单原子气体第二介电维里系数准确计算

doi:10.11949/0438-1157.20190579

摘要/Abstract

摘要：

采用当前文献中已知最佳的从头算势能和极化率计算了多种稀有气体的第二介电维里系数。研究对象包括氦-4、氦-3、氖和氩。根据经典统计力学公式和一二阶量子修正项对第二介电维里系数进行了计算，在此基础上，通过[1/1]帕德近似将研究的温度下限拓展至25 K。第二介电维里系数理论值的不确定度可以由势能和极化率的不确定度进行评估，再结合与文献实验数据的比较可以发现，理论计算结果为计量、仪器标定等领域提供了所需的高精度基础数据。

关键词: 计算化学, 统计热力学, 热力学性质, 稀有气体, 介电维里

Abstract:

The state-of-the-art ab initio potentials and polarizabilities in the literature were used in this work to compute the second dielectric virial coefficient of pure light noble gases. The systems considered here are helium-4, helium-3, neon, and argon. The second dielectric virial coefficient was calculated using the classical statistical-mechanics formulas with quantum corrections up to the second order and the [1/1] Padé approximant was applied to extend the temperature range of the calculated values down to T = 25 K. The possible uncertainty sources of the present predictions and the uncertainty of the theoretical values estimated from the uncertainties of potentials and polarizabilities were identified. The critical assessment of the computed values and the experimental data in the literature with a relative larger uncertainty shows that the calculated values in this work can be used with confidence in research areas relating to the second dielectric virial coefficient of light noble gases.

Key words: computational chemistry, statistical thermodynamics, thermodynamic properties, noble gas, dielectric virial

中图分类号:

TK 123

宋渤,杨敏,安然,王晓坡. 单原子气体第二介电维里系数准确计算[J]. 化工学报, 2019, 70(S2): 50-53.

Bo SONG,Min YANG,Ran AN,Xiaopo WANG. Accurate calculations of second dielectric virial coefficient of noble gases[J]. CIESC Journal, 2019, 70(S2): 50-53.

图/表 6

参考文献 30

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T/K	B _ε/ (cm⁶·mol^-2)	[1/1] Padé/(cm⁶·mol^-2)	σ/ (cm⁶·mol^-2)	σ from V/%	σ from Δα _ave/%
25	-0.01162	-0.008735	0.000177	0.13	99.86
30	-0.01179	-0.01017	0.00018	0.13	99.87
35	-0.01255	-0.01153	0.00017	0.13	99.87
40	-0.01353	-0.01285	0.00017	0.13	99.87
45	-0.01459	-0.01411	0.00017	0.12	99.88
50	-0.01568	-0.01533	0.00017	0.12	99.88
60	-0.01785	-0.01764	0.00017	0.12	99.88
70	-0.01995	-0.01982	0.00017	0.12	99.88
80	-0.02197	-0.02188	0.00017	0.12	99.88
90	-0.02391	-0.02385	0.00017	0.12	99.88
100	-0.02578	-0.02573	0.00017	0.12	99.88
150	-0.03417	-0.03415	0.00017	0.11	99.89
200	-0.04142	-0.04141	0.00017	0.11	99.89
250	-0.04787	-0.04787	0.00018	0.11	99.89
273.15	-0.05065	-0.05065	0.00018	0.11	99.89
273.16	-0.05065	-0.05065	0.00018	0.11	99.89
293.15	-0.05296	-0.05296	0.00018	0.11	99.89
298.15	-0.05353	-0.05352	0.00018	0.11	99.89
300	-0.05373	-0.05373	0.00018	0.11	99.89
350	-0.05913	-0.05912	0.00018	0.11	99.89
400	-0.06414	-0.06414	0.00018	0.11	99.89
450	-0.06884	-0.06884	0.00018	0.11	99.89
500	-0.07327	-0.07326	0.00018	0.11	99.89
600	-0.08145	-0.08145	0.00018	0.11	99.89
?	?	?	?	?	?
10000	-0.29473	-0.29473	0.000199	0.09	99.91

T/K	B _ε/ (cm⁶·mol^-2)	[1/1] Padé/(cm⁶·mol^-2)	σ/ (cm⁶·mol^-2)	σ from V/%	σ from Δα _ave/%
25	-0.01162	-0.008735	0.000177	0.13	99.86
30	-0.01179	-0.01017	0.00018	0.13	99.87
35	-0.01255	-0.01153	0.00017	0.13	99.87
40	-0.01353	-0.01285	0.00017	0.13	99.87
45	-0.01459	-0.01411	0.00017	0.12	99.88
50	-0.01568	-0.01533	0.00017	0.12	99.88
60	-0.01785	-0.01764	0.00017	0.12	99.88
70	-0.01995	-0.01982	0.00017	0.12	99.88
80	-0.02197	-0.02188	0.00017	0.12	99.88
90	-0.02391	-0.02385	0.00017	0.12	99.88
100	-0.02578	-0.02573	0.00017	0.12	99.88
150	-0.03417	-0.03415	0.00017	0.11	99.89
200	-0.04142	-0.04141	0.00017	0.11	99.89
250	-0.04787	-0.04787	0.00018	0.11	99.89
273.15	-0.05065	-0.05065	0.00018	0.11	99.89
273.16	-0.05065	-0.05065	0.00018	0.11	99.89
293.15	-0.05296	-0.05296	0.00018	0.11	99.89
298.15	-0.05353	-0.05352	0.00018	0.11	99.89
300	-0.05373	-0.05373	0.00018	0.11	99.89
350	-0.05913	-0.05912	0.00018	0.11	99.89
400	-0.06414	-0.06414	0.00018	0.11	99.89
450	-0.06884	-0.06884	0.00018	0.11	99.89
500	-0.07327	-0.07326	0.00018	0.11	99.89
600	-0.08145	-0.08145	0.00018	0.11	99.89
?	?	?	?	?	?
10000	-0.29473	-0.29473	0.000199	0.09	99.91