理论研究OH+离子电子态光谱及跃迁性质

doi:10.19596/j.cnki.1001-246x.8297

摘要/Abstract

摘要：

采用高精度的内收缩多参考组态相互作用方法（icMRCI）计算OH⁺离子基态和低激发态的势能曲线和A³П-X³Σ^-跃迁体系的跃迁偶极矩。计算过程中考虑了能量的Davidson修正（+Q）效应和标量相对论修正。根据势能曲线，通过求解核的一维Schrödinger方程得到OH⁺的光谱参数。通过计算A³П-X³Σ^-体系的跃迁偶极矩研究这一跃迁体系的Einstein系数、F-C因子。研究了A³П（ν'=0~6）态的跃迁辐射寿命，结果显示其数量级为10^-6 s。

关键词: 势能曲线, Einstein系数, F-C因子, 辐射寿命

Abstract:

A highly accuracy internally multi-reference configuration interaction method (icMRCI) was used to calculate potential curves of low-lying electronic states and transition dipole moment of A³П-X³Σ^- system for OH⁺ ion. Davidson correction (MRCI+Q) of energy and scalar relativistic effect were considered in the calculation. Based on potential energy curves of low-lying electronic states spectroscopic parameters were determined by solving one-dimensional radial Schr dinger equation of nuclear motion. Einstein coefficient and F-C factor of A³П-X³Σ^- transition system are calculated by using the transition dipole moment. Moreover, radiative lifetimes of A³П(ν'=0-6) vibration states were studied. It shows that the radiative lifetimes are of the order of 10^-6 s.

Key words: potential energy curves, Einstein coefficient, F-C factor, radiative lifetime

中图分类号:

O561.3

王兴炜, 宋晓书. 理论研究OH⁺离子电子态光谱及跃迁性质[J]. 计算物理, 2021, 38(6): 729-734.

Xingwei WANG, Xiaoshu SONG. Theoretical Study of Electronic States Spectrum and Transition Property of OH⁺[J]. Chinese Journal of Computational Physics, 2021, 38(6): 729-734.

图/表 5

参考文献 19

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State	R_e/(10^-1 nm)	ω_e/cm^-1	ω_eχ_e/cm^-1	ω_ey_e/cm^-1	B_e/cm^-1	α_e/cm^-1	Ref.
X³∑^-	1.028	3 125.5	83.11	1.05	16.82	0.74
	1.028	3 113.4	78.52		16.79	0.74	实验[7]
	1.031	3 088.1	72.80		16.58	0.77	理论值[9]
	1.029	3 119.0	83.67				理论值[11]
a¹Δ	1.026	3 153.9	79.94	0.86	16.85	0.70
					16.49		实验值[8]
	1.025	3 263.0			16.91		理论值[10]
	1.033	3 143.0	72.75		16.64	0.60	理论值[15]
A³Π	1.134	2 163.4	81.15	0.36	13.73	0.71
	1.135	2 133.7	79.55		13.79	0.88	实验[16]
	1.134	2 219.8	83.20		13.80	0.88	理论值[9]
	1.147	2 187.0	87.60		13.66	0.80	理论值[17]
b¹∑⁺	1.029	3 102.8	72.54	-1.67	16.61	0.52
b¹∑⁺	1.033	3 120.0	79.95		16.32	0.73	理论值[15]
c¹Π	1.220	1 821.33	53.51	-0.05	11.87	0.53

State	R_e/(10^-1 nm)	ω_e/cm^-1	ω_eχ_e/cm^-1	ω_ey_e/cm^-1	B_e/cm^-1	α_e/cm^-1	Ref.
X³∑^-	1.028	3 125.5	83.11	1.05	16.82	0.74
	1.028	3 113.4	78.52		16.79	0.74	实验[7]
	1.031	3 088.1	72.80		16.58	0.77	理论值[9]
	1.029	3 119.0	83.67				理论值[11]
a¹Δ	1.026	3 153.9	79.94	0.86	16.85	0.70
					16.49		实验值[8]
	1.025	3 263.0			16.91		理论值[10]
	1.033	3 143.0	72.75		16.64	0.60	理论值[15]
A³Π	1.134	2 163.4	81.15	0.36	13.73	0.71
	1.135	2 133.7	79.55		13.79	0.88	实验[16]
	1.134	2 219.8	83.20		13.80	0.88	理论值[9]
	1.147	2 187.0	87.60		13.66	0.80	理论值[17]
b¹∑⁺	1.029	3 102.8	72.54	-1.67	16.61	0.52
b¹∑⁺	1.033	3 120.0	79.95		16.32	0.73	理论值[15]
c¹Π	1.220	1 821.33	53.51	-0.05	11.87	0.53

