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An exact-factorization perspective on quantum-classical approaches to excited-state dynamics

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Abstract

Trajectory-based quantum-classical schemes to excited-state dynamics are the most promising approaches to study photochemical and photophysical phenomena occurring in complex molecular systems. Theoretical developments in this field are mainly directed towards proposing generally-applicable approximations to the full quantum-mechanical problem, able to capture the key features of the mechanisms of interest. The task is indeed hard. Therefore, comparisons among approximate methods, and comparisons with exact results for typical model examples provide guidelines for theoreticians who decide to embark on this path. In this work, Ehrenfest dynamics and surface hopping will be analyzed adopting the exact-factorization perspective. A theoretical investigation will be supported by numerical results on a two-electronic-state one-dimensional model system. Numerical results based on the quantum-classical algorithm derived from the exact factorization will be presented as well, allowing to point out strengths and deficiencies of Ehrenfest dynamics and surface hopping. The combined analysis of the potential that drives classical trajectories and of quantum decoherence is essential to highlight similarities or differences among these quantum-classical approaches.

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References

  1. A. Ishizaki, G.R. Fleming, Proc. Natl. Acad. Sci. USA 106, 17255 (2009)

    Article  ADS  Google Scholar 

  2. J. Strümpfer, M. Sener, K. Schulten, J. Phys. Chem. Lett. 3, 536 (2012)

    Article  Google Scholar 

  3. D. Polli et al., Nature 467, 440 (2010)

    Article  ADS  Google Scholar 

  4. S.K. Min, F. Agostini, I. Tavernelli, E.K.U. Gross, J. Phys. Chem. Lett. 8, 3048 (2017)

    Article  Google Scholar 

  5. B.R. Landry, J.E. Subotnik, J. Chem. Theory Comput. 10, 4253 (2014)

    Article  Google Scholar 

  6. C.A. Rozzi et al., Nat. Comm. 4, 1602 (2013)

    Article  Google Scholar 

  7. A. Perveaux, M. Lorphelin, B. Lasorne, D. Lauvergnat, Phys. Chem. Chem. Phys. 19, 6579 (2017)

    Article  Google Scholar 

  8. A. Perveaux, P.J. Castro, D. Lauvergnat, M. Reguero, B. Lasorne, J. Phys. Chem. Lett. 6, 1316 (2015)

    Article  Google Scholar 

  9. P. Huo, D.F. Coker, J. Phys. Chem. Lett. 2, 825 (2011)

    Article  Google Scholar 

  10. B.F.E. Curchod, F. Agostini, J. Phys. Chem. Lett. 8, 831 (2017)

    Article  Google Scholar 

  11. L. Wang, A. Akimov, O.V. Prezhdo, J. Phys. Chem. Lett. 7, 2100 (2016)

