1. Dynamics of irradiated clusters and molecules Solvated molecules Deposited clusters Free clusters Electron Emission Laser Projectile Irradiation of solvated « bio »molecules - Microscopic mechanisms - Role of water environment - Medical applications - Society applications Deposited/embedded species - Shaping at nanoscale - Defect formation - Chromophore effects and therapy applications Laser irradiations of free clusters - Huge energy absorption in intense laser fields - Production of energetic electrons, ions, photons - Many-body « laboratory » - Time resolved dynamics

2. Specifications Dynamical description of irradiation and response of - Electrons - Ions - Environment Implies: - Variety of systems - Variety of time scales - Variety of scenarios Implies: - Robustness - Flexibility - Modularity Implies: - Use of well tested methods - Simplicity - Documentation

3. Example : Na + 9 + laser I = 5. 10 11 W.cm -2 Pulse in cos 2 Delay = 50 fs FWHM = 125 fs  = 2.3 eV Laser intensity  0 E Laser polarization

4. Time Dependent Density Functional Theory (TDDFT) Ensemble of orbitals (1 electron) / no correlation One body density Effective mean field theory (Kohn-Sham) Explicit ions via pseudo potentials Detail of structure + ionic Molecular Dynamics (MD)  Ions  Electrons Kohn-Sham potentialIons + ext. Local Density Approximation (LDA) Exch. + Corr.Coulomb direct + Self Interaction Correction (SIC) … TDLDA-MD : coupled non adiabatic electrons + ions dynamics Model (cluster/molecule) Semi-classical theory available (Vlasov, VUU)

5. Time Dependent Density Functional Theory (TDDFT) Ensemble of orbitals (1 electron) / no correlation One body density Effective mean field theory (Kohn-Sham) Explicit ions via pseudo potentials Detail of structure + ionic Molecular Dynamics (MD)  Ions  Electrons Kohn-Sham potentialIons + ext. Local Density Approximation (LDA) Exch. + Corr.Coulomb direct + Self Interaction Correction (SIC) … TDLDA-MD : coupled non adiabatic electrons + ions dynamics Model (cluster/molecule) Semi-classical theory available (Vlasov, VUU) fs ps

6. Observables Optical response : Dipole Spectral analysis Photoabsorption cross sections Excitation energy Positions and velocities Kinetic energy, temperature Ionization Total number of emitted electrons Ionization probabilities Kinetic energy spectra of electrons (PES) Angular distributions of emitted electrons (PAD)  Ions  Electrons

7. Electron emission from irradiated clusters Laser ( , I, , z) Electron energy Photoelectrons Yield  (  ) d  /dE Ionization Yield Photon energy

8. I Energy resol. angul. distri. Electron emission from irradiated clusters Laser ( , I, , z) Photoelectrons Electron energy Yield Angle Angular distrib. Yield  (  ) Laser Ionization Yield d  /dE d  /d  Photon energy Electron emission from irradiated clusters III Time resolved dynamics FEL lasers II Optical Response Yield

9. Electron emission from irradiated clusters Laser ( , I, , z) Photoelectrons Electron energy Yield Angle Angular distrib. Yield  (  ) Laser Ionization Yield d  /dE d  /d  Photon energy Electron emission from irradiated clusters FEL lasers I III Time resolved dynamics Energy resol. angul. distri. II Optical Response Yield

10. Exp Freiburg Level energy Exp Energy resolved angular distributions Angle-energy correlation  d  /d  dE Laser polarization Exp. Rostock Angle C 60 Theo PAD Exp Theo

11. Energy resolved angular distributions Laser polarization Exp. Rostock Angle C 60 Theo Na 58 (no 2d) Jellium Orientation Average Angle-energy correlation  d  /d  dE The orientation Problem… Exp Freiburg Level energy Exp PAD Exp Theo

12. Electron emission from irradiated clusters Laser ( , I, , z) Photoelectrons Electron energy Yield Angle Angular distrib. Yield  (  ) Laser Ionization Yield d  /dE d  /d  Photon energy Electron emission from irradiated clusters FEL lasers I III Time resolved dynamics Energy resol. angul. distri. II Optical Response Yield

13. FWHM = 20 fs C2H4C2H4 Laser polariz. Below resonancesResonance regionWell above reson. Ethylene in laser fields Organic molecule as test case for irradiation with very high frequency lasers Comparison to metal clusters (resonance)

14. Electron emission from irradiated clusters Laser ( , I, , z) Photoelectrons Electron energy Yield Angle Angular distrib. Yield  (  ) Laser Ionization Yield d  /dE d  /d  Photon energy Electron emission from irradiated clusters FEL lasers I III Time resolved dynamics Energy resol. angul. distri. II Optical Response Yield

15. Electron emission from irradiated clusters Laser ( , I, , z) Photoelectrons Electron energy Yield Angle Angular distrib. Yield  (  ) Laser Ionization Yield d  /dE d  /d  Photon energy Electron emission from irradiated clusters FEL lasers I III Time resolved dynamics Energy resol. angul. distri. II Optical Response Yield  

16. Laser ( , I, , z) FEL lasers II Electron emission from irradiated clusters Photoelectrons Electron energy Yield Angle Angular distrib. Yield  (  ) Laser Ionization Yield d  /dE d  /d  Photon energy Electron emission from irradiated clusters I III Time resolved dynamics Energy resol. angul. distri. Optical Response Yield 

17. Laser ( , I, , z) FEL lasers II Electron emission from irradiated clusters Photoelectrons Electron energy Yield Angle Angular distrib. Yield  (  ) Laser Ionization Yield d  /dE d  /d  Photon energy Electron emission from irradiated clusters I III Time resolved dynamics Energy resol. angul. distri. Optical Response Yield 

18. Laser ( , I, , z) FEL lasers II Electron emission from irradiated clusters Photoelectrons Electron energy Yield Angle Angular distrib. Yield  (  ) Laser Ionization Yield d  /dE d  /d  Photon energy Electron emission from irradiated clusters I III Time resolved dynamics Energy resol. angul. distri. Optical Response Yield 

19. Pump – probe for vibration Strong Ionization Weak Pump Probe   Mie ~  / R 3 Time / Delay Plasmon Mie / Ioniz. Ionization maps Vibrations Ionization

20. Monopole « Pump – Probe » Dynamics Ionization as a function of delay between pump and probe laser pulses Structure (vibrations…) Dynamics (viscosity…) Pump Probe Ionic vibration period Expansion rate Exp. Gerber

21. Irradiation of clusters and molecules Laser Projectile Signals from electrons Solvated molecules Deposited clusters Free clusters Electron Emission Dynamical description of irradiation and response of - electrons - ions - environment Environment - Hierarchical model Dynamical QM/MM - Na@Ar, Kr, Ne done - Na @ MgO done - Na@H 2 O in the oven - C, N, O @ H 2 O in near future - C, N, O @ H 2 O @Ar in future Dynamics of ionization in TDDFT - Self Interaction problem (SIC) - Benchmark TDSIC calculation done - Simple approximations in the oven - Dynamical correlations in the future (electronic transport) Time resolved dynamics - Key importance of non adiabatic electron/ion couplings - Photoelectron spectroscopy energy, angle done/ in the oven - Pump and probe scenarios done - FEL laser domain in the oven - Collisional scenarios in near future - Atto laser domain in the oven People P. M. Dinh, P. G. Reinhard, ES, Z. Wang

22. Example of collision : Na + 9 + Ar 8+ E = 2.32 keV b = 20 a 0