计算类氦离子基态能级z=1-103从氢到铹

让原子核外有两个电子，让核电荷数z=1-103从H到Lr。

两个1s电子波函数为

能级为

分成三部分，两个电子的动能和势能，加上两个电子之间的排斥能

将第一部分打开

第二部分与第一部分操作方法相同

打开第三部分，单中心双电子排斥能积分

对于两个1s轨道电子的积分有公式

展开

将三部分相加，让z=1-103，得到表格

 

			动能	势能	相互作用能	基态能级Hartrees	基态能级ev	*基态能级实验值ev	计算值/实验值
1	H	1-	1	-2	0.625	-0.375	-10.2
2	He		4	-8	1.25	-2.75	-74.8	-79.00519	0.946773244
3	Li	1+	9	-18	1.875	-7.125	-193.8	-198.06447	0.978469283
4	Be	2+	16	-32	2.5	-13.5	-367.2	-371.61526	0.988118733
5	B	3+	25	-50	3.125	-21.875	-595	-599.60101	0.992326547
6	C	4+	36	-72	3.75	-32.25	-877.2	-882.08034	0.994467239
7	N	5+	49	-98	4.375	-44.625	-1213.8	-1219.1178	0.995637993
8	O	6+	64	-128	5	-59	-1604.8	-1610.7001	0.996336934
9	F	7+	81	-162	5.625	-75.375	-2050.2	-2057.0288	0.99668026
10	Ne	8+	100	-200	6.25	-93.75	-2550	-2558.0281	0.996861606
11	Na	9+	121	-242	6.875	-114.125	-3104.2	-3113.823	0.996909587
12	Mg	10+	144	-288	7.5	-136.5	-3712.8	-3724.47	0.996866668
13	Al	11+	169	-338	8.125	-160.875	-4375.8	-4390.121	0.996737903
14	Si	12+	196	-392	8.75	-187.25	-5093.2	-5110.812	0.996553972
15	p	13+	225	-450	9.375	-215.625	-5865	-5886.752	0.996304923
16	S	14+	256	-512	10	-246	-6691.2
17	Cl	15+	289	-578	10.625	-278.375	-7571.8
18	Ar	16+	324	-648	11.25	-312.75	-8506.8
19	K	17+	361	-722	11.875	-349.125	-9496.2
20	Ca	18+	400	-800	12.5	-387.5	-10540
21	Sc	19+	441	-882	13.125	-427.875	-11638.2
22	Ti	20+	484	-968	13.75	-470.25	-12790.8
23	V	21+	529	-1058	14.375	-514.625	-13997.8
24	Cr	22+	576	-1152	15	-561	-15259.2
25	Mn	23+	625	-1250	15.625	-609.375	-16575
26	Fe	24+	676	-1352	16.25	-659.75	-17945.2
27	Co	25+	729	-1458	16.875	-712.125	-19369.8
28	Ni	26+	784	-1568	17.5	-766.5	-20848.8
29	Cu	27+	841	-1682	18.125	-822.875	-22382.2
30	Zn	28+	900	-1800	18.75	-881.25	-23970
31	Ga	29+	961	-1922	19.375	-941.625	-25612.2
32	Ge	30+	1024	-2048	20	-1004	-27308.8
33	As	31+	1089	-2178	20.625	-1068.375	-29059.8
34	Se	32+	1156	-2312	21.25	-1134.75	-30865.2
35	Br	33+	1225	-2450	21.875	-1203.125	-32725
36	Kr	34+	1296	-2592	22.5	-1273.5	-34639.2
37	Rb	35+	1369	-2738	23.125	-1345.875	-36607.8
38	Sr	36+	1444	-2888	23.75	-1420.25	-38630.8
39	Y	37+	1521	-3042	24.375	-1496.625	-40708.2
40	Zr	38+	1600	-3200	25	-1575	-42840
41	Nb	39+	1681	-3362	25.625	-1655.375	-45026.2
42	Mo	40+	1764	-3528	26.25	-1737.75	-47266.8
43	Tc	41+	1849	-3698	26.875	-1822.125	-49561.8
44	Ru	42+	1936	-3872	27.5	-1908.5	-51911.2
45	Rh	43+	2025	-4050	28.125	-1996.875	-54315
46	Pd	44+	2116	-4232	28.75	-2087.25	-56773.2
47	Ag	45+	2209	-4418	29.375	-2179.625	-59285.8
48	Cd	46+	2304	-4608	30	-2274	-61852.8
