Theoretical Methods for Nonadiabatic Dynamics “on the fly” in Complex Systems and its Control by Laser Fields

  • Roland Mitrić
  • Jens Petersen
  • Ute Werner
  • Vlasta Bonačić-Koutecký
Part of the Progress in Theoretical Chemistry and Physics book series (PTCP, volume 22)


We present a general theoretical approach for the simulation and control of ultrafast processes in complex molecular systems. It is based on the combination of quantum chemical nonadiabatic dynamics “on the fly” with the Wigner distribution approach for simulation and control of laser-induced ultrafast processes. Specifically, we have developed a procedure for the nonadiabatic dynamics in the framework of time-dependent density functional theory using localized basis sets, which is applicable to a large class of molecules and clusters. This has been combined with our general approach for the simulation of time-resolved photoelectron spectra that represents a powerful tool to identify the mechanism of nonadiabatic processes, which has been illustrated on the example of ultrafast photodynamics of furan. Furthermore, we present our “field-induced surface hopping” (FISH) method which allows to include laser fields directly into the nonadiabatic molecular dynamics simulations and thus to realistically model their influence on ultrafast processes. On the example of optimal dynamic discrimination of two almost identical flavin molecules we demonstrate that experimentally optimized laser fields can be directly used in the framework of the FISH method to reveal the dynamical processes behind the optimal control.


Laser Field Classical Trajectory Transition Dipole Moment Fish Method High Excited State 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.



We wish to acknowledge the contribution of our experimental partner Prof. T. Suzuki. We extend our thanks to Prof. J.-P. Wolf and Prof. H. Rabitz for stimulating cooperation and for providing us with experimental results on the discrimination of flavin molecules. Prof. W. Thiel we thank for providing us with the nonadiabatic MNDO code. Finally, we would also like to acknowledge the financial support from the Deutsche Forschungsgemeinschaft in the frame of SPP 1391, FOR 1282, the Emmy Noether Programme, MI-1236 (R.M.), as well as the Fonds der Chemischen Industrie (J.P.).


