Ansari Suleman Jalilahmad, Mohapatra Sipra, Fiorin Giacomo, Klein Michael L, Mogurampelly Santosh
Polymer Electrolytes and Materials Group (PEMG), Department of Physics, Indian Institute of Technology Jodhpur, Karwar, Rajasthan 342037, India.
Institute for Computational Molecular Science (ICMS), Temple Materials Institute (TMI), Temple University, Philadelphia, Pennsylvania 19122, United States.
J Phys Chem B. 2024 Sep 19;128(37):9014-9021. doi: 10.1021/acs.jpcb.4c03349. Epub 2024 Sep 11.
Sulfuric acid (HSO), a highly reactive reagent containing intrinsic protonic charge carriers, has been studied via molecular dynamics simulations. Specifically, we explore the solvation shell structure of the protonic defects, HSO and HSO, as well as the underlying proton transport mechanisms in both the neat and hydrated HSO solutions. Our findings reveal a significant contraction of the dynamic hydrogen-bonded network around the protonic defects, which resembles features seen in water. The simulations provide estimates of the structural relaxation time scales for proton release from both the covalent O-H bonds (∼23 ps) and the hydrogen bonds (∼0.4 ps). In contrast to water, our analysis of the proton transfer scenarios in sulfuric acid reveals correlated events mediated by the formation of longer (up to four) hydrogen-bonded Grotthuss chains.
硫酸（H₂SO₄）是一种含有本征质子电荷载体的高活性试剂，已通过分子动力学模拟进行了研究。具体而言，我们探究了质子缺陷HSO₄⁻和HSO₃⁻的溶剂化壳层结构，以及纯态和水合硫酸溶液中潜在的质子传输机制。我们的研究结果表明，质子缺陷周围的动态氢键网络显著收缩，这与水中观察到的特征相似。模拟提供了质子从共价O - H键（约23皮秒）和氢键（约0.4皮秒）释放的结构弛豫时间尺度估计。与水不同，我们对硫酸中质子转移情况的分析揭示了由形成更长（多达四个）氢键的Grotthuss链介导产生的相关事件。