49	In	47+	2401	-4802	30.625	-2370.375	-64474.2
50	Sn	48+	2500	-5000	31.25	-2468.75	-67150
51	Sb	49+	2601	-5202	31.875	-2569.125	-69880.2
52	Te	50+	2704	-5408	32.5	-2671.5	-72664.8
53	I	51+	2809	-5618	33.125	-2775.875	-75503.8
54	Xe	52+	2916	-5832	33.75	-2882.25	-78397.2
55	Cs	53+	3025	-6050	34.375	-2990.625	-81345
56	Ba	54+	3136	-6272	35	-3101	-84347.2
57	La	55+	3249	-6498	35.625	-3213.375	-87403.8
58	Ce	56+	3364	-6728	36.25	-3327.75	-90514.8
59	Pr	57+	3481	-6962	36.875	-3444.125	-93680.2
60	Nd	58+	3600	-7200	37.5	-3562.5	-96900
61	Pm	59+	3721	-7442	38.125	-3682.875	-100174.2
62	Sm	60+	3844	-7688	38.75	-3805.25	-103502.8
63	Eu	61+	3969	-7938	39.375	-3929.625	-106885.8
64	Gd	62+	4096	-8192	40	-4056	-110323.2
65	Tb	63+	4225	-8450	40.625	-4184.375	-113815
66	Dy	64+	4356	-8712	41.25	-4314.75	-117361.2
67	Ho	65+	4489	-8978	41.875	-4447.125	-120961.8
68	Er	66+	4624	-9248	42.5	-4581.5	-124616.8
69	Tm	67+	4761	-9522	43.125	-4717.875	-128326.2
70	Yb	68+	4900	-9800	43.75	-4856.25	-132090
71	Lu	69+	5041	-10082	44.375	-4996.625	-135908.2
72	Hf	70+	5184	-10368	45	-5139	-139780.8
73	Ta	71+	5329	-10658	45.625	-5283.375	-143707.8
74	W	72+	5476	-10952	46.25	-5429.75	-147689.2
75	Re	73+	5625	-11250	46.875	-5578.125	-151725
76	Os	74+	5776	-11552	47.5	-5728.5	-155815.2
77	Ir	75+	5929	-11858	48.125	-5880.875	-159959.8
78	Pt	76+	6084	-12168	48.75	-6035.25	-164158.8
79	Au	77+	6241	-12482	49.375	-6191.625	-168412.2
80	Hg	78+	6400	-12800	50	-6350	-172720
81	Tl	79+	6561	-13122	50.625	-6510.375	-177082.2
82	Pb	80+	6724	-13448	51.25	-6672.75	-181498.8
83	Bi	81+	6889	-13778	51.875	-6837.125	-185969.8
84	Po	82+	7056	-14112	52.5	-7003.5	-190495.2
85	At	83+	7225	-14450	53.125	-7171.875	-195075
86	Rn	84+	7396	-14792	53.75	-7342.25	-199709.2
87	Fr	85+	7569	-15138	54.375	-7514.625	-204397.8
88	Ra	86+	7744	-15488	55	-7689	-209140.8
89	Ac	87+	7921	-15842	55.625	-7865.375	-213938.2
90	Th	88+	8100	-16200	56.25	-8043.75	-218790
91	Pa	89+	8281	-16562	56.875	-8224.125	-223696.2
92	U	90+	8464	-16928	57.5	-8406.5	-228656.8
93	Np	91+	8649	-17298	58.125	-8590.875	-233671.8
94	Pu	92+	8836	-17672	58.75	-8777.25	-238741.2
95	Am	93+	9025	-18050	59.375	-8965.625	-243865
96	Cm	94+	9216	-18432	60	-9156	-249043.2
97	Bk	95+	9409	-18818	60.625	-9348.375	-254275.8
98	Cf	96+	9604	-19208	61.25	-9542.75	-259562.8
99	Es	97+	9801	-19602	61.875	-9739.125	-264904.2
100	Fm	98+	10000	-20000	62.5	-9937.5	-270300
101	Md	99+	10201	-20402	63.125	-10137.875	-275750.2
102	No	100+	10404	-20808	63.75	-10340.25	-281254.8
103	Lr	101+	10609	-21218	64.375	-10544.625	-286813.8

 

