Chang Jing, Guo Lifen, Wang Ruifang, Mou Jie, Ren Haisheng, Ma Jianyi, Guo Hua
Institute of Atomic and Molecular Physics , Sichuan University , Chengdu , Sichuan 610065 , China.
School of Chemical Engineering , Sichuan University , Chengdu , Sichuan 610065 , China.
J Phys Chem A. 2019 May 16;123(19):4232-4240. doi: 10.1021/acs.jpca.9b02662. Epub 2019 May 2.
The absorption spectra of acetylene (HCCH) and vinylidene (HCC) as well as their deuterated isotopologues are investigated theoretically on a near spectroscopically accurate full-dimensional potential energy surface reported in an earlier publication, using dipole moment surfaces reported in this work, which are constructed with a neural network method from a large number of ab initio data points. These global surfaces cover not only the deep acetylene well but also the vinylidene well, as well as the transition region between the two isomers. The agreement with available experimental data for acetylene is excellent, validating both the potential energy surface and the dipole moment surfaces. The infrared spectra of vinylidene and its deuterated isotopologues are predicted. The potential and dipole moment surfaces lay the foundation for future spectroscopic studies of the acetylene-vinylidene isomerization involving large-amplitude motions.
利用本工作中报道的偶极矩面，在先前发表的接近光谱精度的全维势能面上，从理论上研究了乙炔（HCCH）和亚乙烯基（HCC）及其氘代同位素的吸收光谱。这些偶极矩面是用神经网络方法从大量从头算数据点构建而成的。这些全局表面不仅覆盖了深乙炔阱，还覆盖了亚乙烯基阱以及两种异构体之间的过渡区域。与乙炔现有实验数据的一致性非常好，验证了势能面和偶极矩面。预测了亚乙烯基及其氘代同位素的红外光谱。势能面和偶极矩面为未来涉及大幅度运动的乙炔 - 亚乙烯基异构化光谱研究奠定了基础。
