Quantum Mechanics II (Text Book: B. K.

Agarwal and Hari Prakash)

He Atom
(Z = 2, A = 4) e-

Helium atom is a two electron system. It’s electronic Hamiltonian can be split into sum of
hydrogen-like Hamiltonians and an interaction energy term. r2 r12
H = H0 + H’ = H01 + H02 + H’
Ze
………… (1) r1
e-
Figure 1. Helium Atom
Because of the presence of the interaction term in the Hamiltonian the method of
separation of variable can partially be possible through the stationary perturbation method. Ground State Unperturbed Wave Function:
The unperturbed Hamiltonians H01 and H02 are hydrogen like Hamiltonians and their
solutions are also hydrogen like wave functions and energy. Therefore, the unperturbed
wave function of the helium atom will be

………….. (2)
And Ground State Unperturbed Energy:
where are hydrogen atom wave functions. Clearly, the unperturbed energy is 0 0 2
𝐸 11 =2 𝐸 1=2 𝑍 𝐸 𝐻 =−108.8 𝑒𝑉
, …………… (3)
Experimental Value = -78.98 eV
Therefore, contribution of the
interaction term = 29.82 eV
 Calculation of the interaction energy (E11(1)) of the ground state of the helium atom
The first-order perturbation theory gives Formulae:
2 2 2
𝑍 𝑒 𝑍
2 𝐸𝑛 =− =− 2 13.6 𝑒𝑉
𝑒 0
2
2 𝑎0 𝑛 𝑛
𝐸11 =∫ 𝑢11 (𝒓 𝟏 ,𝒓 𝟐) 𝑢11 (𝒓 𝟏 ,𝒓 𝟐)𝑑 𝑟 1 𝑑 𝑟 2
(1) 0∗ 3 3

′
𝛹 𝑛𝑙𝑚 (𝒓 )=𝛹 𝑛𝑙𝑚 ( 𝑟 , θ , 𝜑 )=𝑅 𝑛𝑙 (𝑟 ) 𝑌 𝑙𝑚 ( θ , 𝜑 )
𝑟 12

( θ , 𝜑 ) 𝑑 𝝮 = δ 𝑙𝑙 δ 𝑚𝑚
− 𝑍𝑟

( )
− 𝑍𝑟 3
𝑍
3
𝑍 𝑍𝑟

′
𝑎0 2 𝑎0
𝑅10 (𝑟 )=( ) 2 2 𝑒
𝑎0 𝑅 20(𝑟 )= (2 − 2
)𝑒
𝑒2 0 2 𝑎0 𝑎0
¿ ∫ 𝛹 ( 𝒓 𝟏 ) 𝛹 ( 𝒓 𝟐 ) 𝛹 100 ( 𝒓 𝟏 ) 𝛹 0100 ( 𝒓 𝟐) 𝑑 3 𝑟 1 𝑑3 𝑟 2
0∗
100
0∗
100
𝑟 12 − 𝑍𝑟

=𝑌 00 1= √ 4 π 𝑌 00
𝑍 32 𝑍𝑟 2𝑎 1 ∗
𝑅 21 (𝑟 )=( ) 𝑒 𝑌 00 = 0

2 𝑎 0 𝑎0 √ 3 √4 π
1
¿∫
1 1
3 2 3 2
¿¿¿

d𝝮 Sinθdθd𝜑 = Element of solid angle

±𝑖 𝜑
𝑌 10 =( ) cos θ 𝑌 1 ,± 1=∓ ( ) 𝑆𝑖𝑛 θ 𝑒
4π 8π
2

′
π

δ 𝑙𝑙 𝑙 ′ 𝑚
∞ 𝑙
1 4 π 𝑟 𝑙¿ ∗

′
=∑ ∑ 𝑌 (θ , 𝜑 1)𝑌 𝑙𝑚 (¿θ 2 ,𝜑 2)¿
𝑙+1 𝑙𝑚 1
𝑟 12 𝑙=0 𝑚=− 𝑙 (2𝑙+1) 𝑟 ¿

(θ ,𝜑 ) 𝑌
𝑟 12=ǀ𝒓 𝟏 −𝒓 𝟐 ǀ= √𝑟 21 +𝑟 22 −2𝑟 1 𝑟 2 𝐶𝑜𝑠γ ∞
𝐼 1=∫ 𝑥 𝑒
𝑛 −𝑥 𝑛 𝑛− 1 −𝑎
𝑑𝑥=(𝑎 +𝑛 𝑎 + …+𝑛 !) 𝑒
𝑎

