The reaction of HNO₃ with hydrated electrons (H₂O)_n⁻ (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⁻(H₂O)_m is formed primarily via a reaction of the hydrated electron with HNO₃ inside the cluster, while proton transfer is not observed and NO₃⁻(H₂O)_m is just a secondary product. The reaction enthalpy was determined using nanocalorimetry, revealing a quite exothermic charge transfer with −241 ± 69 kJ mol⁻¹. Ab initio molecular dynamics simulations indicate that proton transfer is an allowed reaction pathway, but the overall thermochemistry favors charge transfer.

中文翻译：

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通讯：在硝酸与气相水合电子的反应中，电荷转移优于质子转移


使用傅里叶变换离子回旋共振 (FT-ICR) 质谱和从头算分子动力学模拟研究了 HNO ₃与水合电子 (H ₂ O) _n ⁻ ( n = 35–65) 在气相中的反应。实验数据的动力学分析表明，OH ⁻ (H ₂ O) _m主要是通过水合电子与团簇内的HNO ₃反应形成，而没有观察到质子转移，NO ₃ ⁻ (H ₂ O) _m只是一个次要产品。使用纳量热法测定反应焓，揭示了-241 ± 69 kJ mol ^-1的相当放热的电荷转移。从头算分子动力学模拟表明，质子转移是一种允许的反应途径，但总体热化学有利于电荷转移。