Calculation of Matrix Elements in the Two-Center

Harmonic Oscillator Basis

Giacomo Accorto

December 12, 2023

1 Operator ẑ k
In order to constrain the expectation value of multipole moments and other operators one must
calculate their matrix representation in the adopted harmonic oscillator basis. In the case of a
cylindrical two-center basis, a state is an object of the type |n⊥ m⟩ ⊗ |nz d⟩, and the matrix element
of the operator ẑ k reads
Z ∞
k
⟨nzα dα |ẑ |nzβ dβ ⟩ = dz φ∗α (z − dα )z k φ∗β (z − dβ ) (1)
−∞

where φ are eigenfunctions of a one-dimensional harmonic oscillator potential, namely

2
1 z
− 2b 2 z
φnz (z; bz ) = √ 1 1 e z Hnz ( ) (2)
(bz π) 2 (2nz n z !) 2 bz

and Hnz are Hermite polynomials.

The main issue when calculating (1) is that the two wavefunctions are evaluated at different
points in space and the integral is difficult to solve. After a long manipulation involving the har-
monic oscillator generator functions and their properties [1] one is able to rewrite the expression
above as
X µ Z ∞
⟨nzα dα |ẑ k |nzβ dβ ⟩ = Tαβ dz φ∗0 (z − dαβ )z k φµ (z − dαβ ) (3)
µ −∞

d +d
where dαβ = α 2 β , Tαβ are Talman coefficients [1], and the sum runs over |nzα − nzβ | ≤ µ ≤
nzα + nzβ if dα = dβ and 0 ≤ µ ≤ nzα + nzβ otherwise. Inserting the explicit expressions for the
wavefunctions one finds
X µ Z ∞
k
⟨nzα dα |ẑ |nzβ dβ ⟩ = Tαβ dz φ∗0 (z − dαβ )z k φµ (z − dαβ )
µ −∞

∞ (z−dαβ )2
 
z − dαβ
Z
X µ 1 −
= Tαβ
√ 1 dz e b2
z z k Hµ
µ (bz π)(2µ µ!) 2 −∞ bz
Z ∞
X µ 1 2
= Tαβ √ dξ e−ξ (bz ξ + dαβ )k Hµ (ξ) (4)
( π)(2 µ µ!) 21
µ −∞

1
 z−d 2 n 2
d −x
where ξ = bzαβ . Using the Rodrigues’ formula [2] Hn (x) = (−1)n ex dx ne for the Hermite
polynomials and integrating by parts one obtains
Z ∞
X µ (−1)µ dµ 2
k
⟨nzα dα |ẑ |nzβ dβ ⟩ = Tαβ √ 1 dξ (bz ξ + dαβ )k µ e−ξ
µ
µ
( π)(2 µ!) 2 −∞ dξ
Z ∞
X µ bµz k! 2
= Tαβ √ 1 dξ (bz ξ + dαβ )k−µ e−ξ ;
µ
( π)(2 µ!) (k − µ)! −∞
2
µ

(5)
When we integrate by parts we find the condition µ ≤ k. Otherwise, one has an integral of the
+∞
R∞ dµ−k −ξ 2 dµ−k−1 −ξ 2
type −∞ dξ dξ µ−k e = dξ µ−k−1 e = 0. Now one uses the binomial theorem (x + y)n =
Pn −∞
n k n−k


j=0 k x y to obtain the expression
∞ k−µ
bµz k! X 
k − µ j j k−µ−j −ξ2
X Z
µ
⟨nzα dα |ẑ k |nzβ dβ ⟩ = Tαβ √ 1 dξ bz ξ dαβ e
µ ( π)(2µ µ!) 2 (k − µ)! −∞ j=0
j
k
blz dk−l
αβ k!
∞
Z
X µ
X 2
= Tαβ √ 1 dξ ξ l−µ e−ξ . (6)
µ l=µ
( π)(2µ µ!) 2 (l − µ)!(k − l)! −∞

One can read out that µ ≤ l ≤ k and that (l − µ) is even, otherwise the integral vanishes. Since l
takes values between µ and k, it is clear that the three index must all have the same parity, which
is of course defined by k. The integral is known, see Eqs. (3.462.4, 8.950.1) in [2],
Z ∞
2 √
dx xj e−(x−β) = (2i)−n πHn (iβ). (7)
−∞

Inserting Eq. (7) in Eq. (6) one finally gets

X µ
k
X blz dk−l
αβ k!
⟨nzα dα |ẑ k |nzβ dβ ⟩ = Tαβ 1 (2i)µ−l Hl−µ (0) (8)
µ l=µ
(2µ µ!) 2 (l − µ)!(k − l)!

The expression of the Hermite numbers is found in Eqs. (8.956.6, 8.956.7) of [2], and it reads
H2n (0) = (−1)n 2n (2n − 1)!! (9)
H2n+1 (0) = 0. (10)
As mentioned above l − µ = 2j,
 12 (k−µ)/2  2j+µ
2µ (−1)j i−2j 2j (2j − 1)!!

k
X µ
X bz k−µ−2j
⟨nzα dα |ẑ |nzβ dβ ⟩ = k! Tαβ dαβ (11)
µ
µ! j=0
2 (2j)!(k − 2j + µ)!
 12 (k−µ)/2  j+µ
2µ (−1)j (−1)−j

X µ
X bz k−µ−2j
= k! Tαβ dαβ (12)
µ
µ! j=0
2 (2j)!!(k − 2j + µ)!
 12 (k−µ)/2  j+µ
2µ

X µ
X bz k−µ−2j 1
= k! Tαβ dαβ (13)
µ
µ! j=0
2 (2j)!!(k − 2j + µ)!

