Department of Chemistry, University of North Carolina, Chapel Hill, North Carolina 27517, United States.
J Phys Chem A. 2010 Dec 23;114(50):13134-45. doi: 10.1021/jp107561s. Epub 2010 Dec 3.
Threshold photoelectron photoion coincidence has been used to prepare selected internal energy distributions of nitrosobenzene ions [C(6)H(5)NO(+)]. Dissociation to C(6)H(5)(+) + NO products was measured over a range of internal energies and rate constants from 10(3) to 10(7) s(-1) and fitted with the statistical theory of unimolecular decay. A 0 K dissociative photoionization onset energy of 10.607 ± 0.020 eV was derived by using the simplified statistical adiabatic channel model. The thermochemical network of Active Thermochemical Tables (ATcT) was expanded to include phenyl and phenylium, as well as nitrosobenzene. The current ATcT heats of formation of these three species at 0 K (298.15 K) are 350.6 (337.3) ± 0.6, 1148.7 (1136.8) ± 1.0, and 215.6 (198.6) ± 1.5 kJ mol(-1), respectively. The resulting adiabatic ionization energy of phenyl is 8.272 ± 0.010 eV. The new ATcT thermochemistry for phenyl entails a 0 K (298.15 K) C-H bond dissociation enthalpy of benzene of 465.9 (472.1) ± 0.6 kJ mol(-1). Several related thermochemical quantities from ATcT, including the current enthalpies of formation of benzene, monohalobenzenes, and their ions, as well as interim ATcT values for the constituent atoms, are also given.
阈能光电离符合技术已被用于制备选定的亚硝基苯离子[C(6)H(5)NO(+)]的内部能量分布。在一定的内部能量范围内，测量了亚硝基苯离子的离解为 C(6)H(5)(+) + NO 产物的速率常数，其范围为 10(3) 到 10(7) s(-1)，并用单分子离解的统计理论进行了拟合。通过使用简化的统计绝热通道模型，得出 0 K 下的离解光致电离起始能为 10.607 ± 0.020 eV。活性热化学表（ATcT）的热化学网络得到了扩展，包括苯和苯鎓，以及亚硝基苯。这三种物质在 0 K（298.15 K）时的当前 ATcT 生成焓分别为 350.6（337.3）±0.6、1148.7（1136.8）±1.0 和 215.6（198.6）±1.5 kJ mol(-1)。苯的绝热电离能为 8.272 ± 0.010 eV。新的 ATcT 热化学计算得到苯的 0 K（298.15 K）的 C-H 键离解焓为 465.9（472.1）±0.6 kJ mol(-1)。从 ATcT 中得到的几个相关热化学量，包括当前苯、单卤代苯及其离子的生成焓，以及组成原子的临时 ATcT 值，也给出了。
