Theoretical Study on the Reaction Mechanism of Ti with CH3CN in the Gas Phase
| Autor: | Yuwei Zhang, Yong-Cheng Wang, Xiaoli Wang, Pan-Pan Ma, Shuang Li |
|---|---|
| Rok vydání: | 2016 |
| Předmět: |
010405 organic chemistry
Chemistry Atoms in molecules Hydrogen atom 010402 general chemistry Photochemistry 01 natural sciences Molecular physics Electron localization function 0104 chemical sciences Intersystem crossing Singlet fission Density functional theory Singlet state Physics::Chemical Physics Physical and Theoretical Chemistry Natural bond orbital |
| Zdroj: | The journal of physical chemistry. A. 120(28) |
| ISSN: | 1520-5215 |
| Popis: | To gain a deeper understanding of the reaction mechanisms of Ti with acetonitrile molecules, the triplet and singlet spin-state potential energy surfaces (PESs) has been investigated at B3LYP level of density functional theory (DFT). Crossing points between the different PESs and possible spin inversion processes are discussed by spin-orbit coupling (SOC) calculation. In addition, the bonding properties of the species along the reaction were analyzed by electron localization function (ELF), atoms in molecules (AIM) and natural bond orbital (NBO). The results showed that acetonitrile activation by Ti is a typical spin-forbidden process; larger SOC (by 220.12 cm(-1)) and the possibility of crossing between triplet and singlet imply that intersystem crossing (ISC) would occur near the minimum energy crossing point (MECP) during the transfer of the hydrogen atom. |
| Databáze: | OpenAIRE |
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