Institute for Theoretical Chemistry, University of Stuttgart, Stuttgart, Germany.
J Comput Chem. 2023 Jan 30;44(3):298-306. doi: 10.1002/jcc.26893. Epub 2022 May 18.
Aminoborane, H NBH and its isotopologues, H N BH , D NBD , and D N BD , have been studied by high-level ab initio methods. All calculations rely on multidimensional potential energy surfaces and dipole moment surfaces including high-order mode coupling terms, which have been obtained from electronic structure calculations at the level of explicitly correlated coupled-cluster theory, CCSD(T)-F12, or the distinguishable cluster approximation, DCSD. Subsequent vibrational structure calculations based on second-order vibrational perturbation theory, VPT2, and vibrational configuration interaction theory, VCI, were used to determine rotational constants, centrifugal distortion constants, vibrationally averaged geometrical parameters and (an)harmonic vibrational frequencies. The impact of core-correlation effects is discussed in detail. Rovibrational VCI calculations were used to simulate the gas phase spectra of these species and an in-depth analysis of the ν band of aminoborane is provided. Color-coding is used to reveal the identity of the individual progressions of the rovibrational transitions for this particular mode.
氨硼烷、H2NBH 和其同位素 H3NBH、D3NBH、和 D2NBH 已经通过高精度的从头算方法进行了研究。所有的计算都依赖于多维势能面和偶极矩面，包括高阶模式耦合项，这些都是通过电子结构计算在显式相关耦合簇理论、CCSD(T)-F12 或可区分的团簇近似、DCSD 的水平上获得的。随后基于二级振动微扰理论（VPT2）和振动组态相互作用理论（VCI）的振动结构计算用于确定转动常数、离心畸变常数、振动平均几何参数和（谐）振动频率。详细讨论了核相关效应的影响。转动-振动 VCI 计算被用于模拟这些物种的气相光谱，并对氨硼烷的 ν 带进行了深入分析。颜色编码用于揭示该特定模式的转动-振动跃迁的各个进展的身份。
