Predictions of the sulfur and carbon kinetic isotope effects in the OH plus OCS reaction

被引：14

作者：

Schmidt, J. A. ^{[1
]}

Johnson, M. S. ^{[1
]}

Jung, Y. ^{[2
]}

Danielache, S. O. ^{[3
]}

Hattori, S. ^{[4
]}

Yoshida, N. ^{[4
]}

机构：

[1] Univ Copenhagen, Dept Chem, DK-2100 Copenhagen O, Denmark

[2] Korea Adv Inst Sci & Technol, Grad Sch EEWS, Taejon 305701, South Korea

[3] Tokyo Inst Technol, Dept Earth & Planetary Sci, Meguro Ku, Tokyo 1528551, Japan

[4] Tokyo Inst Technol, Dept Environm Chem & Engn, Yokohama, Kanagawa 2268502, Japan

来源：

CHEMICAL PHYSICS LETTERS | 2012年 / 531卷

关键词：

CORRELATED MOLECULAR CALCULATIONS; GAUSSIAN-BASIS SETS; TRIPLE EXCITATIONS; RATE CONSTANTS; AB-INITIO; SULFIDE; FRACTIONATION; STRATOSPHERE; SPECTROSCOPY; RADICALS;

D O I：

10.1016/j.cplett.2012.02.049

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The S-34 and C-13 isotopic fractionations in the OCS + OH reaction are investigated using RRKM-theory. The reaction proceeds via different channels, at low pressures a channel leading to CO + SOH dominates. While with increasing pressure an adduct forming channel becomes competitive. The resulting overall rate constant is not strongly dependent on pressure and agrees well with experiments. The competition between channels makes the fractionation constants highly pressure dependent, however the sulfur-34 fractionation constant varies only from about -5 parts per thousand to 0 parts per thousand in the troposphere and lower stratosphere. The carbon-13 isotopic fractionation is stronger; between -40 parts per thousand and -70 parts per thousand in the troposphere and lower stratosphere. (C) 2012 Elsevier B.V. All rights reserved.

引用

页码：64 / 69

页数：6

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