ν′	ν″=0	ν″=1	ν″=2	ν″=3	ν″=4	ν″=5	ν″=6	ν″=7	ν″=8
0	1.94×10⁶	2.88×10⁴	1.33×10³	1.47×10¹	1.36×10²	9.87×10^-3	2.45×10^-4	8.67×10^-7	6.38×10^-8
0	6.25×10^-1	3.07×10^-1	6.10×10^-2	6.15×10^-3	3.32×10^-4	9.78×10^-6	1.65×10^-7	1.64×10^-9	1.63×10^-11
1	1.52×10⁵	3.55×10⁴	2.63×10⁴	2.43×10³	3.74×10¹	2.80×10^-1	1.09×10^-1	3.72×10^-3	3.24×10^-5
1	2.61×10^-1	1.50×10^-1	3.93×10^-1	1.65×10^-1	2.81×10^-2	2.37×10^-3	1.05×10^-4	2.72×10^-6	4.46×10^-8
2	7.92×10⁴	1.11×10⁵	4.47×10²	1.40×10⁴	2.56810³	4.73×10¹	2.19×10⁰	6.90×10^-1	3.22×10^-2
2	8.01×10^-2	2.64×10^-1	1.01×10^-3	2.98×10^-1	2.70×10^-1	7.60×10^-2	9.70×10^-3	6.49×10^-4	2.55×10⁵
3	3.56×10⁴	1.09×10⁵	4.06×10⁴	4.55×10³	4.33×10³	1.83×10³	3.20×10¹	1.03×10¹	3.19×10⁰
3	2.30×10^-2	1.57×10^-1	1.33×10¹	5.44×10^-2	1.31×10^-1	3.17×10^-1	1.51×10^-1	2.95×10^-2	2.97×10^-3
4	1.53×10⁴	7.54×10⁴	7.84×10⁴	4.79×10³	8.52×10³	4.08×10²	8.83×10²	6.59×10⁰	3.50×10¹
4	6.73×10^-3	7.05×10^-2	1.62×10^-1	1.92×10^-2	1.39×10^-1	1.38×10^-2	2.68×10^-1	2.35×10^-1	7.25×10^-2
5	6.59×10³	4.45×10⁴	8.05×10⁴	3.04×10⁴	6.17×10²	5.53×10³	8.45×10¹	2.47×10²	2.12×10⁰
5	2.08×10³	2.89×10^-2	1.11×10^-1	9.03×10^-2	8.83×10^-3	1.36×10^-1	1.68×10^-2	1.38×10^-1	2.82×10^-1
6	2.92×10³	2.47×10⁴	6.35×10⁴	4.98×10⁴	3.68×10³	4.34×10³	1.38×10³	3.86×10³	3.02×10¹
6	6.97×10^-4	1.19×10^-2	6.23×10^-2	1.03×10^-1	1.40×10^-2	6.75810^-2	5.11×10^-2	9.56×10^-2	1.83×10^-2

ν′	ν″=0	ν″=1	ν″=2	ν″=3	ν″=4	ν″=5	ν″=6	ν″=7	ν″=8
0	1.94×10⁶	2.88×10⁴	1.33×10³	1.47×10¹	1.36×10²	9.87×10^-3	2.45×10^-4	8.67×10^-7	6.38×10^-8
0	6.25×10^-1	3.07×10^-1	6.10×10^-2	6.15×10^-3	3.32×10^-4	9.78×10^-6	1.65×10^-7	1.64×10^-9	1.63×10^-11
1	1.52×10⁵	3.55×10⁴	2.63×10⁴	2.43×10³	3.74×10¹	2.80×10^-1	1.09×10^-1	3.72×10^-3	3.24×10^-5
1	2.61×10^-1	1.50×10^-1	3.93×10^-1	1.65×10^-1	2.81×10^-2	2.37×10^-3	1.05×10^-4	2.72×10^-6	4.46×10^-8
2	7.92×10⁴	1.11×10⁵	4.47×10²	1.40×10⁴	2.56810³	4.73×10¹	2.19×10⁰	6.90×10^-1	3.22×10^-2
2	8.01×10^-2	2.64×10^-1	1.01×10^-3	2.98×10^-1	2.70×10^-1	7.60×10^-2	9.70×10^-3	6.49×10^-4	2.55×10⁵
3	3.56×10⁴	1.09×10⁵	4.06×10⁴	4.55×10³	4.33×10³	1.83×10³	3.20×10¹	1.03×10¹	3.19×10⁰
3	2.30×10^-2	1.57×10^-1	1.33×10¹	5.44×10^-2	1.31×10^-1	3.17×10^-1	1.51×10^-1	2.95×10^-2	2.97×10^-3
4	1.53×10⁴	7.54×10⁴	7.84×10⁴	4.79×10³	8.52×10³	4.08×10²	8.83×10²	6.59×10⁰	3.50×10¹
4	6.73×10^-3	7.05×10^-2	1.62×10^-1	1.92×10^-2	1.39×10^-1	1.38×10^-2	2.68×10^-1	2.35×10^-1	7.25×10^-2
5	6.59×10³	4.45×10⁴	8.05×10⁴	3.04×10⁴	6.17×10²	5.53×10³	8.45×10¹	2.47×10²	2.12×10⁰
5	2.08×10³	2.89×10^-2	1.11×10^-1	9.03×10^-2	8.83×10^-3	1.36×10^-1	1.68×10^-2	1.38×10^-1	2.82×10^-1
6	2.92×10³	2.47×10⁴	6.35×10⁴	4.98×10⁴	3.68×10³	4.34×10³	1.38×10³	3.86×10³	3.02×10¹
6	6.97×10^-4	1.19×10^-2	6.23×10^-2	1.03×10^-1	1.40×10^-2	6.75810^-2	5.11×10^-2	9.56×10^-2	1.83×10^-2

ν′	0	1	2	3	4	5	6
τ/s	4.46×10^-6	4.61×10^-6	4.81×10^-6	5.08×10^-6	5.44×10^-6	5.93×10^-6	6.62×10^-6