School of Chemistry, University of Edinburgh, Edinburgh, Scotland, United Kingdom.
J Chem Phys. 2011 Feb 28;134(8):084309. doi: 10.1063/1.3549812.
The Rydberg states in the vacuum ultraviolet photoabsorption spectrum of 1,2,3-triazole have been measured and analyzed with the aid of comparison to the UV valence photoelectron ionizations and the results of ab initio configuration interaction (CI) calculations. Calculated electronic ionization and excitation energies for singlet, triplet valence, and Rydberg states were obtained using multireference multiroot CI procedures with an aug-cc-pVTZ [5s3p3d1f] basis set and a set of Rydberg [4s3p3d3f] functions. Adiabatic excitation energies obtained for several electronic states using coupled-cluster (singles, doubles, and triples) and complete active space self-consistent field procedures agree well with experimental values. Variations in bond lengths with the electronic state are discussed. The lowest energy UV band (∼5.5-6.5 eV) is assigned to three electronically excited states and demonstrates the occurrence of a nonplanar upper state on the low energy side. A UV photoelectron spectrum with an improved resolution yielded adiabatic and vertical ionization energies and reorganization energies for several of the lowest cationic states. As well as excitations to the s, p, d-Rydberg states are the excitations consistent with an f-series.
在真空紫外光吸收光谱中，1,2,3-三唑的里德堡态已经被测量和分析，借助于与紫外价光电离的比较和从头计算组态相互作用（CI）计算的结果。使用多参考多根 CI 程序，采用 aug-cc-pVTZ [5s3p3d1f] 基组和一组里德堡 [4s3p3d3f] 函数，计算了单重态、三重态价态和里德堡态的电子电离和激发能。使用耦合簇（单、双和三）和完全活性空间自洽场程序获得的几个电子态的绝热激发能与实验值吻合较好。讨论了键长随电子态的变化。最低能量的紫外带（约 5.5-6.5 eV）被分配给三个电子激发态，并证明在低能量侧存在非平面上态。具有改进分辨率的紫外光电子能谱产生了几个最低阳离子态的绝热和垂直电离能和重组能。以及 s、p、d-里德堡态的激发与 f 系列一致。
