绝缘气体介电强度的构效关系

doi:10.7503/cjcu20180530

摘要/Abstract

摘要：

提出了一种全新的构效关系模型, 基于中性分子的静电势参数, 包括总表面积、正负静电势的分离度、局域极性、分子密度及约化正静电势面积等具有明确物理意义的描述符, 直接获得各种类型气体的介电强度. 研究结果表明, 理论值与实验值的平均绝对偏差仅为0.06, 且相关系数达到0.993. 基于构效关系模型, 分析了气体的宏观介电强度受微观电子结构影响的规律, 发现了提高气体介电强度的分子设计思路.

关键词: 介电强度, 绝缘气体, 六氟化硫, 构效关系模型, 静电势

Abstract:

A new structure-activity relationship was obtained on the basis of the electrostatic potential surface of the neutral molecules, including the total surface area, the balanced positive and negative potential separation, the local polarity, molecular density, and the reduced positive surface area. The physical dilemma and computational difficulties in the use of ionic or anionic structures were both removed in the present models. The absolute mean deviation of the theoretical dielectric strengths from the experimental data is as low as 0.06 and the correlation coefficient is 0.993. The effects of electronic structures on the dielectric strength were analyzed to gain insights on the molecular design on the novel insulation gases superior to SF₆.

Key words: Dielectric strength, Insulation gas, Hexafluoride sulfur, Structure-activity relationship, Electrostatic potential

中图分类号:

O641.1

TrendMD:

侯华, 余小娟, 周文俊, 罗运柏, 王宝山. 绝缘气体介电强度的构效关系. 高等学校化学学报, 2018, 39(11): 2477.

HOU Hua, YU Xiaojuan, ZHOU Wenjun, LUO Yunbai, WANG Baoshan. Theoretical Investigations on the Structure-activity Relationship to the Dielectric Strength of the Insulation Gases^†. Chem. J. Chinese Universities, 2018, 39(11): 2477.

图/表 8

Table 1 GIPF parameters and dielectric strengths for a total of 43 insulation gaseous molecules

Species	CAS registry	A_s/nm²	ν $σ tot 2$ /(kJ²·mol^-2)	Π/eV	ρ/(g·cm^-3)	$A s, r +$ /nm²	E_r,cal	$E r, expt *$
H₂	1333-74-0	0.336	6.635	0.131	0.180	0.208	0.16	0.22
O₂	7782-44-7	0.506	1.400	0.091	1.624	0.296	0.34	0.33
N₂	7727-37-9	0.542	44.973	0.173	1.265	0.350	0.35	0.38
N₂O	10024-97-2	0.666	182.831	0.430	1.541	0.342	0.40	0.46
CO	630-08-0	0.545	94.462	0.261	1.254	0.317	0.34	0.40
CO₂	124-38-9	0.647	207.724	0.532	1.591	0.301	0.27	0.35
OCS	463-58-1	0.819	215.830	0.277	1.546	0.518	0.93	0.90
SF₆	2551-62-4	1.034	0.140	0.087	2.777	0.733	0.99	1.00
CH₄	74-82-8	0.602	9.208	0.126	0.624	0.346	0.37	0.43
CH₃Cl	74-87-3	0.816	192.564	0.558	1.299	0.410	0.33	0.32
CH₃Br	74-83-9	0.882	196.293	0.525	2.181	0.429	0.49	0.45
CH₂F₂	75-10-5	0.712	313.110	0.701	1.676	0.320	0.33	0.27
CH₂Cl₂	75-09-2	1.014	194.823	0.481	1.634	0.402	0.69	0.68
CHF₂Cl	75-45-6	0.914	152.353	0.450	1.945	0.345	0.51	0.42
CHFCl₂	75-43-4	1.057	146.752	0.382	1.881	0.424	0.78	0.92
CF₄	75-73-0	0.811	4.219	0.175	2.388	0.382	0.49	0.42
CF₃Cl	75-72-9	0.957	10.906	0.172	2.208	0.550	0.68	0.58
CF₂Cl₂	75-71-8	1.095	38.548	0.176	2.108	0.576	0.91	0.99
CF₃Br	75-63-8	1.023	20.324	0.187	2.864	0.517	0.78	0.75
CH₃CF₃	420-46-2	0.977	170.332	0.564	1.745	0.425	0.43	0.41
CH₃CHCl₂	75-34-3	1.204	214.009	0.461	1.497	0.544	1.01	1.01
C₂F₆	76-16-4	1.118	3.519	0.144	2.427	0.638	0.92	0.80
CF₃CF₂Cl	76-15-3	1.241	9.646	0.158	2.314	0.633	1.05	1.04
F₂C＝CFCl	79-38-9	1.103	76.028	0.251	2.089	0.557	0.89	0.72
CF₃CH＝CH₂	677-21-4	1.114	223.217	0.494	1.674	0.501	0.87	0.80
CF₃CF＝CF₂	116-15-4	1.261	55.424	0.296	2.291	0.609	0.95	0.94
CF₂＝CF—CF＝CF₂	685-63-2	1.401	89.157	0.315	2.184	0.586	1.18	1.20
c-C₆F₁₀	355-75-9	1.786	14.075	0.220	2.428	0.892	1.80	1.90
c-C₄F₈	115-25-3	1.472	5.602	0.241	2.437	0.605	1.18	1.25
c-C₆F₁₂	355-68-0	1.856	0.910	0.107	2.553	1.304	2.33	2.35
c-CF₃(C₄F₆)CF₃	1583-97-7	1.935	7.545	0.176	2.512	1.063	2.19	2.30
CF₃OCF₃	1479-49-8	1.214	8.963	0.163	2.442	0.601	1.01	1.00
c-CF₃(C₂F₂O)CF₃	117642-58-7	1.590	33.769	0.221	2.406	0.793	1.53	1.60
HC≡CH	74-86-2	0.672	304.742	0.534	0.858	0.306	0.57	0.60
SO₂F₂	2699-79-8	0.922	186.140	0.383	2.303	0.543	0.79	0.73
CF₃SO₂F	335-05-7	1.230	216.863	0.346	2.349	0.782	1.36	1.45
CH₃CN	75-05-8	0.851	532.756	0.892	1.021	0.470	0.77	0.80
CF₃CN	353-85-5	1.013	366.065	0.334	1.931	0.706	1.53	1.50
C₂F₅CN	422-04-8	1.304	297.109	0.257	2.110	0.940	1.88	2.00
C₃F₇CN	375-00-8	1.565	280.934	0.230	2.219	1.142	2.32	2.40
i-C₃F₇CN	42532-60-5	1.548	245.345	0.218	2.227	1.138	2.22	2.20
i-C₃F₇COCF₃	756-12-7	1.812	165.640	0.210	2.428	1.045	2.38	2.10
i-C₃F₇COC₂F₅	756-13-8	2.090	125.727	0.184	2.449	1.201	2.85	2.80

