-
在选择合适的活性空间和基组、考虑各种物理效应(标量相对论效应、核–价电子关联效应、完备基组极限和自旋–轨道耦合效应)的基础上, 本文利用优化的icMRCI+ Q方法获得了X 3Σ –/a 1Δ/b 1Σ +/A 3Π/c 1Π(OH +)←X 2Π(OH)精确的电离能、OH +离子14个Λ-S态和相应的27个Ω态势能曲线. 利用全电子icMRCI/cc-pCV5Z + SOC理论获得了6个Ω态 \mathrmX^3\Sigma _0^ + ^ - , \textX^3\Sigma _1^ - , (1)2, (2)2, (2)1和(1)0 –之间的跃迁偶极距. 并且本文获得的电离能、光谱和振动–转动跃迁数据与现有的测量值符合得非常好. 研究发现: 1) (1)2( υ'= 0—6, J'= 2, +)的辐射寿命随着 υ'的增大而逐渐缩短, 辐射宽度随着 υ'的增大而逐渐增宽; (1)2( υ'= 0—6, J'= 2, +)– \textX^3\Sigma _1^ - ( υ'', J''= 1, –)自发辐射较弱. 2)(2)2 第一势阱( υ'= 0—2, J'= 2, +), (2)1( υ'= 0—9, J'= 1, +)和(1)0 –( υ'= 0—8, J'= 0, +)的辐射寿命都是随着 υ'的增大而逐渐增长, 辐射宽度都随着 υ'的增大而逐渐变窄; (2)2 第一势阱( υ'= 0—2, J'= 2, +)– \textX^3\Sigma _1^ - ( υ'', J''= 1, –), (2)1( υ'= 0—9, J'= 1, +)– \textX^3\Sigma _0^ + ^ - ( υ'', J''= 1, –)和(1)0 –( υ'= 0—8, J'= 0, +)– \textX^3\Sigma _1^ - ( υ'', J''= 1, –)的自发辐射很强. 3) (2)2 第一势阱( υ'= 0—2, +), (2)1( υ'= 0—9, +)和(1)0 –( υ'= 0—8, +)的辐射寿命都是随着 J'的增大而逐渐增长. 本文数据集可在科学数据银行数据库 https://www. doi.org/10.57760/sciencedb.j00213.00058中访问获取.Based on the selection of appropriate active space and basis sets, and consideration of various physical effects such as scalar relativistic effect, core-valence electron correlation, complete basis set limit and spin-orbit coupling effect, the precise ionization energy of X 3Σ –/a 1Δ/b 1Σ +/A 3Π/c 1Π(OH +)←X 2Π(OH), and the potential energy curves of 14 Λ-S and 27 Ω states of OH +are obtained by using the optimized icMRCI + Qmethod. The transition dipole moments between six Ω states \mathrmX^3\Sigma _0^ + ^ - , \textX^3\Sigma _1^ - , (1)2, (2)2, (2)1, and (1)0 –are obtained by using the all electron icMRCI/cc-pCV5Z + SOC theory. The ionization energy, spectroscopic and vibrational-rotational transition data obtained in this work are in good agreement with the existing measurements. The findings in this work are as follows. 1) The radiation lifetimes of (1)2( υ'= 0–6, J'= 2, +) gradually decrease with υ'increasing, while the radiation widths correspondingly increase; the spontaneous emissions of (1)2( υ'= 0–6, J'= 2, +)– \textX^3\Sigma _1^ - ( υ'', J''= 1, –) are weak. 2) The radiation lifetimes of (2)2 1st well( υ'= 0–2, J'= 2, +), (2)1( υ'= 0–9, J'= 1, +), and (1)0 –( υ'= 0–8, J'= 0, +) all gradually increase as υ'increases, while their radiation widths narrow with υ'increasing; the spontaneous emissions of (2)2 1st well( υ'= 0–2, J'= 2, +)– \textX^3\Sigma _1^ - ( υ'', J''= 1, –), (2)1( υ'= 0–9, J'= 1, +)– \textX^3\Sigma _0^ + ^ - ( υ'', J''= 1, –), and (1)0 –( υ'= 0–8, J'= 0, +)– \textX^3\Sigma _1^ - ( υ'', J''= 1, –) are strong. 3) The radiation lifetimes of (2)2 1st well( υ'= 0–2, +), (2)1( υ'= 0–9, +), and (1)0 –( υ'= 0–8, +) all gradually increase with J'increasing. The datasets presented in this work, including the potential energy curves of 14 Λ-S and 27 Ω states, 7 pairs of transition dipole moments between the 6 Ω states \mathrmX^3\Sigma _0^ + ^ - , \textX^3\Sigma _1^ - , (1)2, (2)2, (2)1, (1)0 –, and distributions of the radiative lifetime varying with the J'of the (2)2 1st well( υ'= 0–2, +), (2)1( υ'= 0–9, +), and (1)0 –( υ'= 0–8, +) states may be available at https://www.doi.org/10.57760/sciencedb.j00213.00058.
-
Keywords:
- potential energy curves/
- spin-orbit coupling/
- transition dipole moments/
- spectroscopic and transition data
搜索
x
中国物理学会期刊
下载: