Nonlinear spectroscopy characterizing fluctuations
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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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Nonlinear spectroscopy characterizing fluctuations

Nonlinear Spectroscopy:Characterizing Fluctuations

Andrei Tokmakoff

MIT Department of Chemistry

2009


Fluctuations in lineshapes

Fluctuations in lineshapes


System bath interactions

System-Bath Interactions

  • System: Spectroscopically Bright States

  • Bath: Dark States

  • → Energy Gap Fluctuations

  • In spectroscopy … (Condon Approx.)


Energy gap fluctuations

Energy Gap Fluctuations

  • Energy Gap Correlation Function

  • Dipole Correlation Function → Absorption lineshape

  • Second Cumulant approx.


A bath of arbitrary form

A bath of arbitrary form

  • Spectral Density

  • Brownian Oscillator Model


Nonlinear response for fluctuating system

Nonlinear response for fluctuating system

  • Following earlier approach:

  • Cumulant approximation:


Two pulse echo

Two pulse echo

~1/D


Two pulse echo1

Two pulse echo


Lens analogy

Lens analogy


Three pulse echoes peak shift

Three pulse echoes: Peak shift


2d lineshapes

2D Lineshapes


Spectral diffusion and waiting time

Spectral Diffusion and Waiting Time


Time domain 2d spectroscopy

Time-domain 2D Spectroscopy


Time domain echo shape

Time-Domain: Echo shape


2d ir relaxation experiment probes spectral diffusion

2D IR Relaxation Experiment Probes Spectral Diffusion


Ellipticity

Ellipticity


Correlation of spectral broadening

Correlation of Spectral Broadening


Correlation effects in 2d ir spectra

Correlation Effects in 2D IR Spectra


Correlated energy fluctuations

Correlated Energy Fluctuations

Frequency Auto- and Cross-Correlation Functions:


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