Heitler - London model with Gaussian orbitals

I. GAUSSIAN ORBITAL

Defined as
πr2
 
1
φ(r) = √ exp − 2 , (1)
8r̄3 8r̄
where r̄ is a parameter. The bar (¯) is added to distinguish the parameter r̄ from the radius
vector r.
The function φ(r) is normalized so that

Z
dr φ2 (r) = 1. (2)

Scaling in equation (1) is chosen so that

Z
dr r−1 φ2 (r) = r̄−1 . (3)

Integral of the kinetic energy is

∇2
Z  
3π 1.178
dr φ(r) − φ(r) = 2
= . (4)
2 16r̄ 2 r̄2
Other expectation values are
Z Z Z
4 6 π −2
dr rφ2 (r) = r̄, dr r φ (r) = r̄2 ,
2 2
dr r−2 φ2 (r) = r̄ . (5)
π π 2
For comparison, Slater orbital is defined as
1  r
φSlater (r) = √ exp − . (6)
πr̄3 r̄
Slater and Gaussian orbitals for the same value of the parameter r̄ = 1 are plotted on Figure
1.
1
While equations (2) and (3) hold for the Gaussian orbital, the kinetic energy is 2r̄ 2
that
is slightly different from that of Gaussian orbital, equation (4). Other expectation values
are different too,
Z Z Z
3
dr rφ2Slater (r) = r̄, dr r2 φ2Slater (r) 2
= 3r̄ , dr r−2 φ2Slater (r) = 2r̄−2 . (7)
2
Expectation values of the operator rn for Slater and Gaussian orbitals are plotted on Figure
2.
orbgauss.nb 1 2

0.5

0.4

0.3
j

0.2

0.1

0
1 2 3 4 5
r

FIG. 1. A Slater orbital (solid line) and a Gaussian orbital (dashed line) for the same
orbgauss.nb value of r̄ = 1. 1

1000

500

100

50
<rn >

10

1
-2 0 2 4 6 8 10
n

FIG. 2. Expectation values hrn i for a Slater orbital (red dots) and a Gaussian orbital
(blue dots) for the same value of r̄ = 1. For comparison, hrn i = r̄n for the Bohr model
delta-function orbital (horizontal line).
 3

II. HEITLER - LONDON MODEL

A trial variational function is

1
Ψ(r 1 , r 2 ) = p [φa (r 1 )φb (r 2 ) + φa (r 2 )φb (r 1 )] , (8)
2(1 + S 2 )
where
φa (r) = φ(r − Ra ), φb (r) = φ(r − Rb ), |Ra − Rb | = R, (9)

and the overlap integral is

π R2 R2 R4
Z  
S = dr φa (r)φb (r) = exp − = 1 − 0.196 + 0.019 + .... (10)
16 r̄2 r̄2 r̄4
The probability density
Z
1
P (r 1 ) = dr 2 Ψ2 (r 1 , r 2 ) =
 2 2

φ (r 1 ) + 2Sφa (r 1 )φb (r 1 ) + φ (r 1 ) (11)
2(1 + S 2 ) a b

is plotted on Figures 3, 4.
s.nb 1 s.nb 1

10 4

PHr1 L 7.5 PHr1 L 3

5 1 2 1
2.5 1
0 0
-1 0 -1 0
y y
0 0

-1 -1
x 1 x 1

2 2

FIG. 3. Probability density plot for R = 1 and r̄ = 0.3. Slater wave function is to the
left, and Gaussian function to the right.

In comparison,
R 1 R2 R2 R4
  
R
SSlater = exp − 1+ + = 1 − 0.167 + 0.042 + .... (12)
r̄ r̄ 3 r̄2 r̄2 r̄4
The overlap integral as a function of R is plotted on Figure 5.

III. COULOMB INTEGRALS

√
R2 R4
    
1 1 π R 1
f= φa   φa = Erf = − 0.262 3 + 0.062 5 + . . . , (13)
rb R 2 r̄ r̄ r̄ r̄
 4
s.nb 1s.nb 1

2 1

PHr1 L PHr1 L
0.75
1 1 0.5 1
0.25
0 0
-1 0 -1 0
y y
0 0

-1 -1
x 1 x 1

2 2

FIG. 4. Probability density plot for R = 1 and r̄ = 0.5. Slater wave function is to the
s.nb 1
left, and Gaussian function to the right.