可以找到从He到P共14组实验数据，在能找到的14组实验数据里，计算值和实验值都相对符合良好。

从数据可以看到动能/势能=-1/2符合维里定理，并且任意两元素的动能与动能的比值等于势能与势能的比值，并且等于相互作用能比值的平方

 

或简写

比如p与0

Python代码为

import sympy
import csv
import math
from sympy import symbols, cancel

a = sympy.Symbol('a')
e = sympy.Symbol('e')
m = sympy.Symbol('m')
h = sympy.Symbol('h')
l = sympy.Symbol('l')
lp = sympy.Symbol('lp')
r = sympy.Symbol('r')
EE = sympy.Symbol('EE')
r1 = sympy.Symbol('r1')
r2 = sympy.Symbol('r2')
r3 = sympy.Symbol('r3')

x = sympy.Symbol('x')
y = sympy.Symbol('y')
z = sympy.Symbol('z')

θ1= sympy.Symbol('θ1')
θ2= sympy.Symbol('θ2')
Φ1= sympy.Symbol('Φ1')
Φ2= sympy.Symbol('Φ2')

θ= sympy.Symbol('θ')
Ψ= sympy.Symbol('Ψ')
Φ= sympy.Symbol('Φ')
pi=sympy.Symbol('pi')
E=sympy.Symbol('E')
I=sympy.Symbol('I')
sin=sympy.Symbol('sin')
cos=sympy.Symbol('cos')
diff=sympy.Symbol('diff')
integrate=sympy.Symbol('integrate')

pi=sympy.pi
E=sympy.E
sin=sympy.sin
cos=sympy.cos
diff=sympy.diff
integrate=sympy.integrate



def cr( str ):

   z = str
   #波函数
   fx = (z) ** (1.5) * sympy.exp(-z * r) * pi ** (-0.5)
   #拉普拉斯算符
   f1 = (1 / (r * r)) * diff((r * r * diff(fx, r)), r)

   f2 = (1 / (r * r * sin(θ))) * diff((sin(θ) * diff(fx, θ)), θ)

   f3 = (1 / (r * r * sin(θ) * sin(θ))) * diff(fx, Φ, Φ)

   f8 = (-1 / 2) * (f1 + f2 + f3) * fx

   # print   (   f1 )
   # print   (   f2 )
   # print   (   f3 )

   # print    ( f8 )

   # 球坐标积分  动能
   f9 = (integrate((integrate(integrate(f8 * r * r * sin(θ), (r, 0, float('inf'))), (θ, 0, pi))), (Φ, 0, 2 * pi)))

   #print(f9)

   f10 = fx * (-z / r) * fx
   #势能
   f11 = (integrate((integrate(integrate(f10 * r * r * sin(θ), (r, 0, float('inf'))), (θ, 0, pi))), (Φ, 0, 2 * pi)))

   #print(f11)

   #print("H", f9 + f11)

   # 库仑斥力积分
   fr1 = (z) ** (1.5) * sympy.exp(-z * r1) * pi ** (-0.5)
   fr2 = (z) ** (1.5) * sympy.exp(-z * r2) * pi ** (-0.5)

   f21 = fr1 * fr2 * (1 / r1) * fr1 * fr2 * r1 * r1 * r2 * r2

   f22 = fr1 * fr2 * (1 / r2) * fr1 * fr2 * r1 * r1 * r2 * r2


   f23 = (integrate(f21, (r2, 0, r1)))

   f24 = (integrate(f22, (r2, r1, float('inf'))))

   f25 = (16 * pi ** (2) * integrate(f24 + f23, (r1, 0, float('inf'))))

   # print("f23",f23)
   # print("f24",f24)

   print("CR", f25)

   #两个电子的动能和势能+两个电子间的库仑相互作用
   f26 = (f9 + f11) * 2 + f25

   print("Li+", f26, f26 * 27.2)

   str= f9*2 , f11* 2 , f25, f26, f26 * 27.2

   return str

################################

f = open('d:/工业/实验数据/python/cr.csv','w',encoding='gbk')
csv_writer = csv.writer(f)

for i in range(1,104):
 print(" i ", i )
 #cr(i)
 csv_writer.writerow([ i ,cr(i) ])

# 5. 关闭文件
f.close()

John P. Lowe, Kirk Peterson--- Quantum Chemistry p587 Appendix 3  Evaluation of the Coulomb Repulsion Integral Over 1s AOs

*罗淳---类铍原子基态能级多体微优计算一包含Bret相互作用