𝑙𝑚
∗
𝐶𝑜𝑠 γ =𝐶𝑜𝑠 θ1 𝐶𝑜𝑠 θ2 + 𝑆𝑖𝑛 θ1 𝑆𝑖𝑛 θ 2 𝐶𝑜𝑠 (𝜑 1 −𝜑 2 ) ∞
𝑎

𝑌
𝑑𝑥= 𝑛! 𝐼 3=∫
𝑛 −𝑥
𝐼 2=∫ 𝑥 𝑒
𝑛 −𝑥 𝑥 𝑒 𝑑𝑥 = 𝐼 2 − 𝐼 1

∫
0
0
 2 𝑍𝑟 𝑎0 𝑢
Put 𝑢= 𝑟 =
𝑎0 Or 2𝑍

∫𝑌 ∗
𝑙𝑚 ( θ ,𝜑 ) 𝑌 δ 𝑙 𝑚 ( θ,𝜑 ) 𝑑 𝝮 =δ 𝑙𝑙 δ𝑚𝑚
𝑙𝑙
′
′ ′ ′ ′

d𝝮 Sinθdθd𝜑 = Element of solid angle

2 ∞ ∞
𝑍𝑒 1
¿
2 𝑎0
∫𝑢 2
1
− 𝑢1
𝑒 𝑑 𝑢1 ∫ 𝑢2 𝑒
2 −𝑢2
𝑑𝑢 2
𝑢¿
∞
𝐼 1=∫ 𝑥 𝑒
𝑛 −𝑥 𝑛 𝑛− 1 −𝑎
0 0 𝑑𝑥=(𝑎 +𝑛 𝑎 + …+𝑛 !) 𝑒
𝑎
∞ 𝑎

𝐼 2=∫ 𝑥 𝑒 𝑑𝑥= 𝑛! 𝐼 3=∫ 𝑥 𝑒

𝑛 −𝑥 𝑛 −𝑥
𝑑𝑥 = 𝐼 2 − 𝐼 1
0 0
 2 ∞ ∞ ∞
𝑍𝑒 1
∫𝑢 𝑑 𝑢1∫ 𝑢 𝑒 𝐼 1=∫ 𝑥 𝑒
(1) 2 −𝑢1 2 −𝑢 2 𝑛 −𝑥 𝑛 𝑛− 1 −𝑎
𝐸 11 = 1 𝑒 2 𝑑𝑢 2 𝑑𝑥=(𝑎 +𝑛 𝑎 + …+𝑛 !) 𝑒
2 𝑎0 0 0 𝑢¿ 𝑎
∞ 𝑎

𝐼 2=∫ 𝑥 𝑒 𝑑𝑥= 𝑛! 𝐼 3=∫ 𝑥 𝑒

𝑛 −𝑥 𝑛 −𝑥
2 ∞ 𝑢1 ∞ 𝑑𝑥 = 𝐼 2 − 𝐼 1
𝑍𝑒 1 1
¿
2 𝑎0 ∫ 𝑢21 𝑒− 𝑢 𝑑 𝑢1 [∫ 𝑢 22 𝑒−𝑢
1 2
𝑑𝑢2 +∫ 𝑢 22 𝑒
𝑢1 𝑢
−𝑢
𝑑𝑢22

𝑢2
] 0 0

0 0 1

2 ∞
𝑍𝑒
¿
2 𝑎0
∫ 𝑢21 𝑒− 𝑢 𝑑 𝑢1 [ 𝑢1
1
{2! − 𝑒
−𝑢1
( 𝑢21 +2 𝑢1 +2 ) }+ 𝑒− 𝑢 (𝑢1 +1)]
1

