Advanced Quantum Chemistry spring 2012, 5th exercise
Abstract
In this exercise we study the computationally most important aspect of quantum chemistry: com-
puting integrals.
To be discussed in the exercise session on Fri Apr 20 2012 in Physicum linux class room (D211).
To be done before the exercise session (for bonus points)
1. In this problem, we study the radial form of Gaussian type orbitals, which are the most frequently
used basis functions in electronic structure theory:
√ l
GTO GTO
2αr exp −αr2 .
Rαl =Nαl
(a) Using the integral
Z ∞ r
2n 2
(2n − 1)!! π
x exp −αx dx = , n ≥ 0, α > 0,
0 2n+1 α2n+1
verify that the normalization constant is given by
s
3/4
GTO 2 (2α) 2l
Nαl = 1/4
,
π (2l + 1)!!
where n!! is the double factorial, e.g. 5!! = 5 · 3 · 1 = 15, 6!! = 6 · 4 · 2 = 48.
(b) Determine the radial overlap between two GTOs sharing the same center:
Z ∞
GTO GTO
Sα1 α2 l = r 2 Rα1l
(r) Rα2l
(r) dr (1)
0
[The value of l is the same for both functions as the angular parts would make the functions
orthogonal. This integral is essential in completeness-optimization of basis sets.]
(c) Setting α2 = βα1 verify that the overlap of equation (1) is independent of α1 , i.e., that it is
invariant with respect to translation of the (logarithm of the) exponents.
(d) Using the integral
Z ∞
n!
x2n+1 exp −αx2 dx =
0 2αn+1
show that the expectation value of r̂ is
Z ∞
GTO GTO GTO
hri = r3 Rαl (r) Rαl (r) dr
0
r
2 2l (l + 1)!
=
πα (2l + 1)!!
GTO 2
(e) Verify that the radial distribution function 4πr2 Rαl (r) has a maximum at
r
GTO l+1
rmax = .
2α
To be solved during the exercise session
2. The self-overlap integral of a Cartesian Gaussian
j k
Gijk =xiA yA 2
zA exp −arA
is given by
(2i − 1)!! (2j − 1)!! (2k − 1)!! π 3/2
hGijk |Gijk i = i+j+k
. (2)
(4a) 2a
(a) Using the Obara-Saika scheme, verify that the expression in equation (2) holds for the
special cases hpx |px i and hdx2 |dx2 i.
(b) Show that the one-center even-order multipole s integrals are given by
(
n 0, n = 1, 3, . . .
hs |xA | si = −n/2 3/2 .
(n − 1)!! (4a) (π/2a) , n = 0, 2, . . .
(c) For n = 2 verify the expression
π 3/2
n
hs |(−i∂/∂x) | si = (n − 1)!!an/2 , n = 0, 2, . . .
2a
2
To be solved and returned by the end of the course
3. Consider the ground state hydrogen and helium atoms in a basis of a single Gaussian with expo-
nent a:
G1s = exp −ar2 .
In a previous exercise we calculated the overlap and kinetic energy integrals as
π 3/2
S1s1s (a) =
2a
3a π 3/2
T1s1s (a) =
2 2a
(a) Show that the Coulomb integral is given by
π
C1s1s (Z, a) = − ZV1s1s (a) = −Z ,
a
1 π 5/2
g1s1s1s1s (a) = ,
4 a
where Z is the nuclear charge.
(b) Show that the energy expression for the hydrogen and helium atoms in this basis are given
by
r
3 2a
EH (a) = a − 2
2 π
√ a
r
EHe (a) =3a + 2 − 8 2 .
π
(c) Optimize the energies by means of the variation principle and show that we obtain for the
hydrogen atom
8
a∗H = ≈ 0.2829,
9π
4
EH (a∗H ) = − ≈ −0.4244,
3π
and for the helium atom
√
33 − 8 2
a∗He = ≈ 0.7670,
9π
√
8 2 − 33
EHe (a∗He ) = − ≈ −2.3010.
3π
How do the results compare with the exact ground-state energies (here: full configuration
interaction at the complete basis set limit) of the hydrogen and helium atoms? [Helium is
a three-body problem, so for the exact energy the zero-point motion of the nucleus would
need to be taken into account.]
(d) The virial theorem states that the kinetic and total energies are related by
Ekin = − Etot
at the equilibrium geometry (which is always satisfied by a gas-phase atom). Determine
the Gaussian exponent for the hydrogen atom from the virial theorem. How does the result
obtained in this way compare with that obtained from the variation principle? If a difference
occurs, speculate as to the reason why.