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Spectrophotometric Concentration Analysis Without Molar Absorption Coefficients by Two-Dimensional-Infrared and Fourier Transform Infrared Spectroscopy

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Donaldson, Paul M.·2022·Analytical Chemistry
DOI 10.1021/acs.analchem.2c04287PMC PMC9798376
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Abstract

High Resolution Image Download MS PowerPoint Slide A spectrophotometric method for determining relative concentrations of infrared (IR)-active analytes with unknown concentration and unknown molar absorption coefficient is explored. This type of method may be useful for the characterization of complex/heterogeneous liquids or solids, the study of transient species, and for other scenarios where it might be difficult to gain concentration information by other means. Concentration ratios of two species are obtained from their IR absorption and two-dimensional (2D)-IR diagonal bleach signals using simple ratiometric calculations. A simple calculation framework for deriving concentration ratios from spectral data is developed, extended to IR-pump–probe signals, and applied to the calculation of transition dipole ratios. Corrections to account for the attenuation of the 2D-IR signal caused by population relaxation, spectral overlap, wavelength-dependent pump absorption, inhomogeneous broadening, and laser intensity variations are described. A simple formula for calculating the attenuation of the 2D-IR signal due to sample absorption is deduced and by comparison with 2D-IR signals at varying total sample absorbance found to be quantitatively accurate. 2D-IR and Fourier transform infrared spectroscopy of two carbonyl containing species acetone and N -methyl-acetamide dissolved in D 2 O are used to experimentally confirm the validity of the ratiometric calculations. Finally, to address ambiguities over units and scaling of 2D-IR signals, a physical unit of 2D-IR spectral amplitude in mOD/ c m − 1 is proposed.

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Authors
Donaldson, P. M.
Affiliations
Rutherford Appleton Laboratory (GB)
Corresponding author
Donaldson, Paul M.
ORCID
Donaldson, Paul M.
Venue
Analytical Chemistry
Publisher
American Chemical Society (ACS)
Published
2022-12-14
Volume
94
Issue
51
Pages
17988-17999
ISSN
  • 0003-2700 (ISSN-L)
  • 1520-6882
DOI
10.1021/acs.analchem.2c04287
PMC
PMC9798376
OpenAlex
W4311449845
Cited by
18
References
0
Citations by year
2026: 4 · 2025: 6 · 2024: 5 · 2023: 3
FWCI
1.44
Type
journal article
Language
en
Open access
Licence
Locations
  • Analytical Chemistry (publishedVersion, cc-by)
  • PubMed Central (publishedVersion, cc-by)
  • PubMed (publishedVersion)
  • Science and Technology Facilities Council (submittedVersion, cc-by)
Funders
UK Research and Innovation (MR/S015574/1)
Topics
  • Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Spectroscopy and Quantum Chemical Studies
  • Life Sciences › Biochemistry, Genetics and Molecular Biology › Biophysics › Spectroscopy Techniques in Biomedical and Chemical Research
  • Physical Sciences › Chemistry › Spectroscopy › Spectroscopy and Laser Applications
Keywords
two-dimensional infrared spectroscopy, molar absorptivity, ratiometric analysis, population relaxation, spectral overlap, inhomogeneous broadening, acetone, N-methylacetamide

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