0 1

2 ∞ ∞
𝑍𝑒
[ ∫ 2 𝑢1 𝑒 𝑑 𝑢1 −∫ 𝑑 𝑢1 𝑒
−𝑢 −2𝑢 2
¿ 1
(𝑢1 +2 𝑢1 )] 1

2 𝑎0 0 0

2 ∞ 2
𝑍𝑒 𝑑𝑣 − 𝑣 𝑣 𝑣
¿ [ 2 −∫ 𝑒 ( + 𝑣)] By putting 𝑢1= 2 in the second integral
2 𝑎0 0 2 4

2
𝑍𝑒 1 1
¿ [ 2 − ( +1)] Finally, we get the ground state energy of the helium atom up to the first order of
2 𝑎0 2 2
approximation as
2 𝟎 (𝟏)
𝑍𝑒 5 5 𝑍 𝑬 𝟏𝟏= 𝑬 𝟏𝟏 +𝑬 𝟏𝟏 =− 𝟕𝟒 . 𝟖 𝒆𝑽 >𝑬𝒙𝒑𝒆𝒓𝒊𝒎𝒆𝒏𝒕𝒂𝒍 𝒗𝒂𝒍𝒖𝒆(− 𝟕𝟖 .𝟗𝟖 𝒆𝑽 )
¿ = ǀ 𝐸 𝐻 ǀ=34 𝑒𝑉
2 𝑎0 4 4
 More realistic ground state energy of the helium atom can be obtained by evaluating higher order corrections or using
variational technique.
Variational method accounts the fact that each electron of He atom moves in an elliptical orbit around the nucleus and thus
partially screens the other electron. As a result, the effective nuclear charge seen by each electron reduces from Ze to Z’e.
The ground state unperturbed wave function and energy would then be:

0 0 2
and 𝐸11 =2 𝐸 1=2 𝑍 ′ 𝐸 𝐻
e-
e-
In terms of the effective atomic number the Hamiltonian of the helium atom can be written as: r2 r1

Ze
He atom

( )
2 2
ℏ 2 𝑍′ 𝑒
= H01 + H02 + H’ where 𝐻 0 𝑖 = − 𝛻𝑖 − and
2𝑚 𝑟𝑖

The first order energy correction is:

( )
′ ′
𝑍 𝑍 5 ′ 5 ′
=¿ 𝑢 ǀ 𝐻 ǀ 𝑢 > ¿ − ( 𝑍 − 𝑍 ) 𝑒 + 𝑍 ǀ 𝐸 𝐻 ǀ=4 𝑍 ( 𝑍 − 𝑍 ) 𝐸 𝐻 − 𝑍 𝐸 𝐻
(1) 0 ′ 0 ′ 2 ′ ′
𝐸 11 11 11 +
𝑎0 𝑎 0 4 4
Ground State Total Energy of helium atom is:
5 ′ 5 ′
𝐸=𝐸11 + 𝐸11 =2 𝑍 ′ 𝐸 𝐻 + 4 𝑍 ( 𝑍 − 𝑍 ) 𝐸 𝐻 −
0 (1) 2 ′ ′ ′ ′2
𝑍 𝐸 𝐻 =𝐸 𝐻 (4 𝑍 𝑍 − 2 𝑍 − 𝑍 )
4 4

Optimization of E with respect to Z’:

′ 5 5 27
gives 𝑍 =Z − =2− =
16 16 16

2
𝜕 𝐸
Also, 2
=− 4 𝐸 𝐻 >0 Thus, E is minimum at Z’ = 27/16.
𝜕𝑍′

The minimum value of E is:

