VIBRATIONAL-SPECTRA OF MOLECULAR-IONS ISOLATED IN SOLID NEON .6. CO4-

被引:32
|
作者
JACOX, ME [1 ]
THOMPSON, WE [1 ]
机构
[1] NATL SCI FDN,WASHINGTON,DC 20550
来源
JOURNAL OF PHYSICAL CHEMISTRY | 1991年 / 95卷 / 07期
关键词
D O I
10.1021/j100160a028
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
When a Ne:CO2:O2 = 200:1:1 mixture is codeposited at approximately 5 K with a beam of neon atoms that have been excited in a microwave discharge, several prominent infrared absorptions appear in the resulting deposit. In addition to the absorptions of unreacted CO2, absorptions previously assigned to O4+ and O4- are present, and new absorptions appear at 697, 1256, 1865, and 1895 cm-1. Detailed isotopic substitution experiments demonstrate that these new absorptions are contributed by a product of formula CO4 in which the CO2 moiety is joined to O2 in such a way that the two O atoms of each of these groups are nonequivalent. Arguments are presented indicating that this product is the CO4- anion. The infrared frequencies of the isotopically substituted species have been used for a least-squares force constant adjustment calculation, assuming a planar O2C..O2-(C(s)) structure in which most of the negative charge remains on the O2 moiety. The photodestruction threshold of CO4- lies near 260 nm. Evidence has been obtained for the formation of CO3- or of CO3 in an excited state with 3-fold symmetry, for which randomization of the oxygen isotopic substitution occurs.
引用
收藏
页码:2781 / 2787
页数:7
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