  1. 1.
    Car R, Parrinello M (1985) Phys Rev Lett 55:2471CrossRefGoogle Scholar
  2. 2.
    Wigner E (1932) Phys Rev 40:749CrossRefGoogle Scholar
  3. 3.
    Hillery M, O’Connel RF, Scully MO, Wigner EP (1984) Phys Rep 106:121CrossRefGoogle Scholar
  4. 4.
    Hartmann M, Pittner J, Bonačić-Koutecký V (2001) J Chem Phys 114:2123CrossRefGoogle Scholar
  5. 5.
    Li Z, Fang J-Y, Martens CC (1996) J Chem Phys 104:6919CrossRefGoogle Scholar
  6. 6.
    Hartmann M, Pittner J, Bonačić-Koutecký V, Heidenreich A, Jortner J (1998) J Chem Phys 108:3096CrossRefGoogle Scholar
  7. 7.
    Hartmann M, Pittner J, Bonačić-Koutecký V, Heidenreich A, Jortner J (1998) J Phys Chem A 102:4069CrossRefGoogle Scholar
  8. 8.
    Hartmann M, Pittner J, Bonačić-Koutecký V (2001) J Chem Phys 114:2106CrossRefGoogle Scholar
  9. 9.
    Mukamel S (1995) Principles of nonlinear optical spectroscopy. Oxford University Press, New York, NYGoogle Scholar
  10. 10.
    Donoso A, Martens CC (2001) Phys Rev Lett 87:223202CrossRefGoogle Scholar
  11. 11.
    Donoso A, Zheng Y, Martens C (2003) J Chem Phys 119:5010CrossRefGoogle Scholar
  12. 12.
    Ben-Nun M, Quenneville J, Martínez TJ (2000) J Phys Chem A 104:5161CrossRefGoogle Scholar
  13. 13.
    Tully JC (1990) J Chem Phys 93:1061CrossRefGoogle Scholar
  14. 14.
    Tully JC (1998) Faraday Discuss 110:407CrossRefGoogle Scholar
  15. 15.
    Mitrić R, Bonačić-Koutecký V, Pittner J, Lischka H (2006) J Chem Phys 125:024303CrossRefGoogle Scholar
  16. 16.
    Doltsinis NL, Marx D (2002) Phys Rev Lett 88:166402CrossRefGoogle Scholar
  17. 17.
    Werner U, Mitrić R, Suzuki T, Bonačić-Koutecký V (2008) Chem Phys 349:319CrossRefGoogle Scholar
  18. 18.
    Mitrić R, Werner U, Bonačić-Koutecký V (2008) J Chem Phys 129:164118CrossRefGoogle Scholar
  19. 19.
    Werner U, Mitrić R, Bonačić-Koutecký V (2010) J Chem Phys 132:174301CrossRefGoogle Scholar
  20. 20.
    Craig CF, Duncan WR, Prezhdo OV (2005) Phys Rev Lett 95:163001CrossRefGoogle Scholar
  21. 21.
    Tapavicza E, Tavernelli I, Rothlisberger U (2007) Phys Rev Lett 98(2):023001CrossRefGoogle Scholar
  22. 22.
    Tapavicza E, Tavernelli I, Rothlisberger U, Filippi C, Casida ME (2008) J Chem Phys 129:124108CrossRefGoogle Scholar
  23. 23.
    Tavernelli I, Tapavicza E, Rothlisberger U (2009) J Chem Phys 130:124107CrossRefGoogle Scholar
  24. 24.
    Granucci G, Persico M, Toniolo A (2001) J Chem Phys 114:10608CrossRefGoogle Scholar
  25. 25.
    Fabiano E, Thiel W (2008) J Phys Chem A 112:6859CrossRefGoogle Scholar
  26. 26.
    Fabiano E, Keal TW, Thiel W (2008) Chem Phys 349:334CrossRefGoogle Scholar
  27. 27.
    Lan Z, Fabiano E, Thiel W (2009) J Phys Chem B 113:3548CrossRefGoogle Scholar
  28. 28.
    Toniolo A, Olsen S, Manohar L, Martinez TJ (2004) Faraday Discuss 127:149CrossRefGoogle Scholar
  29. 29.
    Virshup AM, Punwong C, Pogorelov TV, Lindquist BA, Ko C, Martinez TJ (2009) J Phys Chem B 113:3280CrossRefGoogle Scholar
  30. 30.
    Schäfer LV, Groenhof G, Boggio-Pasqua M, Robb MA, Grubmüller H (2008) PLoS Comp Biol 4:e1000034CrossRefGoogle Scholar
  31. 31.
    Groenhof G, Schäfer LV, Boggio-Pasqua M, Grubmüller H, Robb MA (2008) J Am Chem Soc 130:3250CrossRefGoogle Scholar
  32. 32.
    Boggio-Pasqua M, Robb MA, Groenhof G (2009) J Am Chem Soc 131:13580CrossRefGoogle Scholar
  33. 33.
    Ciminelli C, Granucci G, Persico M (2008) Chem Phys 349:325CrossRefGoogle Scholar
  34. 34.
