An isomer-specific study of solid nitromethane decomposition pathways - Detection of aci-nitromethane (H2CNO(OH)) and nitrosomethanol (HOCH2NO) intermediates

被引：18

作者：

Maksyutenko, Pavlo ^{[1
,2
]}

Forstel, Marko ^{[1
,2
]}

Crandall, Parker ^{[1
,2
]}

Sun, Bing-Jian ^{[3
]}

Wu, Mei-Hung ^{[3
]}

Chang, Agnes H. H. ^{[3
]}

Kaiser, Ralf I. ^{[1
,2
]}

机构：

[1] Univ Hawaii, Dept Chem, 2545 McCarthy Mall, Honolulu, HI 96822 USA

[2] Univ Hawaii, WM Keck Res Lab Astrochem, 2545 McCarthy Mall, Honolulu, HI 96822 USA

[3] Natl Dong Hwa Univ, Dept Chem, 1 Sec,2 Da Hsueh Rd, Hualien 974, Taiwan

来源：

CHEMICAL PHYSICS LETTERS | 2016年 / 658卷

关键词：

DENSITY-FUNCTIONAL THERMOCHEMISTRY; NONEQUILIBRIUM REACTION PATHWAYS; AB-INITIO; D3-NITROMETHANE CD3NO2; IONIZATION ENERGIES; CH3NO2; PHOTOLYSIS; MECHANISM; NO; PHOTOIONIZATION;

D O I：

10.1016/j.cplett.2016.06.006

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：

An isomer specific study of energetic electron exposed nitromethane ices was performed via photoionization - reflectron time of flight mass spectrometry (PI-ReTOF-MS) of the subliming products employing tunable vacuum ultraviolet light for ionization. Supported by electronic structure calculations, nitromethane (CH3NO2) was found to isomerize to methyl nitrite (CH3ONO) and also via hydrogen migration to the hitherto elusive aci-nitromethane isomer (H2CNO(OH)). The latter isomerizes to nitrosomethanol (HOCH2NO) through hydroxyl group (OH) migration, and, probably, ring closure to the cyclic 2-hydroxy-oxaziridine isomer (c-H2CON(OH)) as well. The importance of hydrogen migrations was also verified via the nitrosomethane (CH3NO) - formaldehyde oxime isomer (CH2NOH) pair. (C) 2016 Elsevier B.V. All rights reserved.

引用

页码：20 / 29

页数：10