title: ONIOM study of isomerization reactions of aromatic hydrocarbons in acidic mordenite zeolite.
abstract: Two different mechanisms: Shift 1,2-isomerization and isomerization via the disproportionation reaction are investigated for aromatic hydrocarbons over acidic mordenite zeolite by using our own n-layered integrated molecular orbital and molecular mechanics (ONIOM) scheme. The picture shows a schematic energy profile for the isomerization of toluene catalyzed by acidic mordenite.The geometrical structures and energies of isomerization reactions of aromatic hydrocarbons catalyzed by the 128T cluster model of acidic mordenite zeolite are studied by using our own n-layered integrated molecular orbital and molecular mechanics (ONIOM) scheme. The aromatic hydrocarbons investigated are toluene, xylenes, and trimethylbenzenes. Two proposed intramolecular reaction mechanisms, that is, shift 1,2-isomerization and isomerization via the disproportionation reaction, are studied and discussed in detail. Both of the mechanisms firstly proceed by protonation of aromatic hydrocarbons to form the aromatic-based carbenium ions. Attempts to determine the prevailing reaction mechanism of the isomerization are evaluated. In most cases, the isomerization reactivity sequence is: trimethylbenzenes>xylenes>toluene. The conclusions obtained using the ONIOM scheme agree with the available periodic DFT and experimental results on acidic mordenite zeolite.
authors.affiliation: School of Chemistry and Chemical Technology, Shanghai Jiao Tong University, 800 Dongchuan Road, Shanghai, China.
authors.forename: Jing
authors.initials: J
authors.lastname: Yang