The role of structured water in the calibration and interpretation of theoretical IR spectra

The purpose of this study was to simulate theoretical infrared (IR) spectra of halogenated acetate salts using density functional theory (DFT), and to calibrate those results with high-resolution ATR-FTIR spectra. Two types of spectra were calculated: one of the solutes solvated in water droplets ra...

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Bibliographic Details
Published in:Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy Molecular and biomolecular spectroscopy, 2006-10, Vol.65 (2), p.324-332
Main Authors: Wander, Matthew C.F., Kubicki, James D., Schoonen, Martin A.A.
Format: Article
Language:English
Subjects:
Acetate
Acetates - analysis
Acetates - chemistry
ATR-FTIR
Bromides - analysis
Bromides - chemistry
Calibration
DFT
Fluoroacetates - analysis
Fluoroacetates - chemistry
Germanium - analysis
Germanium - chemistry
Halogenated acetates
Ions
Models, Chemical
Models, Molecular
Quantum Theory
Sodium Compounds - analysis
Sodium Compounds - chemistry
Sodium Fluoride - analysis
Sodium Fluoride - chemistry
Solutions
Solvation sphere
Solvents - chemistry
Spectroscopy, Fourier Transform Infrared - standards
Water - chemistry
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Summary:The purpose of this study was to simulate theoretical infrared (IR) spectra of halogenated acetate salts using density functional theory (DFT), and to calibrate those results with high-resolution ATR-FTIR spectra. Two types of spectra were calculated: one of the solutes solvated in water droplets ranging in size from 15 to ∼28 H 2O molecules, and the other of a solvent molecule in equivalently sized (16–29 H 2O molecules) droplets. The background-subtracted spectra, composed of solvated (halo)acetate spectra minus calculated solvent spectra, were compared with their experimental counterparts. Changes in the calculated IR spectra were used to determine the effects of dissolved salts on the structure of water. Calibrations of model dissolved salt spectra with observation were good; correlations of >0.90 were observed for all haloacetate species.
ISSN:1386-1425
DOI:10.1016/j.saa.2005.10.048