Premium
Ab initio Mechanism Study on the Reaction of Chlorine Atom with Formic Acid
Author(s) -
HaiTao Yu,
YuJuan Chi,
HongGang Fu,
ZeSheng Li,
JiaZhong Sun
Publication year - 2003
Publication title -
chinese journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.28
H-Index - 41
eISSN - 1614-7065
pISSN - 1001-604X
DOI - 10.1002/cjoc.20030210307
Subject(s) - chemistry , formic acid , hydrogen atom , ab initio , hydrogen atom abstraction , potential energy surface , molecule , reaction mechanism , computational chemistry , atom (system on chip) , ab initio quantum chemistry methods , hydrogen , photochemistry , catalysis , organic chemistry , alkyl , computer science , embedded system
The potential energy surface (PES) for the reaction of Cl atom with HCOOH is predicted using ab initio molecular orbital calculation methods at UQCISD(T, full)/6–311 ++ G(3df,2p)/UMP2(full)/6–311+ G(d, p) level of theory with zero‐point vibrational energy (ZPVE) correction. The calculated results show that the reaction mechanism of Cl atom with formic acid is a C‐site hydrogen abstraction reaction from cis ‐HOC(H)0 molecule by Cl atom with a 3.73 kJ/mol reaction barrier height, leading to the formation of cis ‐HOCO radical which will reacts with Cl atom or other molecules in such a reaction system. Because the reaction barrier height of O ‐site hydrogen abstraction reaction from cis ‐HOC(H)O molecule by Cl atom which leads to the formation of HCO 2 radical is 67.95 kJ/mol, it is a secondary reaction channel in experiment. This is in good agreement with the prediction based on the previous experiments.