2
2 Operator Q̂N

(z−zN )2 Z (z−zN )2
− X µ −
⟨nzα dα |e a2
N |nzβ dβ ⟩ = Tαβ dz φ∗0 (z − dαβ )e a2
N φµ (z − dαβ ) (14)
µ
(z−dαβ )2 (z−zN )2
 
z − dαβ
Z
1 X µ − b2
−
a2
= √ T dz e z e N Hµ (15)
bz π µ αβ bz
Z (bz ξ+dαβ −zN )2
1 X µ 1 2 −
=√ Tαβ √ µ dξ e−ξ e a2
N Hµ (ξ) (16)
π µ 2 µ!

z−d
where the substitution ξ = bzαβ has been made. From here on one may proceed in two directions:
either solve the integral analytically, or expand the exponential in a Taylor series and use the results
obtained for ẑ k in the previous section up to a cut-off value of k. We discuss here the first method,
and present two ways to attack the integral.

2.1 Solution I
One would like to complete the square of product of the two Gaussians to obtain an integrand of
2
the type e(x−y) .

(bz ξ + dαβ − zN )2
− ξ2 − (17)
a2N
b2 bz (dαβ − zN ) (dαβ − zN )2
= − ξ 2 − 2z ξ 2 − 2 2 ξ− (18)
a aN a2N
 2 N 2 
b2z (dαβ − zN )2

aN + bz 2 bz (dαβ − zN )
=− ξ + 2 ξ +
a2N a2N a2N (a2N + b2z )
b2z (dαβ − zN )2 (dαβ − zN )2
+ 2 2 − (19)
aN (aN + b2z ) a2N
 2 1 2
aN + b2z 2 bz (dαβ − zN ) (dαβ − zN )2
=− 2 ξ + − . (20)
aN 1
aN (a2N + b2z ) 2 (a2N + b2z )

Making use of the result,

(z−zN )2
a2
⟨nzα dα |e N |nzβ dβ ⟩
  21 2
(dαβ −zN )2
− a2 2
N +bz
bz (dαβ −zN )
(a2 +b2
z)
Z − ξ +
1 X µ e N a2
N aN (a2 +b2
1
=√ T √ µ dξ e N z)
2
Hµ (ξ)
π µ αβ 2 µ!
(dαβ −zN )2
 2
− 1
a2N +b2z
2 bz (dαβ −zN )
(a2 +bz
2)  12 
1 X µ e N − ζ +
a2N
Z 
1
a2N aN (a2 +b2
=√ T √ dζ e N z)
2
Hµ ζ . (21)
π µ αβ 2µ µ! 2
aN + b2z

3
The integral is known, cfr. Eq. (7.374.8) in [2],
√
Z  
(x−y)2 2 n αy
dx e Hn (αx) = π(1 − α ) Hn
2
1 , (22)
(1 − α2 ) 2

and one obtains

−(z−zN )2
a2
⟨nzα dα |e N |nzβ dβ ⟩
 12
(dαβ −zN )2

− a2N +b2z
− 2
1 a2N bz (dαβ −zN )
(a2 +b2
z)  µ2 −
1 X µ e a2N +b2z 1
N
√ a2N
 
a2N aN (a2N +b2z ) 2
=√ T √ π 1− Hµ
π µ αβ 2µ µ! 2
aN + b2z 
a2N
 12
1− a2N +b2z
 2
zN −dαβ
aN X µ − √ a2 +b2

2µ
 21 
b
µ 
z − dαβ

=p 2 Tαβ e N z
p z Hµ pN (23)
aN + b2z µ µ! 2 a2N + b2z a2N + b2z

2.2 Solution II
On might as well solve the integral using Fourier transformation. In that case one has a double
integral of Gaussian functions (see handwritten notes).

3 Operator dˆ

ˆ zβ dβ ⟩
⟨nzα dα |d|n
X µ Z ∞ Z zN 
= Tαβ dz φ∗0 (z − dαβ )zφµ (z − dαβ ) − dz φ∗0 (z − dαβ )zφµ (z − dαβ )
µ zN −∞
X  Z ∞ Z ∞ 
µ
= Tαβ 2 dz (z + dαβ )φ∗0 (z)φµ (z) − dz (z + dαβ )φ∗0 (z)φµ (z)
µ zN −∞
X µ  Z ∞ Z ∞ 
= Tαβ 2 dz (z + dαβ )φ∗0 (z)φµ (z) − dz zφ∗0 (z)φµ (z) − dαβ δµ0
µ zN −∞

∞  12 (1−µ)/2  j+µ 
2µ
 Z 
X µ 2 2 X bz
= Tαβ 1 dξ (bz ξ + dαβ )e−ξ Hµ (ξ) +
µ (π2µ µ!) 2 ξN µ! j=0
2
0
−dαβ Tαβ (24)
z−dαβ
where ξ = bz

4
4 Operator ξˆ

ˆ zβ dβ ⟩
⟨nzα dα |ξ|n
Z ∞
X µ 2 2
0
= −Tαβ + Tαβ 1 dξ e−ξ Hµ (ξ) (25)
µ
(π2 µ!) 2 ξN
µ

z−dαβ
where ξ = bz

References
[1] J.-F. Berger, PhD thesis, Paris XI (1985)

[2] I.S. Gradshteyn, I.M. Ryzhik, Table of Integrals, Series, and Products, Academic Press (1943)