (1976).
  25. J. R. Stine and J. T. Muckerman, J. Chem. Phys. 68, 185 (1978).
  26. N. C. Blais and D. G. Truhlar, J. Chem. Phys. 79, 1334 (1983).
  27. N. C. Blais, D. G. Truhlar, and C. A. Mead, J. Chem. Phys. 89, 6204 (1988).
  28. L. Xiao and D. F. Coker, J. Phys. Chem. 100, 8646 (1994).
  29. H. Goldstein, Classical Mechanics (Addison-Wesley, Reading, 1980).
  30. E. J. Heller, J. Chem. Phys. 94, 2723 (1991).
  31. E. J. Heller, J. Chem. Phys. 95, 9431 (1991).
  32. W. H. Miller, J. Chem. Phys. 95, 9428 (1991).
  33. J. H. Van Vleck, Proc. Natl. Acad. Sci. 14, 178 (1928).
  34. A similar idea has been used by D. Thirumalai, E. J. Bruskin, and B. J. Berne, J. Chem. Phys. 83, 230 (1985) to justify an expression for the diagonal force terms in the absence of nonadiabatic transitions.
  35. J. C. Tully, Int. J. Quant. Chem. 25, 299 (1991).
  36. M. F. Herman, J. Chem. Phys. 81, 754 (1984).
  37. M. F. Herman, J. Chem. Phys. 81, 764 (1984).
  38. R. Kosloff, J. Phys. Chem. 92, 2087 (1988).
  39. S. Hammes-Schiffer and J. C. Tully, J. Chem. Phys. 101, 4657 (1994).

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