slides for powerpoint: nonlinear and two-dimensional spectroscopy
DESCRIPTION
Slides for PowerPoint: Nonlinear and Two-Dimensional Spectroscopy. Andrei Tokmakoff MIT Department of Chemistry. Complete Slides. Why 2D IR Spectroscopy?. IR spectroscopy IR probes vibrations intrinsic to all molecules Each vibration gives different information Structure and dynamics - PowerPoint PPT PresentationTRANSCRIPT
![Page 1: Slides for PowerPoint: Nonlinear and Two-Dimensional Spectroscopy](https://reader036.vdocuments.net/reader036/viewer/2022062222/568163c9550346895dd50221/html5/thumbnails/1.jpg)
Slides for PowerPoint:
Nonlinear and Two-Dimensional Spectroscopy
Andrei TokmakoffMIT Department of Chemistry
![Page 2: Slides for PowerPoint: Nonlinear and Two-Dimensional Spectroscopy](https://reader036.vdocuments.net/reader036/viewer/2022062222/568163c9550346895dd50221/html5/thumbnails/2.jpg)
Complete Slides
![Page 3: Slides for PowerPoint: Nonlinear and Two-Dimensional Spectroscopy](https://reader036.vdocuments.net/reader036/viewer/2022062222/568163c9550346895dd50221/html5/thumbnails/3.jpg)
Why 2D IR Spectroscopy?
• IR spectroscopy– IR probes vibrations intrinsic to all molecules– Each vibration gives different information
› Structure and dynamics– Intrinsic time-scale of ~1 ps
• 2D IR spectroscopy: A more sensitive probe– Characterize vibrational correlations
» Couplings, orientation, exchange
– Resolves congested spectra & suppresses inhomogeneous broadening
– Quantitative structure-based modeling
![Page 4: Slides for PowerPoint: Nonlinear and Two-Dimensional Spectroscopy](https://reader036.vdocuments.net/reader036/viewer/2022062222/568163c9550346895dd50221/html5/thumbnails/4.jpg)
Fourier transform 2D IR spectroscopy
![Page 5: Slides for PowerPoint: Nonlinear and Two-Dimensional Spectroscopy](https://reader036.vdocuments.net/reader036/viewer/2022062222/568163c9550346895dd50221/html5/thumbnails/5.jpg)
Ultrafast nonlinear spectroscopy
mask
![Page 6: Slides for PowerPoint: Nonlinear and Two-Dimensional Spectroscopy](https://reader036.vdocuments.net/reader036/viewer/2022062222/568163c9550346895dd50221/html5/thumbnails/6.jpg)
Polarization-selective pump-probe experiment
Magic Angle: Vibrational Lifetime
Anisotropy: Reorientation
1T
|| ||r t S S S 2S
![Page 7: Slides for PowerPoint: Nonlinear and Two-Dimensional Spectroscopy](https://reader036.vdocuments.net/reader036/viewer/2022062222/568163c9550346895dd50221/html5/thumbnails/7.jpg)
Peak Shift Measurement
ta – tb (fs)
![Page 8: Slides for PowerPoint: Nonlinear and Two-Dimensional Spectroscopy](https://reader036.vdocuments.net/reader036/viewer/2022062222/568163c9550346895dd50221/html5/thumbnails/8.jpg)
2D IR Interferometer
time/frequencydetection
time/timedetection
![Page 9: Slides for PowerPoint: Nonlinear and Two-Dimensional Spectroscopy](https://reader036.vdocuments.net/reader036/viewer/2022062222/568163c9550346895dd50221/html5/thumbnails/9.jpg)
2D IR Spectroscopy in pump-probe geometry
![Page 10: Slides for PowerPoint: Nonlinear and Two-Dimensional Spectroscopy](https://reader036.vdocuments.net/reader036/viewer/2022062222/568163c9550346895dd50221/html5/thumbnails/10.jpg)
Obtaining an Absorptive 2D IR Spectrum
![Page 11: Slides for PowerPoint: Nonlinear and Two-Dimensional Spectroscopy](https://reader036.vdocuments.net/reader036/viewer/2022062222/568163c9550346895dd50221/html5/thumbnails/11.jpg)
2D IR spectroscopy
Frequency Fluctuations Vibrational Couplings Chemical Exchange
• Related to the joint probability
3,final 2 1,initialP , ;
2 = 0 2 > c
![Page 12: Slides for PowerPoint: Nonlinear and Two-Dimensional Spectroscopy](https://reader036.vdocuments.net/reader036/viewer/2022062222/568163c9550346895dd50221/html5/thumbnails/12.jpg)
• Excite: Initial frequency 1
• Wait for period 2
• Detect: Final frequency 3
Chemical exchange and spectral diffusion
2 = 0
2 →
![Page 13: Slides for PowerPoint: Nonlinear and Two-Dimensional Spectroscopy](https://reader036.vdocuments.net/reader036/viewer/2022062222/568163c9550346895dd50221/html5/thumbnails/13.jpg)
AbsorptiveCS
2D lineshapes: Loss of frequency correlation
Phase
a
b
Phase slope
Ellipticity
![Page 14: Slides for PowerPoint: Nonlinear and Two-Dimensional Spectroscopy](https://reader036.vdocuments.net/reader036/viewer/2022062222/568163c9550346895dd50221/html5/thumbnails/14.jpg)
Extra Graphics
![Page 15: Slides for PowerPoint: Nonlinear and Two-Dimensional Spectroscopy](https://reader036.vdocuments.net/reader036/viewer/2022062222/568163c9550346895dd50221/html5/thumbnails/15.jpg)
2D Lineshapes
![Page 16: Slides for PowerPoint: Nonlinear and Two-Dimensional Spectroscopy](https://reader036.vdocuments.net/reader036/viewer/2022062222/568163c9550346895dd50221/html5/thumbnails/16.jpg)
Rephasing and Non-rephasing
![Page 17: Slides for PowerPoint: Nonlinear and Two-Dimensional Spectroscopy](https://reader036.vdocuments.net/reader036/viewer/2022062222/568163c9550346895dd50221/html5/thumbnails/17.jpg)
Rephasing and Non-rephasing
![Page 18: Slides for PowerPoint: Nonlinear and Two-Dimensional Spectroscopy](https://reader036.vdocuments.net/reader036/viewer/2022062222/568163c9550346895dd50221/html5/thumbnails/18.jpg)
2D IR Spectrum of RDC in Hexane
![Page 19: Slides for PowerPoint: Nonlinear and Two-Dimensional Spectroscopy](https://reader036.vdocuments.net/reader036/viewer/2022062222/568163c9550346895dd50221/html5/thumbnails/19.jpg)
2D IR Spectrum of RDC in Hexane
![Page 20: Slides for PowerPoint: Nonlinear and Two-Dimensional Spectroscopy](https://reader036.vdocuments.net/reader036/viewer/2022062222/568163c9550346895dd50221/html5/thumbnails/20.jpg)
Polarization-Selective 2D IR Spectroscopy
![Page 21: Slides for PowerPoint: Nonlinear and Two-Dimensional Spectroscopy](https://reader036.vdocuments.net/reader036/viewer/2022062222/568163c9550346895dd50221/html5/thumbnails/21.jpg)
Projection Angle from Peak Amplitudes