Computational Studies on the Kinetics and Mechanisms for NH3Reactions with ClOx(x0−4) Radicals.
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| Title: | Computational Studies on the Kinetics and Mechanisms for NH3Reactions with ClOx(x0−4) Radicals. |
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| Authors: | Z. F. Xu1, M. C. Lin1 |
| Source: | Journal of Physical Chemistry A. Feb2007, Vol. 111 Issue 4, p584-590. 7p. |
| Subjects: | Hydrogen, Nonmetals, Mathematical complexes, Coordinates |
| Abstract: | Kinetics and mechanisms for NH3reactions with ClOx(x0−4) radicals have been investigated at the G2M level of theory in conjunction with statistical theory calculations. The geometric parameters of the species and stationary points involved in the reactions have been optimized at the B3LYP/6-311G(3df,2p) level of theory. Their energetics have been further refined with the G2M method. The results show that the H-abstraction process is the most favorable channel in each reaction and the barriers predicted in decreasing order are OClO > ClO > Cl > ClO3> ClO4. All reactions were found to occur by hydrogen-bonding complexes; the rate constants for these complex metathetical processes have been calculated in the temperature range 200−2000 K by the microcanonical VTST and/or RRKM theory (for ClO4NH3) with Eckart tunneling and multiple reflection corrections. The predicted rate constants are in good agreement with the available experimental data. [ABSTRACT FROM AUTHOR] |
| Copyright of Journal of Physical Chemistry A is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract. (Copyright applies to all Abstracts.) | |
| Database: | Engineering Source |
| FullText | Text: Availability: 0 |
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| Header | DbId: egs DbLabel: Engineering Source An: 23926280 AccessLevel: 6 PubType: Academic Journal PubTypeId: academicJournal PreciseRelevancyScore: 0 |
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| Items | – Name: Title Label: Title Group: Ti Data: Computational Studies on the Kinetics and Mechanisms for NH3Reactions with ClOx(x0−4) Radicals. – Name: Author Label: Authors Group: Au Data: <searchLink fieldCode="AR" term="%22Z%2E+F%2E+Xu%22">Z. F. Xu</searchLink><relatesTo>1</relatesTo><br /><searchLink fieldCode="AR" term="%22M%2E+C%2E+Lin%22">M. C. Lin</searchLink><relatesTo>1</relatesTo> – Name: TitleSource Label: Source Group: Src Data: <searchLink fieldCode="JN" term="%22Journal+of+Physical+Chemistry+A%22">Journal of Physical Chemistry A</searchLink>. Feb2007, Vol. 111 Issue 4, p584-590. 7p. – Name: Subject Label: Subjects Group: Su Data: <searchLink fieldCode="DE" term="%22Hydrogen%22">Hydrogen</searchLink><br /><searchLink fieldCode="DE" term="%22Nonmetals%22">Nonmetals</searchLink><br /><searchLink fieldCode="DE" term="%22Mathematical+complexes%22">Mathematical complexes</searchLink><br /><searchLink fieldCode="DE" term="%22Coordinates%22">Coordinates</searchLink> – Name: Abstract Label: Abstract Group: Ab Data: Kinetics and mechanisms for NH3reactions with ClOx(x0−4) radicals have been investigated at the G2M level of theory in conjunction with statistical theory calculations. The geometric parameters of the species and stationary points involved in the reactions have been optimized at the B3LYP/6-311G(3df,2p) level of theory. Their energetics have been further refined with the G2M method. The results show that the H-abstraction process is the most favorable channel in each reaction and the barriers predicted in decreasing order are OClO > ClO > Cl > ClO3> ClO4. All reactions were found to occur by hydrogen-bonding complexes; the rate constants for these complex metathetical processes have been calculated in the temperature range 200−2000 K by the microcanonical VTST and/or RRKM theory (for ClO4NH3) with Eckart tunneling and multiple reflection corrections. The predicted rate constants are in good agreement with the available experimental data. [ABSTRACT FROM AUTHOR] – Name: AbstractSuppliedCopyright Label: Group: Ab Data: <i>Copyright of Journal of Physical Chemistry A is the property of American Chemical Society and its content may not be copied or emailed to multiple sites without the copyright holder's express written permission. Additionally, content may not be used with any artificial intelligence tools or machine learning technologies. However, users may print, download, or email articles for individual use. This abstract may be abridged. No warranty is given about the accuracy of the copy. Users should refer to the original published version of the material for the full abstract.</i> (Copyright applies to all Abstracts.) |
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| RecordInfo | BibRecord: BibEntity: Identifiers: – Type: doi Value: 10.1021/jp065397t Languages: – Code: eng Text: English PhysicalDescription: Pagination: PageCount: 7 StartPage: 584 Subjects: – SubjectFull: Hydrogen Type: general – SubjectFull: Nonmetals Type: general – SubjectFull: Mathematical complexes Type: general – SubjectFull: Coordinates Type: general Titles: – TitleFull: Computational Studies on the Kinetics and Mechanisms for NH3Reactions with ClOx(x0−4) Radicals. Type: main BibRelationships: HasContributorRelationships: – PersonEntity: Name: NameFull: Z. F. Xu – PersonEntity: Name: NameFull: M. C. Lin IsPartOfRelationships: – BibEntity: Dates: – D: 01 M: 02 Text: Feb2007 Type: published Y: 2007 Identifiers: – Type: issn-print Value: 10895639 Numbering: – Type: volume Value: 111 – Type: issue Value: 4 Titles: – TitleFull: Journal of Physical Chemistry A Type: main |
| ResultId | 1 |