    Article  Google Scholar 

  12. B.F.E. Curchod, U. Rothlisberger, I. Tavernelli, Chem. Phys. Chem. 14, 1314 (2013)

    Article  Google Scholar 

  13. J.E. Subotnik, A. Jain, B. Landry, A. Petit, W. Ouyang, N. Bellonzi, Ann. Rev. Phys. Chem. 67, 387 (2016)

    Article  ADS  Google Scholar 

  14. J.C. Tully, J. Chem. Phys. 93, 1061 (1990)

    Article  ADS  Google Scholar 

  15. J.C. Tully, Faraday Discuss. 110, 407 (1998)

    Article  ADS  Google Scholar 

  16. F. Agostini, S.K. Min, A. Abedi, E.K.U. Gross, J. Chem. Theory Comput. 12, 2127 (2016)

    Article  Google Scholar 

  17. M. Ben-Nun, J. Quenneville, T.J. Martínez, J. Phys. Chem. A 104, 5161 (2000)

    Article  Google Scholar 

  18. B.F.E. Curchod, A. Sisto, T.J. Martínez, J. Phys. Chem. A 121, 265 (2017)

    Article  Google Scholar 

  19. E. Tapavicza, I. Tavernelli, U. Rothlisberger, Phys. Rev. Lett. 98, 023001 (2007)

    Article  ADS  Google Scholar 

  20. A. Abedi, F. Agostini, E.K.U. Gross, Europhys. Lett. 106, 33001 (2014)

    Article  ADS  Google Scholar 

  21. F. Agostini, S.K. Min, E.K.U. Gross, Ann. Phys. 527, 546 (2015)

    Article  MathSciNet  Google Scholar 

  22. F. Agostini, A. Abedi, E.K.U. Gross, J. Chem. Phys. 141, 214101 (2014)

    Article  ADS  Google Scholar 

  23. A. Schild, F. Agostini, E.K.U. Gross, J. Phys. Chem. A 120, 3316 (2016)

    Article  Google Scholar 

  24. N.L. Doltsinis, D. Marx, Phys. Rev. Lett. 88, 166402 (2002)

    Article  ADS  Google Scholar 

  25. A.W. Jasper, S. Nangia, C. Zhu, D.G. Truhlar, Acc. Chem. Res. 39, 101 (2006)

    Article  Google Scholar 

  26. B.F.E. Curchod, I. Tavernelli, U. Rothlisberger, Phys. Chem. Chem. Phys. 13, 3231 (2011)

    Article  Google Scholar 

  27. P. Huo, D.F. Coker, J. Chem. Phys. 137, 22A535 (2012)

    Article  Google Scholar 

  28. R. Kapral, G. Ciccotti, J. Chem. Phys. 110, 8916 (1999)

    Article  ADS  Google Scholar 

  29. R. Kapral, Annu. Rev. Phys. Chem. 57, 129 (2006)

    Article  ADS  Google Scholar 

  30. E.R. Dunkel, S. Bonella, D.F. Coker, J. Chem. Phys. 129, 114106 (2008)

    Article  ADS  Google Scholar 

  31. G.S. Engel, T.R. Calhoun, E.L. Read, T.K. Ahn, T. Mančal, Y.C. Cheng, R.E. Blankenship, G.R. Fleming, Nature 446, 782 (2007)

    Article  ADS  Google Scholar 

  32. G.D. Scholes, J. Phys. Chem. Lett. 1, 2 (2010)

    Article  Google Scholar 

  33. E. Collini, C.Y. Wong, K.E. Wilk, P.M.G. Curmi, P. Brumer, G.D. Scholes, Nature 463, 644 (2010)

    Article  ADS  Google Scholar 

  34. G. Panitchayangkoon, D. Hayes, K.A. Fransted, J.R. Caram, E. Harel, J. Wen, R.E. Blankenship, G.S. Engel, Proc. Natl. Acad. Sci. USA 107, 12766 (2010)