(
𝐸=𝐸 𝐻 4 𝑍 𝑍 ′ − 2 𝑍 ′2 −
5 ′
4 ) (27
𝑍 =−13.6 𝑒𝑉 4 𝑥 2 𝑥 − 2 𝑥
16
27 𝑥 27 5 𝑥 27
−
16 𝑥 16 4 𝑥 16 )
=−77.46 𝑒𝑉 ≈ 𝐸 𝑒𝑥𝑝𝑡 =−78.98 𝑒𝑉
Excited State of He Atom
Electrons are Fermions. Thus, total wave function of two electrons n=2
in the helium atom should be anti-symmetric with respect to S=1 S=0
exchange of electrons. This anti-symmetric wave function can be
formed from the product of the symmetric/anti-symmetric spatial n=1
wave function and the anti-symmetric/symmetric spin state.
Therefore, Figure: Spin Orientations of
𝛹 𝐴𝑆 =𝑢+¿ 0
electrons in He atom when one
𝝌 𝐴𝑆 ∨𝑢0− 𝝌 𝑆 ¿
electron is in the excited state
1
where 0
𝑢± = [𝛹 100 ( 𝒓 𝟏) 𝛹 𝑛𝑙𝑚 ( 𝒓 𝟐 ) ± 𝛹 𝑛𝑙𝑚 ( 𝒓 𝟏 ) 𝛹 100 ( 𝒓 𝟐) ]
√2 Addition of two half spins:
[𝝰(1)𝞫(2) - 𝝰(2)𝞫(1)] is the spin singlet state (S = 0). 𝑺=𝑺 𝟏+ 𝑺 𝟐
is one of the spin triplet states (S = 1): S ms State Comments
𝝰(1)𝝰(2), 𝞫(1)𝞫(2) and ] 1 1 𝝰(1)𝝰(2)
1 0 ]
Finally, the singlet and triplet states are defined as:
1 -1 𝞫(1)𝞫(2)
( 0)
𝛹 (𝑠 ) =𝑢 ¿ ¿ (Para-state) 0 0 [𝝰(1)𝞫(2) - 𝝰(2)𝞫(1)]

(0) (0)
𝛹 (𝑡 ) =𝑢− 𝝌 𝑡𝑟𝑖𝑝𝑙𝑒𝑡 (Ortho-states)
 𝑟 12 = ǀ 𝒓 𝟏 − 𝒓 𝟐 ǀ= √ 𝑟 21 + 𝑟 22 − 2 𝑟 1 𝑟 2 𝐶𝑜𝑠 γ
The electron-electron interaction term () does not operate on the spin states and also commutes with
Lz = . As a result, the spin states and m (azimuthal quantum number) values do not alter the interaction
energy. Therefore, it is enough to calculate E(1) for m = 0 states.

𝐶𝑜𝑠γ=𝐶𝑜𝑠θ1 𝐶𝑜𝑠θ2 +𝑆𝑖𝑛θ1 𝑆𝑖𝑛θ 2 𝐶𝑜𝑠(𝜑1 −𝜑2 )

We have the interaction energy:
2
(1) (0 ) 𝑒 (0 )
𝐸(𝑠 , 𝑡 )=¿ 𝑢± ǀ ǀ 𝑢± >¿ J ± 𝐾
𝑟 12
Where
1
𝐽=𝑒2∫ 𝑑 3 𝑟 1 𝑑 3 𝑟 2 ǀ𝛹 100 (𝒓 𝟏 )ǀ 2 ǀ𝛹 𝑛𝑙𝑚 (𝒓 𝟐)ǀ2 =𝐶𝑜𝑢𝑙𝑜𝑚𝑏𝑖𝑛𝑡𝑒𝑟𝑎𝑐𝑡𝑖𝑜𝑛𝑒𝑛𝑒𝑟𝑔𝑦
𝑟 12
And
1
𝐾 =𝑒 ∫ 𝑑 𝑟 1 𝑑 𝑟 2 𝛹 100 (𝒓 𝟏)𝛹 𝑛𝑙𝑚 (𝒓 𝟐)
2 3 3 ∗ ∗
𝛹 𝑛𝑙𝑚 (𝒓 𝟏)𝛹 100 (𝒓 𝟐 )= 𝐸𝑥𝑐h𝑎𝑛𝑔𝑒𝑖𝑛𝑡𝑒𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑒𝑛𝑒𝑟𝑔𝑦
𝑟 12
 2
Rough (1) (0 ) 𝑒 (0 )
𝐸(𝑠 , 𝑡 )=¿ 𝑢± ǀ ǀ 𝑢± >¿ J ± 𝐾
𝑟 12

[]

r1 and r2 are dummy variables of integration. In this sense, first and last integrals are equal to each other. Similarly,
second and third integrals are also equal to each other.

