Role of vibrational anharmonicity in atmospheric radical hydrogen-bonded complexes

Harmonic and anharmonic vibrational frequency calculations are reported for the most stable hydrogen bonded complexes formed between the hydroperoxyl radical and formic, acetic, nitric, and sulfuric acids which are of atmospheric interest. A comparison between the calculated IR spectra of the hydrog...

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Bibliographic Details
Published in:Physical chemistry chemical physics : PCCP 2009-01, Vol.11 (30), p.6377-6388
Main Authors: TORRENT-SUCARRAT, M, ANGLADA, J. M, LUIS, J. M
Format: Article
Language:English
Subjects:
Acetic Acid - chemistry
Atmosphere
Biochemistry - methods
Chemistry
Chemistry, Physical - methods
Exact sciences and technology
Formates - chemistry
Free Radicals
General and physical chemistry
Hydrogen Bonding
Hydroxyl Radical
Molecular Conformation
Nitric Acid - chemistry
Normal Distribution
Photochemistry - methods
Software
Spectrophotometry, Infrared - methods
Sulfuric Acids - chemistry
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Summary:Harmonic and anharmonic vibrational frequency calculations are reported for the most stable hydrogen bonded complexes formed between the hydroperoxyl radical and formic, acetic, nitric, and sulfuric acids which are of atmospheric interest. A comparison between the calculated IR spectra of the hydrogen bonded complexes with the corresponding separate monomers is also reported with the aim to facilitate a possible experimental identification of these complexes. The calculations have been carried out using the second-order vibrational perturbative treatment implemented by Barone applied to the PES obtained with the B3LYP functional using the 6-31+G(d,p) and 6-311+G(2d,2p) basis sets. Our calculations for the separate monomers predict vibrational frequencies with quite a good agreement with the experimental values. The anharmonic contribution results in differences of around 40 cm(-1) with respect to the harmonic values; although in some cases involving highly anharmonic modes, these differences can rise up to 300 and 450 cm(-1).
ISSN:1463-9076
1463-9084
DOI:10.1039/b904736k