引用本文:
【打印本页】   【HTML】   【下载PDF全文】   查看/发表评论  【EndNote】   【RefMan】   【BibTex】
←前一篇|后一篇→ 过刊浏览    高级检索
本文已被:浏览 506次   下载 355 本文二维码信息
码上扫一扫!
分享到: 微信 更多
高次激发相关能在构建HCN-He亚光谱精度势能面中的角色:通过实验高分辨率光谱进行严格检测
侯丹,张晓龙,翟羽,李辉*
作者单位E-mail
侯丹 江西农业大学理学院功能材料和农业应用化学研究所, 南昌 330045  
张晓龙 吉林大学理论化学研究所, 长春 130023  
翟羽 吉林大学理论化学研究所, 长春 130023  
李辉* 吉林大学理论化学研究所, 长春 130023 Prof-huili@jlu.edu.cn 
摘要:
关键词:  
DOI:10.1063/1674-0068/30/cjcp1712231
分类号:
基金项目:This work was supported by the National Key Research and Development Program (No.2016YFB0700801 and No.2017YFB0203401) and the National Natural Science Foundation of China (No.21533003, No.21773081 and No.91541124).
The Role of High Excitations in Constructing Sub-spectroscopic Accuracy Intermolecular Potential of He-HCN: Critically Examined by the High-Resolution Spectra with Resonance States
Dan Hou,Xiao-Long Zhang,Yu Zhai,Hui Li*
Abstract:
Interpreting high-resolution rovibrational spectra of weakly bound complexes commonly requires spectroscopic accuracy (<1 cm-1) potential energy surfaces (PES). Constructing high-accuracy ab initio PES relies on the high-level electronic structure approaches and the accurate physical models to represent the potentials. The coupled cluster approaches including single and double excitations with a perturbational estimate of triple excitations (CCSD(T)) have been termed the "gold standard" of electronic structure theory, and widely used in generating intermolecular interaction energies for most van der Waals complexes. However, for HCN-He complex, the observed millimeter-wave spectroscopy with high-excited resonance states has not been assigned and interpreted even on the ab initio PES computed at CCSD(T) level of theory with the complete basis set (CBS) limit. In this work, an effective three-dimensional ab initio PES for HCN-He, which explicitly incorporates dependence on the Q1 (C-H) normal-mode coordinate of the HCN monomer has been calculated at the CCSD(T)/CBS level. The post-CCSD(T) interaction energy has been examined and included in our PES. Analytic two-dimensional PESs are obtained by least-squares fitting vibrationally averaged interaction energies for v1(C-H)=0, and 1 to the Morse/Long-Range potential function form with root-mean-square deviations (RMSD) smaller than 0.011 cm-1. The role and significance of the post-CCSD(T) interaction energy contribution are clearly illustrated by comparison with the predicted rovibrational energy levels. With or without post-CCSD(T) corrections, the value of dissociation limit (D0) is 8.919 or 9.403 cm-1, respectively. The predicted millimeter-wave transitions and intensities from the PES with post-CCSD(T) excitation corrections are in good agreement with the available experimental data with RMS discrepancy of 0.072 cm-1. Moreover, the infrared spectrum for HCN-He complex is predicted for the first time. These results will serve as a good starting point and provide reliable guidance for future infrared studies of HCN doped in (He)n clusters.
Key words:  Potential energy surface  Rovibrational spectra  van der Waals complex