## 摘要

Kinetics and mechanisms for the C_{6}H_{5} + CH_{3}C(O)CH_{3} and CD_{3}C(O)CD_{3} reactions have been investigated by cavity ring-down spectrometry (CRDS) and hybrid density functional theory (DFT) calculations. The rate constants measured for the two reactions at the constant pressure of 45 Torr using Ar as a carrier gas can be represented by the following Arrhenius expressions in units of cm^{3} mol^{-1} s^{-1}: k_{H} = (4.2 ± 0.4) × 10^{11} exp[-(955 ± 30)/T] and k_{D} = (5.1 ± 0.6) × 10^{11} exp[-(1114 ± 43)/T] in the temperature ranges of 299-451 and 328-455 K, respectively. The significant kinetic isotope effect observed suggests that H-abstraction is the major path, according to their activation energies, with the C_{6}H_{5} + CD_{3}C(O)CD_{3} reaction being higher by 0.3 kcal/mol. DFT calculations at the B3LYP/aug-cc-PVTZ//B3LYP/cc-PVDZ level of theory indicate the reaction can in principle take place by three reaction paths, one H-abstraction and two addition reactions to the C=O double bond at both C and O atom sites, with the latter two processes having significantly higher reaction barriers. The rate constants predicted by canonical variational transition state theory (CVT) with small curvature tunneling (SCT) corrections for the direct H- and D-abstraction reactions are in reasonable agreement with the experimental data after slightly decreasing the calculated barriers from 3.9 kcal/mol to 3.3 kcal/mol and from 4.7 kcal/mol to 4.1 kcal/mol, respectively. The predicted rate constants for C_{6}H_{5} + CH_{3}COCH_{3} in the temperature range of 298-1200 K can be represented reasonably by the expression, k_{H} = (1.7 ± 0.6) × 10^{-1} T^{(4.2 ± 0.1)} exp[-(466 ± 26)/T] cm^{3} mol^{-1} s^{-1}.

原文 | English |
---|---|

頁（從 - 到） | 7755-7761 |

頁數 | 7 |

期刊 | Journal of Physical Chemistry A |

卷 | 107 |

發行號 | 39 |

DOIs | |

出版狀態 | Published - 2 10月 2003 |

## 指紋

深入研究「Experimental and computational studies of the kinetics and mechanisms for C_{6}H

_{5}reactions with acetone-h

_{6}and -d

_{6}」主題。共同形成了獨特的指紋。