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Nonlinear Spectroscopy: Characterizing Fluctuations

Nonlinear Spectroscopy: Characterizing Fluctuations. Andrei Tokmakoff MIT Department of Chemistry 2009. Fluctuations in lineshapes. System-Bath Interactions . System: Spectroscopically Bright States Bath: Dark States → Energy Gap Fluctuations In spectroscopy … (Condon Approx.).

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Nonlinear Spectroscopy: Characterizing Fluctuations

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  1. Nonlinear Spectroscopy:Characterizing Fluctuations Andrei Tokmakoff MIT Department of Chemistry 2009

  2. Fluctuations in lineshapes

  3. System-Bath Interactions • System: Spectroscopically Bright States • Bath: Dark States • → Energy Gap Fluctuations • In spectroscopy … (Condon Approx.)

  4. Energy Gap Fluctuations • Energy Gap Correlation Function • Dipole Correlation Function → Absorption lineshape • Second Cumulant approx.

  5. A bath of arbitrary form • Spectral Density • Brownian Oscillator Model

  6. Nonlinear response for fluctuating system • Following earlier approach: • Cumulant approximation:

  7. Two pulse echo ~1/D

  8. Two pulse echo

  9. Lens analogy

  10. Three pulse echoes: Peak shift

  11. 2D Lineshapes

  12. Spectral Diffusion and Waiting Time

  13. Time-domain 2D Spectroscopy

  14. Time-Domain: Echo shape

  15. 2D IR Relaxation Experiment Probes Spectral Diffusion

  16. Ellipticity

  17. Correlation of Spectral Broadening

  18. Correlation Effects in 2D IR Spectra

  19. Correlated Energy Fluctuations Frequency Auto- and Cross-Correlation Functions:

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