Harvard-Smithsonian Center for Astrophysics , 60 Garden Street, Cambridge, Massachusetts 02138, United States.
J Phys Chem A. 2013 Oct 3;117(39):9950-8. doi: 10.1021/jp400080j. Epub 2013 Apr 22.
The fundamental molecular ion H3(+) has impacted astronomy, chemistry, and physics, particularly since the discovery of its rovibrational spectrum. Consisting of three identical fermions, its properties are profoundly influenced by the requirements of exchange symmetry, most notably the nonexistence of its ground rotational state. Spectroscopy of H3(+) is often used to infer the relative abundances of its two nuclear spin modifications, ortho- and para-H3(+), which are important in areas as diverse as electron dissociative recombination and deuterium fractionation in cold interstellar clouds. In this paper, we explore in detail the impact of exchange symmetry on the states of H3(+), with a particular focus on the state degeneracies necessary for converting spectral transition intensities to relative abundances. We address points of confusion in the literature surrounding these issues and discuss the implications for proton-transfer reactions of H3(+) at low temperatures.
三原子正氢离子(H3(+))作为基本的分子离子,对天文学、化学和物理学都产生了深远的影响,特别是自其转动-振动光谱被发现以来。由三个相同的费米子组成,其性质受到交换对称性的强烈影响,最显著的是其基态转动状态不存在。H3(+)的光谱学经常被用于推断其两种核自旋修饰体的相对丰度,即正 H3(+)和仲 H3(+),这在电子离解复合和冷星际云的氘分馏等领域都很重要。在本文中,我们详细探讨了交换对称性对 H3(+)状态的影响,特别关注了将光谱跃迁强度转换为相对丰度所需的态简并。我们解决了围绕这些问题的文献中的一些混淆点,并讨论了其对低温下 H3(+)质子转移反应的影响。