OH^(+)离子14个Λ-S态和27个Ω态光谱性质的理论研究

Theoretical investigation on spectroscopic characteristics of 14Λ-S and 27Ωstates of OH^(+)cation

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^(3)Σ^(-)/a^(1)Δ/b^(1)Σ^(+)/A^(3)Π/c^(1)Π(OH^(+))←X^(2)Π(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[X^(3)Σ_(0+)^(-),X^(3)Σ_(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(v′=0-6,J′=2,+)的辐射寿命随着v′的增大而逐渐缩短,辐射宽度随着v′的增大而逐渐增宽;(1)2(v′=0-6,J'=2,+)-X^(3)Σ_(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-(v′=0-8,J′=0,+)-X^(3)Σ_(1)^(-)(v″,J″=1,-)的自发辐射很强.3)(2)2第一势阱(v′=0-2,+),(2)1(v′=0-9,+)和(1)0-(v′=0-8,+)的辐射寿命都是随着J′的增大而逐渐增长.

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^(3)∑^(-)/a^(1)Δ/b^(1)∑+/A^(3)Π/c^(1)Π(OH^(+))←X^(2)Π(OH),and the potential energy curves of 14Λ-S and 27Ωstates of OH+are obtained by using the optimized icMRCI+Q method.The transition dipole moments between sixΩstates[X^(3)∑_(0+)^(-),X^(3)∑_(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 vibrationalrotational 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(v′=0-6,J′=2,+)gradually decrease with v′increasing,while the radiation widths correspondingly increase;the spontaneous emissions of(1)2(v′=0-6,Jr=2,+)-X^(3)∑^(1)-(v",J"=1,-)are weak.2)The radiation lifetimes of(2)2(1st well)(v′=0-2,J′=2,+),(2)1(v′=0-9,J′=1,+),and(1)0-(v′=0-8,J′=0,+)all gradually increase as v′increases,while their radiation widths narrow with v′increasing;the spontaneous emissions of(2)2(1st well)(v′=0-2,J′=2,+)-X^(3)∑_(1)^(-)(v",J"=1,-),(2)1(v′=0-9,J′=1,+)-X3∑0+-(v",J"=1,-),and(1)0-(v′=0-8,J′=0,+)-X^(3)∑_(1)^(-)(v",J"=1,-)are strong.3)The radiation lifetimes of(2)2(1st well)(v′=0-2,+),(2)1(v′=0-9,+),and(1)0-(v′=0-8,+)all gradually increase with J′increasing.The datasets presented in this work,including the potential energy curves of 14 A-S and 27Ωstates,7 pairs of transition dipole moments between the 6Ωstates[X^(3)∑_(0+)^(-),X_(3)∑_(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)(v′=0-2,+),(2)1(v′=0-9,+),and(1)0-(v′=0-8,+)states may be available at https://www.doi.org/10.57760/sciencedb.j00213.00058.