Table 1 GIPF parameters and dielectric strengths for a total of 43 insulation gaseous molecules

Species	CAS registry	A_s/nm²	ν $σ tot 2$ /(kJ²·mol^-2)	Π/eV	ρ/(g·cm^-3)	$A s, r +$ /nm²	E_r,cal	$E r, expt *$
H₂	1333-74-0	0.336	6.635	0.131	0.180	0.208	0.16	0.22
O₂	7782-44-7	0.506	1.400	0.091	1.624	0.296	0.34	0.33
N₂	7727-37-9	0.542	44.973	0.173	1.265	0.350	0.35	0.38
N₂O	10024-97-2	0.666	182.831	0.430	1.541	0.342	0.40	0.46
CO	630-08-0	0.545	94.462	0.261	1.254	0.317	0.34	0.40
CO₂	124-38-9	0.647	207.724	0.532	1.591	0.301	0.27	0.35
OCS	463-58-1	0.819	215.830	0.277	1.546	0.518	0.93	0.90
SF₆	2551-62-4	1.034	0.140	0.087	2.777	0.733	0.99	1.00
CH₄	74-82-8	0.602	9.208	0.126	0.624	0.346	0.37	0.43
CH₃Cl	74-87-3	0.816	192.564	0.558	1.299	0.410	0.33	0.32
CH₃Br	74-83-9	0.882	196.293	0.525	2.181	0.429	0.49	0.45
CH₂F₂	75-10-5	0.712	313.110	0.701	1.676	0.320	0.33	0.27
CH₂Cl₂	75-09-2	1.014	194.823	0.481	1.634	0.402	0.69	0.68
CHF₂Cl	75-45-6	0.914	152.353	0.450	1.945	0.345	0.51	0.42
CHFCl₂	75-43-4	1.057	146.752	0.382	1.881	0.424	0.78	0.92
CF₄	75-73-0	0.811	4.219	0.175	2.388	0.382	0.49	0.42
CF₃Cl	75-72-9	0.957	10.906	0.172	2.208	0.550	0.68	0.58
CF₂Cl₂	75-71-8	1.095	38.548	0.176	2.108	0.576	0.91	0.99
CF₃Br	75-63-8	1.023	20.324	0.187	2.864	0.517	0.78	0.75
CH₃CF₃	420-46-2	0.977	170.332	0.564	1.745	0.425	0.43	0.41
CH₃CHCl₂	75-34-3	1.204	214.009	0.461	1.497	0.544	1.01	1.01
C₂F₆	76-16-4	1.118	3.519	0.144	2.427	0.638	0.92	0.80
CF₃CF₂Cl	76-15-3	1.241	9.646	0.158	2.314	0.633	1.05	1.04
F₂C＝CFCl	79-38-9	1.103	76.028	0.251	2.089	0.557	0.89	0.72
CF₃CH＝CH₂	677-21-4	1.114	223.217	0.494	1.674	0.501	0.87	0.80
CF₃CF＝CF₂	116-15-4	1.261	55.424	0.296	2.291	0.609	0.95	0.94
CF₂＝CF—CF＝CF₂	685-63-2	1.401	89.157	0.315	2.184	0.586	1.18	1.20
c-C₆F₁₀	355-75-9	1.786	14.075	0.220	2.428	0.892	1.80	1.90
c-C₄F₈	115-25-3	1.472	5.602	0.241	2.437	0.605	1.18	1.25
c-C₆F₁₂	355-68-0	1.856	0.910	0.107	2.553	1.304	2.33	2.35
c-CF₃(C₄F₆)CF₃	1583-97-7	1.935	7.545	0.176	2.512	1.063	2.19	2.30
CF₃OCF₃	1479-49-8	1.214	8.963	0.163	2.442	0.601	1.01	1.00
c-CF₃(C₂F₂O)CF₃	117642-58-7	1.590	33.769	0.221	2.406	0.793	1.53	1.60
HC≡CH	74-86-2	0.672	304.742	0.534	0.858	0.306	0.57	0.60
SO₂F₂	2699-79-8	0.922	186.140	0.383	2.303	0.543	0.79	0.73
CF₃SO₂F	335-05-7	1.230	216.863	0.346	2.349	0.782	1.36	1.45
CH₃CN	75-05-8	0.851	532.756	0.892	1.021	0.470	0.77	0.80
CF₃CN	353-85-5	1.013	366.065	0.334	1.931	0.706	1.53	1.50
C₂F₅CN	422-04-8	1.304	297.109	0.257	2.110	0.940	1.88	2.00
C₃F₇CN	375-00-8	1.565	280.934	0.230	2.219	1.142	2.32	2.40
i-C₃F₇CN	42532-60-5	1.548	245.345	0.218	2.227	1.138	2.22	2.20
i-C₃F₇COCF₃	756-12-7	1.812	165.640	0.210	2.428	1.045	2.38	2.10
i-C₃F₇COC₂F₅	756-13-8	2.090	125.727	0.184	2.449	1.201	2.85	2.80