Finally, we get:
2
𝑒
ǀ 𝑢 ± > ¿∫ 𝑑
( 0) ( 0) 3 3
¿ 𝑢± ǀ 𝑟1 𝑑 𝑟 2 ¿¿
𝑟 12
 1S2S State (
∫ 𝑙𝑚 ( θ ,𝜑 ) 𝑌 δ 𝑙 𝑚 ( θ,𝜑 ) 𝑑 𝝮 =δ 𝑙𝑙 δ𝑚𝑚
𝑌 ∗
𝑙𝑙
′
′ ′ ′ ′

𝛹 𝑛𝑙𝑚 (𝒓 )=𝛹 𝑛𝑙𝑚 ( 𝑟 , θ , 𝜑 )=𝑅 𝑛𝑙 (𝑟 ) 𝑌 𝑙𝑚 ( θ , 𝜑 )

The unperturbed energy: ∞ 𝑙
1 4 π 𝑟 𝑙¿ ∗
0 0 0 0
𝐸12 = 𝐸1 + 𝐸 2=− 54.4 𝑒𝑉 + ( −13.6 𝑒𝑉 )=−68 𝑒𝑉 = 𝐸 11 + 40.8 𝑒𝑉 =∑ ∑ 𝑌 (θ , 𝜑 1)𝑌 𝑙𝑚 (¿θ 2 ,𝜑 2)¿
𝑙+1 𝑙𝑚 1
𝑟 12 𝑙=0 𝑚=− 𝑙 (2𝑙+1) 𝑟 ¿
Results are taken from Quantum
The electron-electron interaction energy:
Chemistry by Ira N. Levine
(1)
𝐸1 𝑆2 𝑆 (±) = 𝐽 1 𝑆2 𝑆 ± 𝐾 1 𝑆 2 𝑆 17 𝑍 𝑒
2
𝐽 1 𝑆2 𝑆 = =11.42 𝑒𝑉
81 𝑎0
1
𝐽 1 𝑆2 𝑆 =𝑒 ∫ 𝑑 𝑟 1 𝑑 𝑟 2 ǀ𝛹 100 (𝒓 𝟏)ǀ ǀ𝛹 200 (𝒓 𝟐)ǀ
2 3 3 2 2
where 59 𝑍 𝑒
2

𝑟 12 𝐽 1 𝑆2 𝑃 = =13.21 𝑒𝑉
243 𝑎0
2
∞ ∞ 𝑙 16 𝑍 𝑒
4π 2 𝑟¿ 𝐾 1 𝑆 2 𝑆= =1.19 𝑒𝑉
∞ 𝑙 ∫
(2𝑙+1) 0
𝑟
2
1 𝑑𝑟 1 ǀ 𝑅 10 1 ∫ 2
(𝑟 )ǀ
2
𝑟
2
𝑑𝑟 2 ǀ 𝑅 (𝑟
20 2 )ǀ 𝑙+1
𝑟¿
729 𝑎0
¿𝑒 ∑ ∑
2 2
0 ¿¿ 𝐾 1𝑆2𝑃=
112 𝑍 𝑒
=0.93 𝑒𝑉
¿ ∫ 𝑑 𝝮1 ǀ𝑌 00 (θ 1 ,𝜑 1 )ǀ ∫ 𝑑 𝝮2 ǀ𝑌 00 (θ 2 ,𝜑 2 )ǀ 𝑌 𝑙𝑚 (θ1 ,𝜑 1)𝑌 𝑙𝑚 (¿ ¿ ¿θ2 ,𝜑 2)
2 2 ∗ 6561 𝑎0
𝑙=0 𝑚=− 𝑙

¿ 𝑍
𝑅10 (𝑟 )=( ) 2 2 𝑒
3 − 𝑍𝑟
𝑎0

Result of the angular integration = 𝑎0

− 𝑍𝑟

Also
∞

∑∑
𝑙
1 𝑟 𝑙¿
δ δ =
1
𝑅 20(𝑟 )=
𝑍 32
2 𝑎0 ( )
(2 −
𝑍𝑟 2 𝑎
𝑎0
)𝑒 0

𝑙0 𝑚0
𝑙= 0 𝑚=−𝑙 (2 𝑙+1) 𝑟 𝑙+1
¿
𝑟 ¿❑ 𝑌 00 =
1 ∗
=𝑌 00
√4 π
 ∞ ∞
1
𝐽 1 𝑆2 𝑆 =𝑒
2
∫ 𝑟 𝑑 𝑟 1 ǀ 𝑅 10 (𝑟 1 )ǀ
2
1
2
∫ 𝑟 2 𝑑 𝑟 2 ǀ 𝑅 20 (𝑟 2 )ǀ
2 2
𝑟¿
0 0

