| Title: | Molecular dynamics simulation of gas-phase ozone reactions with sabinene and benzene |
| Author(s): | Ridgway HF; Mohan B; Cui X; Chua KJ; Islam MR; |
| Address: | "AquaMem Scientific Consultants, Rodeo, NM, USA. Department of Mechanical Engineering, National University of Singapore, 9 Engineering Drive 1, Singapore 117576, Singapore. Department of Mechanical Engineering, National University of Singapore, 9 Engineering Drive 1, Singapore 117576, Singapore; Engineering Science Programme, National University of Singapore, 9 Engineering Drive 1, Singapore 117575, Singapore. Electronic address: mpeckje@nus.edu.sg. Department of Mechanical Engineering, National University of Singapore, 9 Engineering Drive 1, Singapore 117576, Singapore; Engineering Science Programme, National University of Singapore, 9 Engineering Drive 1, Singapore 117575, Singapore" |
| DOI: | 10.1016/j.jmgm.2017.04.020 |
| ISSN/ISBN: | 1873-4243 (Electronic) 1093-3263 (Linking) |
| Abstract: | "Gas-phase reactions of ozone (O(3)) with volatile organic compounds were investigated both by experiment and molecular simulations. From our experiments, it was found ozone readily reacts with VOC pure components and reduces it effectively. By introducing ozone intermittently, the reaction between VOC and ozone is markedly enhanced. In order to understand the relationship between intermediate reactions and end products, ozone reaction with benzene and alicyclic monoterpene sabinene were simulated via a novel hybrid quantum mechanical/molecular mechanics (QM/MM) algorithm that forced repeated bimolecular collisions. Molecular orbital (MO) rearrangements (manifested as bond dissociation or formation), resulting from the collisions, were computed by semi-empirical unrestricted Hartree-Fock methods (e.g., RM1). A minimum of 975 collisions between ozone and targeted organic species were performed to generate a distribution of reaction products. Results indicated that benzene and sabinene reacted with ozone to produce a range of stable products and intermediates, including carbocations, ring-scission products, as well as peroxy (HO(2) and HO(3)) and hydroxyl (OH) radicals. Among the stable sabinene products observed included formaldehyde and sabina-ketone, which have been experimentally demonstrated in gas-phase ozonation reactions. Among the benzene ozonation products detected composed of oxygen mono-substituted aromatic C(6)H(5)O, which may undergo further transformation or rearrangement to phenol, benzene oxide or 2,4-cyclohexadienone; a phenomenon which has been experimentally observed in vapor-phase photocatalytic ozonation reactions" |
| Keywords: | Acetone/chemistry Air Pollutants/chemistry Benzene Derivatives/chemistry Bicyclic Monoterpenes Construction Materials Molecular Dynamics Simulation Monoterpenes/*chemistry Oxidation-Reduction Ozone/*chemistry Xylenes/*chemistry Formaldehyde Molecular mech; |
| Notes: | "MedlineRidgway, H F Mohan, B Cui, X Chua, K J Islam, M R eng 2017/05/02 J Mol Graph Model. 2017 Jun; 74:241-250. doi: 10.1016/j.jmgm.2017.04.020. Epub 2017 Apr 20" |