0.8

0.6
S

0.4

0.2

0
1 2 3 4 5
R

FIG. 5. Overlap integral as a function of separation distance R for a Slater orbital (solid
line) and a Gaussian orbital (dashed line) for the same value of r̄ = 1.

√
R2 R4
    
1 2S π R 1
g = φa   φb = Erf = − 0.262 3 + 0.036 5 + . . . . (14)
rb R 4 r̄ r̄ r̄ r̄
In comparison,
R2 R3
  
1 2R 1 1 1
fSlater = − exp − + = − 0.667 3 + 0.667 4 + . . . , (15)
R r̄ R r̄ r̄ r̄ r̄
R2 R3
  
1 R R 1
gSlater = exp − 1+ = − 0.5 3 + 0.333 4 + . . . . (16)
r r̄ r̄ r̄ r̄ r̄
The function f for Slater and Gaussian orbitals is plotted on Figure 6. The function g for
Slater and Gaussian orbitals is plotted on Figure 7.
 fg.nb 1 5

0.8

0.6
f

0.4

0.2
1 2 3 4 5
R

FIG. 6. The function f for a Slater orbital (solid line) and a Gaussian orbital (dashed
fg.nb 1
line) for the same value of r̄ = 1.

0.8

0.6
g

0.4

0.2

0
1 2 3 4 5
R

FIG. 7. The function g for a Slater orbital (solid line) and a Gaussian orbital (dashed
line) for the same value of r̄ = 1.
 6

IV. BOHR MODEL WITH A CONSTRAINT

A constraint is defined through a function Φ(r̄, R) according to equation (8) from the
paper in Phys. Lett. A (2006):
f + Sg
Φ(r̄, R) = (17)
1 + S2
for Heitler - London model or as
f +g
Φ(r̄, R) = (18)
1+S
for Hund - Mulliken model.
The energy is calculated according to a recipe of the paper in Phys. Lett. A (2006) as

E(R) = min (x, y, R) (19)

x,y>0

under a constraint
1
− = Φ(ra , R), (20)
rb
where

1 2 2 1 1
(x, y, R) = 2
− − + + , (21)
ra ra rb r12 R

1/2
ra = x 2 + y 2 , (22)
1/2
rb = (x − R)2 + y 2

, (23)
1/2
r12 = (2x − R)2 + 4y 2

. (24)

Result of calculation of energy are shown on Figures 8, 9 for HL and HM models respec-
tively.

V. HYBRID HL - BOHR MODEL

The energy is determined as

EHL−B (R) = min HL−B (x, y, R) (25)

x,y>0

under a constraint
(1) (1)
EB = EHL , (26)
h2s.nb 1 7

-0.4

-0.6

-0.8
E

-1

-1.2

1 2 3 4 5
R

FIG.
h2s.nb
8. Energy calculated within Heitler - London model. Solid line is based on Slater 1
orbitals, and dashed line is based on Gaussian orbitals. Dotted line is exact energy.

-0.4

-0.6

-0.8
E

-1

-1.2

1 2 3 4 5
R

FIG. 9. Energy calculated within Hund - Mulliken model. Solid line is based on Slater
orbitals, and dashed line is based on Gaussian orbitals. Dotted line is exact energy.
 8

where

(1) 1 1
HL−B (x, y, R) = EHL + + , (27)
r12 R
(1) 1 2 2
EB = 2− − , (28)
ra ra rb
(1)
EHL = T + V1 , (29)
 
2 1
V1 = − + f + 2Sg , (30)
1 + S 2 r̄
3π π 2 R2
TGauss = − , (31)
8r̄2 64r̄4 (1 + S 2 )


9r̄4 1 + e2R/r̄ + 18r̄3 R + 9r̄2 R2 − R4
TSlater = , (32)
9r̄6 e2R/r̄ + r̄2 (3r̄2 + 3r̄R + R2 )2

1/2
ra = r̄ = x2 + y 2 , (33)
1/2
rb = (x − R)2 + y 2
 
, (34)
1/2
r12 = (2x − R)2 + 4y 2
 
. (35)
h2var.nb 1
Result of calculation of energy are shown on Figure 10. At infinite separation, Gaussian

-0.4

-0.6

-0.8
E

-1

-1.2

1 2 3 4 5
R

FIG. 10. Energy calculated using hybrid Heitler - London - Bohr model. Solid line is
based on Slater orbitals, and dashed line is based on Gaussian orbitals. Dotted line is
exact energy.

energy is higher than −1 because the gaussian variational energy is higher then −1/2 for a
hydrogen atom.