Journal article
Line shape analysis of two-dimensional infrared spectra
The Journal of chemical physics, Vol.142(21), pp.212427-212427
06/07/2015
DOI: 10.1063/1.4918350
PMCID: PMC4409623
PMID: 26049447
Abstract
Ultrafast two-dimensional infrared (2D IR) spectroscopy probes femtosecond to picosecond time scale dynamics ranging from solvation to protein motions. The frequency-frequency correlation function (FFCF) is the quantitative measure of the spectral diffusion that reports those dynamics and, within certain approximations, can be extracted directly from 2D IR line shapes. A variety of methods have been developed to extract the FFCF from 2D IR spectra, which, in principle, should give the same FFCF parameters, but the complexity of real experimental systems will affect the results of these analyses differently. Here, we compare five common analysis methods using both simulated and experimental 2D IR spectra to understand the effects of apodization, anharmonicity, phasing errors, and finite signal-to-noise ratios on the results of each of these analyses. Our results show that although all of the methods can, in principle, yield the FFCF under idealized circumstances, under more realistic experimental conditions they behave quite differently, and we find that the centerline slope analysis yields the best compromise between the effects we test and is most robust to the distortions that they cause.
Details
- Title: Subtitle
- Line shape analysis of two-dimensional infrared spectra
- Creators
- Qi Guo - Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, USA and Optical Science and Technology Center, University of Iowa, Iowa City, Iowa 52242, USAPhilip Pagano - Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, USA and Optical Science and Technology Center, University of Iowa, Iowa City, Iowa 52242, USAYun-Liang Li - Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, USA and Optical Science and Technology Center, University of Iowa, Iowa City, Iowa 52242, USAAmnon Kohen - Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, USA and Optical Science and Technology Center, University of Iowa, Iowa City, Iowa 52242, USAChristopher M Cheatum - Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, USA and Optical Science and Technology Center, University of Iowa, Iowa City, Iowa 52242, USA
- Resource Type
- Journal article
- Publication Details
- The Journal of chemical physics, Vol.142(21), pp.212427-212427
- DOI
- 10.1063/1.4918350
- PMID
- 26049447
- PMCID
- PMC4409623
- ISSN
- 0021-9606
- eISSN
- 1089-7690
- Grant note
- R01 GM079368 / NIGMS NIH HHS R01 GM79368 / NIGMS NIH HHS
- Language
- English
- Date published
- 06/07/2015
- Academic Unit
- Liberal Arts and Science Admin; Chemistry
- Record Identifier
- 9984216703802771
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