Amaral Paulo H R, Stanke Monika, Adamowicz Ludwik, Diniz Leonardo G, Mohallem José R, Alijah Alexander
Department of Physics, Federal University of Minas Gerais, PO Box 702, 30123-970 Belo Horizonte, Minas Gerais, Brazil.
Institute of Physics, Faculty of Physics, Astronomy and Informatics, Nicolaus Copernicus University, ul. Grudzia̧dzka 5, Toruń 87-100, Poland.
Philos Trans A Math Phys Eng Sci. 2019 Sep 23;377(2154):20180411. doi: 10.1098/rsta.2018.0411. Epub 2019 Aug 5.
The effect of non-adiabatic coupling on the computed rovibrational energy levels amounts to about 2 cm for H and must be included in high-accuracy calculations. Different strategies to obtain the corresponding energy shifts are reviewed in the article. A promising way is to introduce effective vibrational reduced masses that depend on the nuclear configuration. A new empirical method that uses the stockholder atoms-in-molecules approach to this effect is presented and applied to H. Furthermore, a highly accurate potential energy surface for the D isotopologue, which includes relativistic and leading quantum electrodynamic terms, is constructed and used to analyse the observed rovibrational frequencies for this molecule. Accurate band origins are obtained that improve existing data. This article is part of a discussion meeting issue 'Advances in hydrogen molecular ions: H, H and beyond'.
非绝热耦合对计算得到的H分子振转能级的影响约为2厘米，在高精度计算中必须予以考虑。本文综述了获得相应能量位移的不同策略。一种有前景的方法是引入依赖于核构型的有效振动折合质量。提出了一种利用分子中原子股东方法来处理这种效应的新经验方法，并将其应用于H分子。此外，构建了包含相对论和主要量子电动力学项的D同位素分子的高精度势能面，并用于分析该分子观测到的振转频率。获得了精确的谱带起源，改进了现有数据。本文是“氢分子离子的进展：H₂⁺、HD⁺及其他”讨论会议文集的一部分。