    Brixner T, Gerber G (2003) ChemPhysChem 4:418CrossRefGoogle Scholar
  35. 35.
    Dantus M, Lozovoy VV (2004) Chem Rev 104:1813CrossRefGoogle Scholar
  36. 36.
    Tannor DJ, Rice SA (1985) J Chem Phys 83:5013CrossRefGoogle Scholar
  37. 37.
    Tannor DJ, Rice SA (1988) Adv Chem Phys 70:441CrossRefGoogle Scholar
  38. 38.
    Brumer P, Shapiro M (1986) Faraday Discuss Chem Soc 82:177CrossRefGoogle Scholar
  39. 39.
    Shapiro M, Brumer P (1986) J Chem Phys 84:4103CrossRefGoogle Scholar
  40. 40.
    Shapiro M, Brumer P (1994) Int Rev Phys Chem 13:187CrossRefGoogle Scholar
  41. 41.
    Tannor DJ, Rice SA (1986) J Chem Phys 85:5805CrossRefGoogle Scholar
  42. 42.
    Peirce AP, Dahleh MA, Rabitz H (1988) Phys Rev A 37:4950CrossRefGoogle Scholar
  43. 43.
    Shi S, Rabitz H (1989) Chem Phys 139:185CrossRefGoogle Scholar
  44. 44.
    Kosloff R, Rice SA, Gaspard P, Tersigni S, Tannor DJ (1989) Chem Phys 139:201CrossRefGoogle Scholar
  45. 45.
    Tersigni SH, Gaspard P, Rice SA (1990) J Chem Phys 93:1670CrossRefGoogle Scholar
  46. 46.
    Rabitz H, Shi S (1991) Adv Mol Vibr Collision Dyn 1A:187Google Scholar
  47. 47.
    Warren WS, Rabitz H, Dahleh M (1993) Science 259:1581CrossRefGoogle Scholar
  48. 48.
    Baumert T, Brixner T, Seyfried V, Strehle M, Gerber G (1997) Appl Phys B 65:779CrossRefGoogle Scholar
  49. 49.
    Yelin D, Meshulach D, Silberberg Y (1997) Opt Lett 22:1793CrossRefGoogle Scholar
  50. 50.
    Efimov A, Moores MD, Beach NM, Krause JL, Reitze DH (1998) Opt Lett 23:1915CrossRefGoogle Scholar
  51. 51.
    Zeek E, Maginnis K, Backus S, Russek U, Murnane MM, Mourou G, Kapteyn HC, Vdovin G (1999) Opt Lett 24:493CrossRefGoogle Scholar
  52. 52.
    Zeek E, Bartels R, Murnane MM, Kapteyn HC, Backus S, Vdovin G (2000) Opt Lett 25:587CrossRefGoogle Scholar
  53. 53.
    Judson RS, Rabitz H (1992) Phys Rev Lett 62:1500CrossRefGoogle Scholar
  54. 54.
    Assion A, Baumert T, Bergt M, Brixner T, Kiefer B, Seyfried V, Strehle M, Gerber G (1998) Science 282:919CrossRefGoogle Scholar
  55. 55.
    Wöste L, Kühn O (eds) (2007) Analysis and control of ultrafast photoinduced reactions. In: Springer series in chemical physics, vol 87. Springer, BerlinGoogle Scholar
  56. 56.
    Bonačić-Koutecký V, Mitrić R (2005) Chem Rev 105:11CrossRefGoogle Scholar
  57. 57.
    Mitrić R, Hartmann M, Pittner J, Bonačić-Koutecký V (2002) J Phys Chem A 106:10477CrossRefGoogle Scholar
  58. 58.
    Mitrić R, Bonačić-Koutecký V (2007) Phys Rev A 76:031405(R)Google Scholar
  59. 59.
    Mitrić R, Petersen J, Bonačić-Koutecký V (2009) Phys Rev A 79:053416CrossRefGoogle Scholar
  60. 60.
    Li B, Turinici G, Ramakrishna V, Rabitz H (2002) J Phys Chem B 106:8125CrossRefGoogle Scholar
  61. 61.
    Li B, Rabitz H, Wolf J-P (2005) J Chem Phys 122:154103CrossRefGoogle Scholar
  62. 62.
    Roth M, Guyon L, Roslund J, Boutou V, Courvoisier F, Wolf J-P, Rabitz H (2009) Phys Rev Lett 102:253001CrossRefGoogle Scholar
  63. 63.
    Petersen J, Mitrić R, Bonačić-Koutecký V, Wolf J-P, Roslund J, Rabitz H (2010) Phys Rev Lett 105:073003CrossRefGoogle Scholar
  64. 64.
    Dreuw A, Head-Gordon M (2005) Chem Rev 105:4009CrossRefGoogle Scholar
  65. 65.
    Kümmel S, Kronik L (2008) Rev Mod Phys 80:3CrossRefGoogle Scholar
  66. 66.
    Leininger T, Stoll H, Werner H-J, Savin A (1997) Chem Phys Lett 275:151CrossRefGoogle Scholar
  67. 67.
    Iikura H, Tsuneda T, Yanai T, Hirao KJ (2001) Chem Phys 115:3540Google Scholar
  68. 68.
