Institut für Ionenphysik und Angewandte Physik, Universität Innsbruck, Technikerstraße 25, 6020 Innsbruck, Austria.
Department of Physical Chemistry, University of Chemistry and Technology Prague, Technická 5, 16628 Prague, Czech Republic.
J Chem Phys. 2017 Sep 14;147(10):101101. doi: 10.1063/1.4999392.
The reaction of HNO with hydrated electrons (HO) (n = 35-65) in the gas phase was studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry and ab initio molecular dynamics simulations. Kinetic analysis of the experimental data shows that OH(HO) is formed primarily via a reaction of the hydrated electron with HNO inside the cluster, while proton transfer is not observed and NO(HO) is just a secondary product. The reaction enthalpy was determined using nanocalorimetry, revealing a quite exothermic charge transfer with -241 ± 69 kJ mol. Ab initio molecular dynamics simulations indicate that proton transfer is an allowed reaction pathway, but the overall thermochemistry favors charge transfer.
采用傅里叶变换离子回旋共振（FT-ICR）质谱法和从头算分子动力学模拟研究了气相中 HNO 与水合电子（HO）（n = 35-65）的反应。对实验数据的动力学分析表明，OH(HO)主要通过在团簇内水合电子与 HNO 的反应形成，而未观察到质子转移，并且 NO(HO)只是次要产物。通过纳米量热法确定了反应焓，表明这是一个非常放热的电荷转移反应，-241 ± 69 kJ mol。从头算分子动力学模拟表明，质子转移是允许的反应途径，但总体热化学更有利于电荷转移。
