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Analysis of the Derivative Coupling Vector for the $1,2^2$ A' States of $H_3$


Abstract

Near the conical intersection for the 1,2 $^{2}A'$ states of $H_3$ the derivative coupling vector is calculated and analyzed on the plane of internal coordinates, (U,V) or its polar coordinates $(S{\theta})$, based on the squares of the internuclear distances. It is shown that in the vicinity of the conical intersection the derivative coupling vector behaves like ${\theta}/2S$, which is responsible for the sign changes of the real-valued electronic wave function when the nuclear configuration traverses a closed path enclosing a conical intersection. The analytic property of the wave functions is studied and especially the observation of the sign change in the configuration state function (CSF) coefficients of the real-valued electronic wave functions is demonstrated.

Keywords

References

  1. Proc. R. Soc. London, Ser. A v.161 Jahn, H. A.;Teller, E.
  2. Chem. Phys. Lett. v.61 Varandas, J. C.;Tennyson, J.;Murrel, J. N.
  3. Ann. Phys. v.84 Born, M.; Oppenheimer, J. R.
  4. J. Chem. Phys. v.70 Mead, C. A.;Truhlar, D. G.
  5. Chem. Phys. v.49 Mead, C. A.
  6. J. Chem. Phys. v.104 Kendrick, B.;Pack, R. T.
  7. J. Chem. Phys. v.104 Kendrick, B.;Pack, R. T.
  8. Rev. Mod. Phys. v.68 Yarkony, D. R.
  9. J. Chem. Phys. v.97 Adelman, D. E.;Shafer, N. E.;Kliner, D. A. V.;Zare, R. N.
  10. Chem. Phys. Lett. v.188 Mielke, S. L.;Friedman, R. S.;Truhlar, D. G.;Schwenke, D. W.
  11. Science v.257 Neuhauser, D.;Judson, R. S.;Kouri, D. J.;Adelman, D. E.;Shafer, N. E.;Kliner, D. A. V.;Zare, R. N.
  12. Chem. Phys. Lett. v.205 Kuppermann, A.;Wu, Y.-S. M.
  13. J. Chem. Phys. v.105 Yarkony, D. R.
  14. State-Selected and State to State Ion-Molecule Reaction Dynamics: Part 2 Theory v.82 Lengsfield, B. H.;Yarkony, D. R.;Baer, M.(ed.);Ng, C.-Y.(ed.)
  15. J. Chem. Phys. no.93 Xantheas, S.;Elbert, S. T.;Ruedenberg, K.
  16. J. Chem. Phys. no.94 Xantheas, S. S.;Atchity, G. J.;Elbert, S. T.;Ruedenberg, K.
  17. J. Comput. Chem. no.14 Schmidt, M. W.;Baldridge, K. K.;Boatz, J. A.;Elbert, S. T.;Gordon, M. S.;Jensen, J. J.;Koseko, S.;Matsunaga, N.;Nguyen, K. A.;Su, S.;Windus, T. L.;Dupuis, M.;Montgomery, J. A.
  18. J. Chem. Phys. no.89 Blais, N. C.;Truhlar, D. G.;Mead, C. A.