As the angular integrations of both J and K for 1S2S state are the same, the exchange integral will also be reduces to:

∞ ∞
1
𝐾 1 𝑆 2 𝑆 =𝑒 ∫ 𝑟 𝑑 𝑟 1 𝑅10 (𝑟 1 ) 𝑅2 0 (𝑟 1)∫ 𝑟 𝑑 𝑟 2 𝑅 10 ( 𝑟 2) 𝑅 20 (𝑟 2 )
2 2 2
1 2
0 0 𝑟¿

Use the technique already applied in slide # 4 to calculate J and K.

 1S2PZ State (
∫ 𝑙𝑚 ( θ ,𝜑 ) 𝑌 δ 𝑙 𝑚 ( θ,𝜑 ) 𝑑 𝝮 =δ 𝑙𝑙 δ𝑚𝑚
𝑌 ∗
𝑙𝑙
′
′ ′ ′ ′

𝛹 𝑛𝑙𝑚 (𝒓 )=𝛹 𝑛𝑙𝑚 ( 𝑟 , θ , 𝜑 )=𝑅 𝑛𝑙 (𝑟 ) 𝑌 𝑙𝑚 ( θ , 𝜑 )

The unperturbed energy: ∞ 𝑙
1 4 π 𝑟 𝑙¿ ∗
0 0 0 0
𝐸12 = 𝐸1 + 𝐸 2=− 54.4 𝑒𝑉 + ( −13.6 𝑒𝑉 )=−68 𝑒𝑉 = 𝐸 11 + 40.8 𝑒𝑉 =∑ ∑ 𝑌 (θ , 𝜑 1)𝑌 𝑙𝑚 (¿θ 2 ,𝜑 2)¿
𝑙+1 𝑙𝑚 1
𝑟 12 𝑙=0 𝑚=− 𝑙 (2𝑙+1) 𝑟 ¿
Result taken from Quantum
The electron-electron interaction energy:
Chemistry by Ira N. Levine
(1)
𝐸1 𝑆2 𝑃 𝑍 (±) = 𝐽 1 𝑆 2 𝑃 𝑍 ± 𝐾 1 𝑆 2 𝑃 𝑍 17 𝑍 𝑒
2
𝐽 1 𝑆2 𝑆 = =11.42 𝑒𝑉
81 𝑎0
1
𝐽 1𝑆2 𝑃 𝑍 =𝑒 ∫ 𝑑 𝑟 1 𝑑 𝑟 2 ǀ𝛹 100 (𝒓 𝟏)ǀ ǀ𝛹 2 10 (𝒓 𝟐)ǀ
2 3 3 2 2
where 59 𝑍 𝑒
2

𝑟 12 𝐽 1 𝑆2 𝑃 =
243 𝑎0
=13.21 𝑒𝑉
2
∞ ∞ 𝑙 16 𝑍 𝑒
4π 2 𝑟¿ 𝐾 1 𝑆 2 𝑆= =1.19 𝑒𝑉
∞ 𝑙 ∫
(2𝑙+1) 0
𝑟
2
1 𝑑𝑟 1 ǀ 𝑅 10 1 ∫ 2
(𝑟 )ǀ
2
𝑟
2
𝑑𝑟 2 ǀ 𝑅 (𝑟
21 2 )ǀ
𝑟¿
𝑙+ 1
729 𝑎0
¿𝑒 ∑ ∑
2
¿¿
2
0 112 𝑍 𝑒
𝐾 1𝑆2𝑃= =0.93 𝑒𝑉
¿ ∫ 𝑑 𝝮1 ǀ𝑌 00 (θ 1 ,𝜑 1 )ǀ 𝑌 𝑙𝑚 (θ 1 ,𝜑 1 )∫ 𝑑 𝝮2 ǀ𝑌 10 (θ2 ,𝜑 2)ǀ 𝑌 𝑙𝑚 (¿ ¿ ¿θ2 ,𝜑 2)
2 ∗ 2 6561 𝑎0
𝑙=0 𝑚=− 𝑙