Fig.1 Dependence of the polarizabilities(α) on the total surface area(As) for 43 moleculesLine: least-square linear fit.

Fig.2 Electrostatic potential surfaces of SF6(A) and (CF3)2CFC≡N(B) mapping on the electron density at an isovalue of 0.001 a.u.

Fig.3 Dependence of the dielectric strength on the reduced positive electrostatic surface area of 43 moleculesLine: least-square linear fit.

Fig.4 Theoretical dielectric strength predicted by the structure-activity relationship model S4 versus the experimental dataLine: diagonal line with y=x.

Table 2 M06-2X/6-31++G(d,p) calculated GIPF parameters and dielectric strengths for the prototypical insulation gaseous molecules

Species	A_s/nm²	ν $σ tot 2$ /(kJ²·mol^-2)	Π/eV	ρ/(g·cm^-3)	$A s, red +$ /nm²	E_r,cal	$E r, expt *$
SF₅CF₃	1.308	17.628	0.167	2.716	0.746	1.19	1.2—1.6
NSF₃	0.942	350.030	0.378	2.252	0.704	1.34	1.4
SO₂	0.754	462.050	0.762	1.849	0.361	0.71	0.52—1.0
SeF₆	1.101	0.858	0.131	3.413	0.687	1.00	1.03—1.14
C₆F₆	1.551	35.222	0.380	2.150	0.738	1.11	1.05—1.15
C₄F₁₀	1.639	2.661	0.129	2.502	1.125	1.76	1.0—1.58

Table 2 M06-2X/6-31++G(d,p) calculated GIPF parameters and dielectric strengths for the prototypical insulation gaseous molecules

Species	A_s/nm²	ν $σ tot 2$ /(kJ²·mol^-2)	Π/eV	ρ/(g·cm^-3)	$A s, red +$ /nm²	E_r,cal	$E r, expt *$
SF₅CF₃	1.308	17.628	0.167	2.716	0.746	1.19	1.2—1.6
NSF₃	0.942	350.030	0.378	2.252	0.704	1.34	1.4
SO₂	0.754	462.050	0.762	1.849	0.361	0.71	0.52—1.0
SeF₆	1.101	0.858	0.131	3.413	0.687	1.00	1.03—1.14
C₆F₆	1.551	35.222	0.380	2.150	0.738	1.11	1.05—1.15
C₄F₁₀	1.639	2.661	0.129	2.502	1.125	1.76	1.0—1.58

Fig.5 Dependence of the contribution percentages of νσtot2 to the dielectric strength on those of As predicted by the structure-activity relationship model S5

Fig.6 Contribution percentages of Π and ρAs,r+ to the theoretical dielectric strength

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