    Article  ADS  Google Scholar 

  35. D.B. Turner, K.E. Wilk, P.M.G. Curmi, G.D. Scholes, J. Phys. Chem. Lett. 2, 1904 2011

  36. K.E. Dorfman, D.V. Voronine, S. Mukamel, M.O. Scully, Proc. Natl. Acad. Sci. USA 110, 2746 (2013)

    Article  ADS  Google Scholar 

  37. A.V. Akimov, O.V. Prezhdo, J. Phys. Chem. Lett. 4, 3857 (2013)

    Article  Google Scholar 

  38. C. Curutchet, B. Mennucci, Chem. Rev. 117, 294 (2017)

    Article  Google Scholar 

  39. J.K. Ha, I.S. Lee, S.K. Min, J. Phys. Chem. Lett. 9, 1097 (2018)

    Article  Google Scholar 

  40. B.J. Schwartz, E.R. Bittner, O.V. Prezhdo, P.J. Rossky, J. Chem. Phys. 104, 5942 (1996)

    Article  ADS  Google Scholar 

  41. J.Y. Fang, S. Hammes-Schiffer, J. Phys. Chem. A 103, 9399 (1999)

    Article  Google Scholar 

  42. G. Granucci, M. Persico, J. Chem. Phys. 126, 134114 (2007)

    Article  ADS  Google Scholar 

  43. N. Shenvi, J.E. Subotnik, W. Yang, J. Chem. Phys. 134, 144102 (2011)

    Article  ADS  Google Scholar 

  44. N. Shenvi, J.E. Subotnik, W. Yang, J. Chem. Phys. 135, 024101 (2011)

    Article  ADS  Google Scholar 

  45. N. Shenvi, W. Yang, J. Chem. Phys. 137, 22A528 (2012)

    Article  Google Scholar 

  46. J.E. Subotnik, N. Shenvi, J. Chem. Phys. 134, 024105 (2011)

    Article  ADS  Google Scholar 

  47. J.E. Subotnik, N. Shenvi, J. Chem. Phys. 134, 244114 (2011)

    Article  ADS  Google Scholar 

  48. S.K. Min, F. Agostini, E.K.U. Gross, Phys. Rev. Lett. 115, 073001 (2015)

    Article  ADS  Google Scholar 

  49. A. Abedi, N.T. Maitra, E.K.U. Gross, Phys. Rev. Lett. 105, 123002 (2010)

    Article  ADS  Google Scholar 

  50. A. Abedi, N.T. Maitra, E.K.U. Gross, J. Chem. Phys. 137, 22A530 (2012)

    Article  Google Scholar 

  51. J.C. Tully, Mixed quantum-classical dynamics: mean-field ans surface-hopping, in Classical and quantum dynamics in condensed phase simulations, Proceedings of the international school of physics edited by B.B. Berne, G. Ciccotti, D.F. Coker (World Scientific, Singapore, 1998)

  52. Y. Suzuki, A. Abedi, N.T. Maitra, E.K.U. Gross, Phys. Chem. Chem. Phys. 17, 29271 (2015)

    Article  Google Scholar 

  53. F. Agostini, A. Abedi, Y. Suzuki, E.K.U. Gross, Mol. Phys. 111, 3625 (2013)

    Article  ADS  Google Scholar 

  54. A. Abedi, F. Agostini, Y. Suzuki, E.K.U. Gross, Phys. Rev. Lett. 110, 263001 (2013)

    Article  ADS  Google Scholar 

  55. F. Agostini, A. Abedi, Y. Suzuki, S.K. Min, N.T. Maitra, E.K.U. Gross, J. Chem. Phys. 142, 084303 (2015)

    Article  ADS  Google Scholar 

  56. B.F.E. Curchod, F. Agostini, E.K.U. Gross, J. Chem. Phys. 145, 034103 (2016)

    Article  ADS  Google Scholar 

  57. S. Garashchuk, V.A. Rassolov, Chem. Phys. Lett. 376, 358 (2003)

    Article  ADS  Google Scholar 

  58. J.E. Subotnik, N. Shenvi, J. Chem. Phys. 134, 024105 (2011)

    Article  ADS  Google Scholar 

  59. J.E. Subotnik, W. Ouyang, B.R. Landry, J. Chem. Phys. 139, 214107 (2013)

    Article  ADS  Google Scholar 

  60. C. Zhu, S. Nangia, A.W. Jasper, D.G. Truhlar, J. Chem. Phys. 121, 7658 (2004)

    Article  ADS  Google Scholar 

  61. S.C. Cheng, C. Zhu, K.K. Liang, S.H. Lin, D.G. Truhlar, J. Chem. Phys. 129, 024112 (2008)

    Article  ADS  Google Scholar 

  62. M.D. Feit, J.A. Fleck, A. Steiger, J. Comput. Phys. 47, 412 (1982)

    Article  MathSciNet  ADS  Google Scholar 

  63. F. Agostini, I. Tavernelli, G. Ciccotti, Eur. Phys. J. B 91, 139 (2018)

    Article  Google Scholar 

  64. A.V. Akimov, R. Long, O.V. Prezhdo, J. Chem. Phys. 140, 194107 (2014)

    Article  ADS  Google Scholar 

  65. J.L. Alonso, J. Clemente-Gallardo, J.C. Cuchí, P. Echenique, F. Falceto, J. Chem. Phys. 137, 054106 (2012)

    Article  ADS  Google Scholar 

  66. O.V. Prezhdo, P.J. Rossky, J. Chem. Phys. 107, 825 (1997)

    Article  ADS  Google Scholar 

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Authors and Affiliations

  1. Laboratoire de Chimie Physique, UMR 8000 CNRS/University Paris-Sud, 91405, Orsay, France

    Federica Agostini

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  1. Federica Agostini
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Correspondence to Federica Agostini.

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Contribution to the Topical Issue “Special issue in honor of Hardy Gross”, edited by C.A. Ullrich, F.M.S. Nogueira, A. Rubio, and M.A.L. Marques.

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Agostini, F. An exact-factorization perspective on quantum-classical approaches to excited-state dynamics. Eur. Phys. J. B 91, 143 (2018). https://doi.org/10.1140/epjb/e2018-90085-9

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  • DOI: https://doi.org/10.1140/epjb/e2018-90085-9

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