¿ 𝑍
𝑅10 (𝑟 )=( ) 2 2 𝑒
3 − 𝑍𝑟
𝑎0

Result of the angular integration of the first integral = 𝑎0

− 𝑍𝑟

∞ 𝑙
4π 𝑟
∑ ∑ ( 2 𝑙+1 ) 𝑟
𝑙
¿ 1
Also
2π
δ δ 𝑚 0∫ 𝑑 𝝮2 ǀ𝑌 10 ( θ 2 , 𝜑 2 ) ǀ 𝑌 𝑙𝑚 ( θ2 , 𝜑 2 ) = ∫
2
π
3
𝐶𝑜𝑠 2 θ 𝑆𝑖𝑛θ 𝑑θ
𝑅 21 (𝑟 )=
𝑍 32 𝑍𝑟
(
2 𝑎0 𝑎0 √ 3 ( )
)𝑒
2𝑎 0

𝑙= 0 𝑚=−𝑙
𝑙+1
¿ √ 4 π 𝑙0 𝑟¿ 0 4π
𝑌 00 =
1 ∗ 3 2
1

=𝑌 00𝑌 10=( 4 π ) cos θ

√4 π
 ∞ ∞
𝐽 1 𝑆2 𝑃 =𝑒
𝑍
2
∫𝑟 2
1 𝑑 𝑟 1 ǀ 𝑅10 (𝑟 1) ǀ
2
∫ 𝑟 22 𝑑 𝑟 2 ǀ 𝑅 21(𝑟 2) ǀ2 𝑟1
0 0 ¿

Also
1
=𝑒 ∫ 𝑑 𝑟 1 𝑑 𝑟 2 𝛹 ( 𝒓 𝟏) 𝛹 ( 𝒓 𝟐) 𝛹 210 ( 𝒓 𝟏 ) 𝛹 100 ( 𝒓 𝟐 )
2 3 3 ∗ ∗
𝐾 1𝑆2𝑃 100 210
𝑍
𝑟 12
∞ 𝑙 ∞ ∞ 𝑙
4π 𝑟¿ ∗
¿𝑒 ∑ ∑ ∫ ∫ ∫ ∫
2 2 2 ∗ ∗
𝑟 1 𝑑𝑟 𝑅 (𝑟
1 10 1 ) 𝑅 (𝑟
21 1 ) 𝑟 2 𝑑𝑟 𝑅 (𝑟
2 10 2 ) 𝑅 (𝑟
21 2 ) 𝑙+ 1
𝑑 𝝮 𝑌 (θ
1 00 1 , 𝜑 1 )𝑌 (θ
10 1 , 𝜑 1 )𝑌 (θ
𝑙𝑚 1
, 𝜑 1 ) 𝑑 𝝮 2 1 0 (θ 2 ,𝜑 2)𝑌 0 0 (θ2 , 𝜑 2 )𝑌 𝑙𝑚 (¿ θ2 , 𝜑 2)¿
𝑌
𝑙=0 𝑚=− 𝑙 (2 𝑙+1) 0 0 𝑟¿

∞ 𝑙 ∞ ∞ 𝑙
4π 𝑟¿ 1
¿𝑒 ∑ ∑ ∫ 21 1 ∫ 2
2 2 2
𝑟 1 𝑑𝑟 𝑅
1 10 (𝑟 1 ) 𝑅 (𝑟 ) 𝑟 𝑑𝑟 𝑅
2 10 (𝑟 2 ) 𝑅21 (𝑟 2 ) 𝑙+ 1
δ 𝑙 1 δ 𝑚0
𝑙=0 𝑚=− 𝑙 (2 𝑙+1) 0 0 𝑟¿ 4π ❑

∞ ∞
1 𝑟
𝐾 1𝑆2𝑃 =𝑒 ∫ 𝑟 21 𝑑 𝑟 1 𝑅10 (𝑟 1 ) 𝑅21 (𝑟 1 )∫ 𝑟 22 𝑑 𝑟 2 𝑅10 (𝑟 2) 𝑅21 (𝑟 2) ¿2
2
𝑍
3 0 0 𝑟¿