Reaction of atomic hydrogen with formic acid

被引：23

作者：

Cao, Qian ^{[1
]}

Berski, Slawomir ^{[2
]}

Latajka, Zdzislaw ^{[2
]}

Rasanen, Markku ^{[1
]}

Khriachtchev, Leonid ^{[1
]}

机构：

[1] Univ Helsinki, Dept Chem, FI-00014 Helsinki, Finland

[2] Univ Wroclaw, Fac Chem, PL-50383 Wroclaw, Poland

来源：

PHYSICAL CHEMISTRY CHEMICAL PHYSICS | 2014年 / 16卷 / 13期

基金：

芬兰科学院;

关键词：

GAS-PHASE; RARE-GAS; CONFORMATIONAL ISOMERIZATION; CHEMICAL-REACTION; ENERGY CONFORMER; ACETIC-ACID; SOLID ARGON; CL ATOMS; HCOOH; RADICALS;

D O I：

10.1039/c3cp55265a

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：

We study the reaction of atomic hydrogen with formic acid and characterize the radical products using IR spectroscopy in a Kr matrix and quantum chemical calculations. The reaction first leads to the formation of an intermediate radical trans-H2COOH, which converts to the more stable radical transcis-HC(OH) 2 via hydrogen atom tunneling on a timescale of hours at 4.3 K. These open-shell species are observed for the first time as well as a reaction between atomic hydrogen and formic acid. The structural assignment is aided by extensive deuteration experiments and ab initio calculations at the UMP2 and UCCSD(T) levels of theory. The simplest geminal diol radical trans-cis-HC(OH)(2) identified in the present work as the final product of the reaction should be very reactive, and further reaction channels are of particular interest. These reactions and species may constitute new channels for the initiation and propagation of more complex organic species in the interstellar clouds.

引用

页码：5993 / 6001

页数：9

共 40 条

[1] Electronic Effects on Atom Tunneling: Conformational Isomerization of Monomeric Para-Substituted Benzoic Acid Derivatives [J].