Ultrafast photochemistry of methyl hydroperoxide on ice particles

被引：18

作者：

Kamboures, M. A. ^{[1
]}

Nizkorodov, S. A. ^{[1
]}

Gerber, R. B. ^{[1
,2
,3
]}

机构：

[1] Univ Calif Irvine, Dept Chem, Irvine, CA 92697 USA

[2] Hebrew Univ Jerusalem, Inst Chem, IL-91904 Jerusalem, Israel

[3] Hebrew Univ Jerusalem, Fritz Haber Ctr, IL-91904 Jerusalem, Israel

来源：

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA | 2010年 / 107卷 / 15期

基金：

以色列科学基金会; 美国国家科学基金会;

关键词：

air-water interface; molecular dynamics; peroxides; photodissociation; HYDROGEN-PEROXIDE; ORGANIC HYDROPEROXIDES; HYDROXYL RADICALS; AQUEOUS-PHASE; GAS-PHASE; PHOTODISSOCIATION; CH3OOH; OH; NM; METHYLHYDROPEROXIDE;

D O I：

10.1073/pnas.0907922106

中图分类号：

O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];

学科分类号：

07 ; 0710 ; 09 ;

摘要：

Simulations show that photodissociation of methyl hydroperoxide, CH3OOH, on water clusters produces a surprisingly wide range of products on a subpicosecond time scale, pointing to the possibility of complex photodegradation pathways for organic peroxides on aerosols and water droplets. Dynamics are computed at several excitation energies at 50 K using a semiempirical PM3 potential surface. CH3OOH is found to prefer the exterior of the cluster, with the CH3O group sticking out and the OH group immersed within the cluster. At atmospherically relevant photodissociation wavelengths the OH and CH3O photofragments remain at the surface of the cluster or embedded within it. However, none of the 25 completed trajectories carried out at the atmospherically relevant photodissociation energies led to recombination of OH and CH3O to form CH3OOH. Within the limited statistics of the available trajectories the predicted yield for the recombination is zero. Instead, various reactions involving the initial fragments and water promptly form a wide range of stable molecular products such as CH2O, H2O, H-2, CO, CH3OH, and H2O2.

引用

页码：6600 / 6604

页数：5