A quantum reactive scattering perspective on electronic nonadiabaticity

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• 作者：Yang Peng (1)
  Luca M. Ghiringhelli (1)
  Heiko Appel (1)
  
• 关键词：Computational Methods
• 刊名：The European Physical Journal B - Condensed Matter
• 出版年：2014
• 出版时间：July 2014
• 年：2014
• 卷：87
• 期：7
• 全文大小：1,239 KB
• 参考文献：1. J. Mikosch et al., Science 319, 183 (2008) CrossRef
  2. J. Mikosch et al., J. Am. Chem. Soc. 135, 4250 (2013) CrossRef
  3. H. Guo, Int. Rev. Phys. Chem. 31, 1 (2012) CrossRef
  4. J. Hirschfelder, H. Eyring, B. Topley, J. Chem. Phys. 4, 170 (1936) CrossRef
  5. H.M. Hulburt, J.O. Hirschfelder, J. Chem. Phys. 11, 276 (1943) CrossRef
  6. L. Bonnet, Int. Rev. Phys. Chem. 32, 171 (2013) CrossRef
  7. G. Nyman, H.-G. Yu, Int. Rev. Phys. Chem 32, 39 (2013) CrossRef
  8. W. Hu, G.C. Schatz, J. Chem. Phys. 125, 132301 (2006) CrossRef
  9. L.J. Butler, Ann. Rev. Phys. Chem. 49, 125 (1998) CrossRef
  10. D.R. Yarkony, J. Phys. Chem. 100, 18612 (1996) CrossRef
  11. T.-S. Chu, Y. Zhang, K.-L. Han, Int. Rev. Phys. Chem. 25, 201 (2006) CrossRef
  12. G.J. Hal谩sz, A. Vib贸k, R. Baer, M. Baer, J. Chem. Phys. 124, 081106 (2006) CrossRef
  13. J.C. Tully, J. Chem. Phys. 137, 22A301 (2012) CrossRef
  14. L. Sheps et al., Science 328, 220 (2010) CrossRef
  15. H.J. Woerner et al., Science 334, 208 (2011) CrossRef
  16. E. Garand, J. Zhou, D.E. Manolopoulos, M.H. Alexander, D.M. Neumark, Science 319, 72 (2008) CrossRef
  17. C. Shin, S. Shin, J. Chem. Phys. 113, 6528 (2000) CrossRef
  18. M. Baer, Phys. Rep. 358, 75 (2002) CrossRef
  19. R. Baer, Chem. Phys. Lett. 364, 75 (2002) CrossRef
  20. I. Tavernelli, E. Tapavicza, U. Rothlisberger, J. Chem. Phys. 130, 124107 (2009) CrossRef
  21. I. Tavernelli, B.F.E. Curchod, A. Laktionov, U. Rothlisberger, J. Chem. Phys. 133, 194104 (2010) CrossRef
  22. C. Hu, O. Sugino, K. Watanabe, J. Chem. Phys. 135, 074101 (2011) CrossRef
  23. S. Shin, H. Metiu, J. Chem. Phys. 102, 9285 (1995) CrossRef
  24. O.I. Tolstikhin, L.B. Madsen, Phys. Rev. Lett. 111, 153003 (2013) CrossRef
  25. A. Abedi, F. Agostini, Y. Suzuki, E.K.U. Gross, Phys. Rev. Lett. 110, 263001 (2013) CrossRef
  26. P. Vindel-Zandbergen, M. Falge, B. Chang, V. Engel, I. Sola, Theor. Chem. Acc. 132, 1359 (2013) CrossRef
  27. M. Falge, V. Engel, S. Gr盲fe, J. Phys. Chem. Lett. 3, 2617 (2012) CrossRef
  28. K. Hader, V. Engel, J. Chem. Phys. 136, 104306 (2012) CrossRef
  29. M. Falge, V. Engel, S. Gr盲fe, J. Chem. Phys. 134, 184307 (2011) CrossRef
  30. K. Hader, V. Engel, Chem. Phys. Lett. 509, 119 (2011) CrossRef
  31. A. Kuppermann, J.A. Kaye, J.P. Dwyer, Chem. Phys. Lett. 74, 257 (1980) CrossRef
  32. V. Lopez, V.K. Babamov, R.A. Marcus, J. Chem. Phys. 81, 3962 (1984) CrossRef
  33. V.K. Babamov, V. Lopez, R.A. Marcus, J. Chem. Phys. 78, 5621 (1983) CrossRef
  34. V.K. Babamov, V. Lopez, R. Marcus, Chem. Phys. Lett. 101, 507 (1983) CrossRef
  35. R. Levine, Mol. Phys. 22, 497 (1971) CrossRef
  36. V. Aquilanti, S. Cavalli, J. Chem. Soc. Faraday Trans. 93, 801 (1997) CrossRef
  37. N.E. Henriksen, F.Y. Hansen, / Theories of Molecular Reaction Dynamics (Oxford University Press, New York, 2008)
  38. L.E. Fernandez, S. Horvath, S. Hammes-Schiffer, J. Phys. Chem. Lett. 4, 542 (2013) CrossRef
  39. B. Auer, A.V. Soudackov, S. Hammes-Schiffer, J. Phys. Chem. B 116, 7695 (2012) CrossRef
  40. L.E. Fernandez, S. Horvath, S. Hammes-Schiffer, J. Phys. Chem. C 116, 3171 (2012) CrossRef
  
• 作者单位：Yang Peng (1)
  Luca M. Ghiringhelli (1)
  Heiko Appel (1)
  
  1. Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, 14195, Berlin, Germany
  
• ISSN：1434-6036

文摘

Based on quantum reactive-scattering theory, we propose a method for studying the electronic nonadiabaticity in collision processes involving electron-ion rearrangements. We investigate the state-to-state transition probability for electron-ion rearrangements with two comparable approaches. In the first approach the information of the electron is only contained in the ground-state Born-Oppenheimer potential-energy surface, which is the starting point of common reactive-scattering calculations. In the second approach, the electron is explicitly taken into account and included in the calculations at the same level as the ions. Hence, the deviation in the results between the two approaches directly reflects the electronic nonadiabaticity during the collision process. To illustrate the method, we apply it to the well-known proton-transfer model of Shin and Metiu, generalized in order to allow for reactive scattering channels. We show that our explicit electron approach is able to capture electronic nonadiabaticity and the renormalization of the reaction barrier near the classical turning points of the potential in nuclear configuration space. In contrast, system properties near the equilibrium geometry of the asymptotic scattering channels are hardly affected by electronic nonadiabatic effects. We also present an analytical expression for the transition amplitude of the asymmetric proton-transfer model based on the direct evaluation of integrals over the involved Airy functions.