1 / 53

Multidimensional Quantum Dynamics: Methods and Applications

Explore multidimensional quantum dynamics methods and applications in the study of chemical reactions. Topics include ESIPT in tautomerization, time-sliced simulations, electron tunneling, and more.

garykthomas
Download Presentation

Multidimensional Quantum Dynamics: Methods and Applications

An Image/Link below is provided (as is) to download presentation Download Policy: Content on the Website is provided to you AS IS for your information and personal use and may not be sold / licensed / shared on other websites without getting consent from its author. Content is provided to you AS IS for your information and personal use only. Download presentation by click this link. While downloading, if for some reason you are not able to download a presentation, the publisher may have deleted the file from their server. During download, if you can't get a presentation, the file might be deleted by the publisher.

E N D

Presentation Transcript

  1. Tuesday, September 28th, 2004 - Physical Chemistry Seminar 11:00 a.m., Room 1315 Chemistry Building Department of Chemistry, University of Wisconsin-Madison Multidimensional Quantum Dynamics: Methods and Applications Xin Chen, Yinghua Wu and Victor S. Batista Department of Chemistry, Yale University, New Haven, CT 06520-8107 Xin Chen Yinghua Wu* *Current address: Department of Chemistry, Tulane University.

  2. ESIPT in the keto-enolic tautomerization of 2-(2’-hydroxyphenyl)-oxazole (HPO). Changes in hybridization and connectivity Classical Dynamics (HPMO) Vendrell, O.; Moreno, M.; Lluch J.M.; Hammes-Schiffer, S. J. Phys. Chem. B 108, 6745 (2004) Quantum Dynamics (7-d simulation, related ESIPT system) Petkovic, M.; Kuhn, O. J. Phys. Chem. A 107, 8458 (2003) SC-IVR (HPO) Guallar, V.; Batista, V.S.; Miller, W.H. J. Chem. Phys. 113, 9510 (2000) Batista, V.S.; Brumer, P. Phys. Rev. Lett. 89, 143201 (2002) Batista, V.S.; Brumer, P. Phys. Rev. Lett. 89, 249903 (2002)

  3. Computation of Observables Time Dependent Reactant Population: Absorption Spectrum: Time Dependent Survival Amplitude

  4. Reaction Surface 35-dimensional Model V(r1,r2,z) = V0(r1,r2) + 1/2 [z- z0(r1,r2)] F(r1,r2) [z-z0(r1,r2)] V0 : Reaction surface r1,r2 : reaction coordinates z0 : ab initio geometries F : ab initio force constants

  5. Reaction Coordinates in HPO r1: H-stretching

  6. Reaction Coordinates in HPO r2: internal bending

  7. CASSCF Reaction Surface Potential V0(r1,r2)

  8. Time-Sliced Simulations of Quantum Processes

  9. Trotter Expansion MP/SOFT Method Wu,Y.; Batista, V.S. J. Chem. Phys. 118, 6720 (2003) Wu,Y.; Batista, V.S. J. Chem. Phys. 119, 7606 (2003) Wu,Y.; Batista, V.S. J. Chem. Phys. 121, 1676 (2004) Chen, X., Wu,Y.; Batista, V.S. J. Chem. Phys. submitted (2004) Wu,Y.; Batista, V.S. J. Chem. Phys. in prep. (2004)

  10. Time-Dependent Survival Amplitude HK SC-IVR vs. MP/SOFT

  11. Time-Dependent Survival Amplitude HK SC-IVR vs. Classical Wigner Wigner SC-IVR

  12. Comparison with experimental data Douhal et.al. JPC 100, 19789 (1997), HPMO in n-hexane S1 S0

  13. Early Time Relaxation Dynamics Time Dependent Reactant Population WIGNER, TD-SCF, HK SC-IVR, MP/SOFT

  14. Longer Time Relaxation Dynamics Time Dependent Reactant Population WIGNER, TD-SCF, HK SC-IVR, MP/SOFT [1] [2] [1] Wu,Y.; Batista, V.S. J. Chem. Phys. in prep. (2004) [2] Guallar, V.; Batista, V.S.; Miller, W.H. J. Chem. Phys. 113, 9510 (2000)

  15. Time Dependent Reactant Population HK SC-IVR, Classical Wigner (SC/L) and WKB

  16. Comparison with experimental data Time dependent reactant (enol) population Femtosecond fluorescent transient at 420nm for HPMO in 3-methylpentane JPC 102,1657 (1998) Zewail and co-workers

  17. Decoherence Dynamics HK SC-IVR vs. MP/SOFT [1] [2] [1] Wu,Y.; Batista, V.S. J. Chem. Phys. in prep. (2004) [2] Batista, V.S.; Brumer, P. Phys. Rev. Lett. 89, 143201 (2002)

  18. Development of new methodologies for studies of Decoherence and Coherent-Control

  19. Coherent-Control of the keto-enolic isomerization in HPO Contour plot of the percentage product yield for bichromatic coherent-control at 100 fs after photoexcitation of the system, as a function of the laser controllable parameters.

  20. Electron Tunneling in Multidimensional Systems Wu,Y.; Batista, V.S. J. Chem. Phys. 121, 1676 (2004)

  21. 2-dimensional (Model I)

  22. 2-dimensional (Model I)

  23. 2-dimensional (Model I)

  24. 2-dimensional (model I)

  25. 5-dimensional (model I)

  26. 5-dimensional (model I)

  27. 5-dimensional (model I)

  28. 5-dimensional (model I)

  29. 5-dimensional (model I)

  30. 5-dimensional (model I)

  31. 5-dimensional (model I)

  32. 10-dimensional (model I)

  33. Electron Tunneling in Multidimensional Systems Model II

  34. (2-dimension Model II)

  35. 2-dimensional (model II)

  36. 2-dimensional (model II)

  37. 2-dimensional (Model II)

  38. 20-dimensional (Model II)

  39. Benchmark calculation: 20-dimensional (model II)

  40. Thermal Correlation Functions Chen, X., Wu,Y.; Batista, V.S. J. Chem. Phys. submitted (2004) Boltzmann Ensemble Averages

  41. Bloch Equation: MP/SOFT Integration Partition Function Boltzmann Matrix:

  42. Calculations of Thermal Correlation Functions Position-Position Correlation Function: Time-Dependent Position Ensemble Average Model System:

  43. Classical density Model System, cont’d Quantum density Ground State, V0 Excited State, V1

  44. Position-Position Correlation Function

More Related