1. Femtochemistry: A theoretical overview Mario Barbatti mario.barbatti@univie.ac.at VII – Methods in quantum dynamics This lecture can be downloaded at http://homepage.univie.ac.at/mario.barbatti/femtochem.html lecture7.ppt

2. 2 nuclear wave function Multiply by  i at left and integrate in the electronic coordinates Time dependent Schrödinger equation for the nuclei Quantum dynamics

3. 3 Expand nuclear wave function in a basis of n k functions  k for each coordinate R k : Wavepacket program: http://page.mi.fu-berlin.de/burkhard/WavePacket/ Kosloff, J. Phys. Chem. 92, 2087 (1988) Wave-packet propagation

4. 4

5. 5 Multiconfiguration time-dependent Hartree (MCTDH) method Variational method leads to equations of motion for A and . Heidelberg MCDTH program: http://www.pci.uni-heidelberg.de/tc/usr/mctdh/ Meyer and Worth, Theor. Chem. Acc. 109, 251 (2003) Conventional: 1 – 4 degrees of freedom MCTDH: 4 -12 degrees of freedom

6. 6 UV absorption spectrum of pyrazine (24 degrees of freedom!) MCTDH Exp. Raab, et al. J. Chem. Phys. 110, 936 (1999)

7. 7 Multiple spawning dynamics Nuclear wavefunction is expanded in a Gaussian basis set centered at the classical trajectory Note that the number of gaussian functions (N i ) depends on time. Ben-Nun, Quenneville, Martínez, J. Phys. Chem. A 104, 5161 (2000)

8. 8 Multiple spawning dynamics with and

9. 9 Multiple spawning dynamics The non-adiabatic coupling within H ij is computed and monitored along the trajectory. When it become larger than some pre-define threshold, new gaussian functions are created (spawned).

10. 10 Multiple spawning dynamics Saddle point approximation

11. 11 S1S1 S0S0

12. 12 QM (FOMO-AM1)/MM Virshup et al. J. Phys. Chem. B 113, 3280 (2009)

13. 13 Global nature of the nuclear wavefunction R’ R E t t’ E1E1

14. 14 Global nature of the nuclear wavefunction R’ R E t t’ E1E1

15. 15 Within this approximation, the nuclear wavefunction is local: it does not depend on the wavefunction values at other positions of the space This opens two possibilities: 1)On-the-fly approaches (global PESs are no more needed) 2)Classical independent trajectories approximations However, because of the non-adiabatic coupling between different electronic states, the problem cannot be reduced to the Newton’s equations We use, therefore, Mixed Quantum-Classical Dynamics approaches (MQCD)

16. 16 Mixed Quantum-Classical Dynamics Is the classical position x y

17. 17 Mixed Quantum-Classical Dynamics Is the classical position Nuclear motion: Multiply at left by  (R-R c ) 1/2 and integrate in R.

18. 18 Ehrenfest (Average Field) Dynamics With which solves: (adiabatic basis) Weighted average over all gradients Meyer and Miller, J. Chem. Phys. 70, 3214 (1979) Prove! Remember we assumed

19. 19 t E 0 t ci Average surface

20. 20  * n*n* cs Energy N-H dissociation 10 fs  * Ehrenfest dynamics fails for dissociation

21. 21 0.43 0.57 In this case, Ehrenfest dynamics would predict the dissociation on a surface that is ~half/half S 0 and S 1, which does not correspond to the truth. Landau-Zener predicts the populations at t = ∞

22. 22 The problem with the Ehrenfest dynamics is the lack of decoherence. The non-diagonal terms should quickly go to zero because of the coupling among the several degrees of freedom. The approximation  i (R(t)) ~  i (t) does not describe this behavior adequately. Ad hoc corrections may be imposed. Zhu, Jasper and Truhlar, J. Chem. Phys. 120, 5543 (2004) Decoherence

23. 23 Mixed Quantum-Classical Dynamics Is the classical position Nuclear motion:

24. 24 Surface hopping dynamics Tully, J. Chem. Phys. 93, 1061 (1990) Dynamics runs always on a single surface (diabatic or adiabatic). Every time step a stochastic algorithm decides based on the non-adiabatic transition probabilities on which surface the molecule will stay. The wavepacket information is recovered repeating the procedure for a large number of independent trajectories. Because the dynamics runs on a single surface, the decoherence problem is largely reduced (but not eliminated).

25. 25 t E 0 t ci

26. 26 Tully, Faraday Discuss. 110, 407 (1998). Burant and Tully, JCP 112, 6097 (2000) wave-packet surface-hopping (adiabatic) mean-field Landau-Zener surface-hopping (diabatic) Comparison between methods

27. 27 Worth, hunt and Robb, JPCA 127, 621 (2003). Oscillation patterns are not necessarily quantum interferences Butatriene cation Barbatti, Granucci, Persico, Lischka, CPL 401, 276 (2005). Ethylene

28. 28 Quantum Classical Multiple spawning MQCD dynamics Wave packet (MCTDH) Hierarchy of methods

29. 29 Next lecture: Implementation of surface hopping dynamics Contact mario.barbatti@univie.ac.at This lecture can be downloaded at http://homepage.univie.ac.at/mario.barbatti/femtochem.html lecture7.ppt