Journal article
Least-Squares Fitting of Multidimensional Spectra to Kubo Line-Shape Models
The journal of physical chemistry. B, Vol.125(46), pp.12876-12891
11/25/2021
DOI: 10.1021/acs.jpcb.1c08764
PMCID: PMC8630800
PMID: 34783568
Appears in UI Libraries Support Open Access
Abstract
We report a comprehensive study of the efficacy of least-squares fitting of multidimensional spectra to generalized Kubo line-shape models and introduce a novel least-squares fitting metric, termed the scale invariant gradient norm (SIGN), that enables a highly reliable and versatile algorithm. The precision of dephasing parameters is between 8× and 50× better for nonlinear model fitting compared to that for the centerline-slope (CLS) method, which effectively increases data acquisition efficiency by 1-2 orders of magnitude. Whereas the CLS method requires sequential fitting of both the nonlinear and linear spectra, our model fitting algorithm only requires nonlinear spectra but accurately predicts the linear spectrum. We show an experimental example in which the CLS time constants differ by 60% for independent measurements of the same system, while the Kubo time constants differ by only 10% for model fitting. This suggests that model fitting is a far more robust method of measuring spectral diffusion than the CLS method, which is more susceptible to structured residual signals that are not removable by pure solvent subtraction. Statistical analysis of the CLS method reveals a fundamental oversight in accounting for the propagation of uncertainty by Kubo time constants in the process of fitting to the linear absorption spectrum. A standalone desktop app and source code for the least-squares fitting algorithm are freely available, with example line-shape models and data. We have written the MATLAB source code in a generic framework where users may supply custom line-shape models. Using this application, a standard desktop fits a 12-parameter generalized Kubo model to a 10
data-point spectrum in a few minutes.
Details
- Title: Subtitle
- Least-Squares Fitting of Multidimensional Spectra to Kubo Line-Shape Models
- Creators
- Kevin C Robben - Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, United StatesChristopher M Cheatum - Department of Chemistry, University of Iowa, Iowa City, Iowa 52242, United States
- Resource Type
- Journal article
- Publication Details
- The journal of physical chemistry. B, Vol.125(46), pp.12876-12891
- DOI
- 10.1021/acs.jpcb.1c08764
- PMID
- 34783568
- PMCID
- PMC8630800
- NLM abbreviation
- J Phys Chem B
- ISSN
- 1520-6106
- eISSN
- 1520-5207
- Publisher
- American Chemical Society
- Grant note
- R21 GM143710 / NIGMS NIH HHS
- Language
- English
- Date published
- 11/25/2021
- Academic Unit
- Liberal Arts and Science Admin; Chemistry
- Record Identifier
- 9984216687002771
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