The catalytic effects of H2CO3, CH3COOH, HCOOH and H2O on the addition reaction of CH2OO + H2O → CH2(OH)OOH. (18th July 2018)

• Record Type: Journal Article
• Authors: Zhang, Tianlei; Lan, Xinguang; Wang, Rui; Roy, Soumendra; Qiao, Zhangyu; Lu, Yousong; Wang, Zhuqing
• Is Part Of: Molecular physics. Volume 116:Number 14(2018)
• Page Start: 1783
• Page End: 1794
• Publication Date: 2018-07-18
• Subjects: Criegee intermediate -- hydrogen transfer -- reaction mechanism -- rate constant; Molecules -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Molécules -- Périodiques; Chimie physique et théorique -- Périodiques; 539.6.05
• DOI: 10.1080/00268976.2018.1454612
• Languages: English
• ISSNs: 0026-8976

Abstract

ABSTRACT: The addition reaction of CH2 OO + H2 O→ CH2 (OH)OOH without and with X (X = H2 CO3, CH3 COOH and HCOOH) and H2 O was studied at CCSD(T)/6-311+ G(3df, 2dp)//B3LYP/6-311+G(2d, 2p) level of theory. Our results show that X can catalyse CH2 OO + H2 O → CH2 (OH)OOH reaction both by increasing the number of rings, and by adding the size of the ring in which ring enlargement by COOH moiety of X inserting into CH2 OO···H2 O is favourable one. Water-assisted CH2 OO + H2 O → CH2 (OH)OOH can occur by H2 O moiety of (H2 O)2 or the whole (H2 O)2 forming cyclic structure with CH2 OO, where the latter form is more favourable. Because the concentration of H2 CO3 is unknown, the influence of CH3 COOH, HCOOH and H2 O were calculated within 0–30 km altitude of the Earth's atmosphere. The results calculated within 0–5 km altitude show that H2 O and HCOOH have obvious effect on enhancing the rate with the enhancement factors are, respectively, 62.47%–77.26% and 0.04%–1.76%. Within 5–30 km altitude, HCOOH has obvious effect on enhancing the title rate with the enhancement factor of 2.69%–98.28%. However, compared with the reaction of CH2 OO + HCOOH, the rate of CH2 OO···H2 O + HCOOH is much slower. Abstract :