Standard Article

Quantum chemical studies of carbonyl oxide chemistry in combustion and in the lower atmosphere

Peroxides (2014)

  1. Keith T. Kuwata

Published Online: 28 APR 2014

DOI: 10.1002/9780470682531.pat0826

Patai's Chemistry of Functional Groups

Patai's Chemistry of Functional Groups

How to Cite

Kuwata, K. T. 2014. Quantum chemical studies of carbonyl oxide chemistry in combustion and in the lower atmosphere. Patai's Chemistry of Functional Groups. 1–48.

Author Information

  1. Department of Chemistry, Macalester College, Saint Paul, MN, USA

Publication History

  1. Published Online: 28 APR 2014

Chemistry Terms

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Abstract

Carbonyl oxides have multiple impacts on the atmosphere and on combustion. This review focuses on what electronic structure calculations, particularly those involving ab initio composite methods and density functional theory (DFT), have revealed about carbonyl oxide chemistry in combustion and atmospheric systems. Reliable electronic structure calculations consistently reveal that carbonyl oxides have little diradical character, which means that much of their chemistry can be modeled accurately by single-reference methods. Computation predicts that carbonyl oxides form in the low-temperature combustion of ethers, and, given that carbonyl oxides form hydroxyl radical (OH), they likely contribute to chain branching. The atmospheric ozonolysis of acyclic alkenes leads to moderately chemically activated carbonyl oxides, making it necessary to treat both their unimolecular and bimolecular reactions. CCSD(T) calculations with triple-zeta basis sets and CCSD(T)-based composite methods can predict aspects of carbonyl oxide chemistry like the yield of OH that agree with experiment, but the accuracy of these predictions also depend on statistical thermodynamic assumptions. DFT predictions regarding carbonyl oxide chemistry are often inaccurate. Recent experimental studies have corroborated the long-standing quantum chemical prediction that carbonyl oxides with alkyl substituents either syn or anti to the peroxy bond have dramatically different unimolecular and bimolecular reactivity.

Keywords:

  • Carbonyl oxides;
  • combustion;
  • atmospheric chemistry;
  • ethers;
  • ozonolysis;
  • electronic structure theory;
  • quantum chemistry;
  • composite methods;
  • CBS-QB3;
  • B3LYP;
  • density functional theory;
  • basis sets;
  • barrier heights;
  • hydroxyl radical;
  • unimolecular reactions

Featured Compounds

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  1. 1 - 28
Compound 17a
Molecular Weight:86.0892
Molecular Formula:C4H6O2
InChIKey:WHIGGEYDDWFYON-UHFFFAOYSA-N
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Compound 17b
Molecular Weight:86.0892
Molecular Formula:C4H6O2
InChIKey:WHIGGEYDDWFYON-UHFFFAOYSA-N
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Compound 17c
Molecular Weight:86.0892
Molecular Formula:C4H6O2
InChIKey:WHIGGEYDDWFYON-UHFFFAOYSA-N
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Compound 17d
Molecular Weight:86.0892
Molecular Formula:C4H6O2
InChIKey:WHIGGEYDDWFYON-UHFFFAOYSA-N
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Compound 29
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 22
Molecular Weight:86.0892
Molecular Formula:C4H6O2
InChIKey:LVSQXDHWDCMMRJ-UHFFFAOYSA-N
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Compound 1
Molecular Weight:60.052
Molecular Formula:C2H4O2
InChIKey:OATRENYCMVOEIQ-UHFFFAOYSA-N
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Compound 2
Molecular Weight:60.052
Molecular Formula:C2H4O2
InChIKey:OATRENYCMVOEIQ-UHFFFAOYSA-N
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Compound 25x
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound B
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 25a
Molecular Weight:62.0678
Molecular Formula:C2H6O2
InChIKey:ILHIHKRJJMKBEE-UHFFFAOYSA-N
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Compound 25b
Molecular Weight:62.0678
Molecular Formula:C2H6O2
InChIKey:ILHIHKRJJMKBEE-UHFFFAOYSA-N
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Compound 32
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 30
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound C
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 16
Molecular Weight:60.052
Molecular Formula:C2H4O2
InChIKey:Not Available
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Compound 32
Molecular Weight:74.0785
Molecular Formula:C3H6O2
InChIKey:BKMVYAGOHSKLMQ-UHFFFAOYSA-N
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Compound 31
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 24
Molecular Weight:86.0892
Molecular Formula:C4H6O2
InChIKey:PKQIDSVLSKFZQC-UHFFFAOYSA-N
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Compound A
Molecular Weight:Not Available
Molecular Formula:Not Available
InChIKey:Not Available
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Compound 34
Molecular Weight:74.0785
Molecular Formula:C3H6O2
InChIKey:BFFQFGGITJXTFP-UHFFFAOYSA-N
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Compound 4
Molecular Weight:60.052
Molecular Formula:C2H4O2
InChIKey:NOZLREUTKGWBPY-UHFFFAOYSA-N
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Compound 12
Molecular Weight:60.052
Molecular Formula:C2H4O2
InChIKey:AZHSSKPUVBVXLK-UHFFFAOYSA-N
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Compound 3
Molecular Weight:60.052
Molecular Formula:C2H4O2
InChIKey:IEZWOVIWXFLQTP-UHFFFAOYSA-N
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Compound 13
Molecular Weight:60.052
Molecular Formula:C2H4O2
InChIKey:QTBSBXVTEAMEQO-UHFFFAOYSA-N
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Compound 33
Molecular Weight:74.0785
Molecular Formula:C3H6O2
InChIKey:SGJUFIMCHSLMRJ-UHFFFAOYSA-N
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Compound 21
Molecular Weight:86.0892
Molecular Formula:C4H6O2
InChIKey:HFNXPZQXFIEKOI-UHFFFAOYSA-N
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Compound 23
Molecular Weight:86.0892
Molecular Formula:C4H6O2
InChIKey:YBWJKTAELMMCHQ-UHFFFAOYSA-N
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  1. 1 - 28