    Yanai T, Tew DP, Handy NC (2004) Chem Phys Lett 393:51CrossRefGoogle Scholar
  69. 69.
    Baer R, Neuhauser D (2005) Phys Rev Lett 94:043002CrossRefGoogle Scholar
  70. 70.
    Stein T, Kronik L, Baer R (2009) J Am Chem Soc 131:2818CrossRefGoogle Scholar
  71. 71.
    Prezhdo OV (2009) Acc Chem Res 42:2005CrossRefGoogle Scholar
  72. 72.
    Suzuki Y-I, Fuji T, Horio T, Suzuki T (2010) J Chem Phys 132:174302CrossRefGoogle Scholar
  73. 73.
    Hammes-Schiffer S, Tully JC (1994) J Chem Phys 101(6):4657CrossRefGoogle Scholar
  74. 74.
    Mitrić R, Petersen J, Bonačić-Koutecký V (2011) In: Conical intersections – theory, computation and experiment. Advanced series in physical chemistry, vol 17. World Scientific, SingaporeGoogle Scholar
  75. 75.
    Lisinetskaya PG, Mitrić R (2011) Phys Rev A 83:033408CrossRefGoogle Scholar
  76. 76.
    Horio T, Fuji T, Suzuki Y-I, Suzuki T (2009) J Am Chem Soc 113:10392CrossRefGoogle Scholar
  77. 77.
    Mitrić R, Petersen J, Wohlgemuth M, Werner U, Bonačić-Koutecký V, Wöste L, Jortner J (2010) J Phys Chem A 115:3755CrossRefGoogle Scholar
  78. 78.
    Hudock HR, Levine BG, Thompson AL, Satzger H, Tonwnsend D, Gador N, Ullrich S, Stolow A, Martinez TJ (2007) J Phys Chem A 111:8500CrossRefGoogle Scholar
  79. 79.
    Fuji T, Suzuki Y-I, Horio T, Suzuki T, Mitrić R, Werner U, Bonačić-Koutecký V (2010) J Chem Phys 133:234303CrossRefGoogle Scholar
  80. 80.
    Fuji T, Horio T, Suzuki T (2007) Opt Lett 32(17):2481CrossRefGoogle Scholar
  81. 81.
    Fuji T, Suzuki T, Serebryannikov EE, Zheltikov A (2009) Phys Rev A 80:063822CrossRefGoogle Scholar
  82. 82.
    Adamo C, Barone V (1999) J Chem Phys 110:6158CrossRefGoogle Scholar
  83. 83.
    Krishnan R, Binkley JS, Seeger R, Pople JA (1980) J Chem Phys 72:650CrossRefGoogle Scholar
  84. 84.
    Barbatti M, Pittner J, Pederzoli M, Werner U, Mitrić R, Bonačić-Koutecký V (2010) Chem Phys 375:26CrossRefGoogle Scholar
  85. 85.
    Gromov EV, Tromifov AB, Vitkovskaya NM, Schirmer J, Köppel H (2003) J Chem Phys 119:737CrossRefGoogle Scholar
  86. 86.
    Gromov EV, Tromifov AB, Vitkovskaya NM, Köppel H, Schirmer J, Meyer HD, Cederbaum LS (2004) J Chem Phys 121:4585CrossRefGoogle Scholar
  87. 87.
    Yang J, Li J, Mo Y (2006) J Chem Phys 125:174313CrossRefGoogle Scholar
  88. 88.
    Derrick P, Asbrink L, Edqvist O, Lindholm E (1971) Spectrochim Acta A 27:2525CrossRefGoogle Scholar
  89. 89.
    Goldberg DE (1989) Genetic algorithms in search, optimization and machine learning. Addison-Wesley, ReadingGoogle Scholar
  90. 90.
    Stewart JJP (1989) J Comput Chem 10:209CrossRefGoogle Scholar
  91. 91.
    Koslowski A, Beck ME, Thiel W (2003) J Comput Chem 24:714CrossRefGoogle Scholar
  92. 92.
    Patchkovskii S, Koslowski A, Thiel W (2005) Theor Chem Acc 114:84CrossRefGoogle Scholar
  93. 93.
    van Gunsteren WF, Berendsen HJC (1982) Mol Phys 45:637CrossRefGoogle Scholar
  94. 94.
    Getoff N, Solar S, McCormick DB (1978) Science 201:616CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media B.V. 2012

Authors and Affiliations

  • Roland Mitrić
    • 1
  • Jens Petersen
    • 1
    • 2
  • Ute Werner
    • 2
  • Vlasta Bonačić-Koutecký
    • 2
    • 3
  1. 1.Fachbereich PhysikFreie Universität BerlinBerlinGermany
  2. 2.Institut für ChemieHumboldt-Universität zu BerlinBerlinGermany
  3. 3.Interdisciplinary Center for Science and TechnologyUniversity of SplitSplitCroatia

Personalised recommendations