Comp QM ch1
Comp QM ch1
~2 2
− ∇ ψ (r) + V (r) ψ (r) = Eψ (r) (1.1)
2me
in atomi ~ = me = e = 4πε0 = 1 [so from now on we shall
units, that is
always work in energy units of Hartrees (27.2eV ) and in length units of Bohr
radii (a0 = 0.529 Å)℄ and so :
1
− ∇2 ψ + V ψ = Eψ (1.2)
2
or in terms of the Hamiltonian operator b,
H
b = Eψ
Hψ (1.3)
7
8 CHAPTER 1. TIME INDEPENDENT SCHRÖDINGER EQUATION
The rst term in equation 1.1 orresponds to the kineti energy of the
state, and so we see that a smoothly varying wavefun tion (small ∇2 ψ ) will
generally be a lower energy state than a rapidly varying one. This an also
be related to the number of nodes (zero rossings) in the wavefun tion - a
smooth wavefun tion will have less nodes than a rapidly varying one.
V (x) = 0 −a ≤ x ≤ a
(1.4)
→ ∞ otherwise
whi h then gives the general solution of equation 4.1 as
√
k= 2E (1.6)
k = nπ/2a (1.7)
where n is an integer. For odd n we get cos (ka) = 0 and hen e A = 0 whilst
for even n we get sin (ka) = 0 and hen e B = 0. As the well is innitely deep,
then all solutions are bound states. As usual, bound states have quantized
energies, given in this ase by
π 2 n2
En = (1.8)
8a2
Note that as the potential has a denite parity then so do the eigenfun tions.
Note also that the ground state wavefun tion has no nodes, whilst the rst
ex ited state has one node, and su essive ex ited states have more nodes.
See gure 1.1 for a simple sket h of the three lowest energy solutions.
We an also solve analyti ally problems su h as the nite square well, or
the harmoni os illator, or the spheri al well, et . Remember that these an
be used to demonstrate the existen e of zero-point motion, tunnelling into
lassi ally forbidden regions and the Heisenberg Un ertainty Prin iple.
V
E3 ψ3
E2 ψ2
E1 ψ1
−a a x
Figure 1.1: Sket h of innite square well, showing lowest three eigenvalues
and orresponding eigenfun tions.
10 CHAPTER 1. TIME INDEPENDENT SCHRÖDINGER EQUATION
where {n, l, m} are quantum numbers (integers) whi h hara terise the solu-
tion. If we substitute equation 1.9 into equation 4.1 and apply the method of
separation of variables, we get two equations - a 2D angular equation, whose
solution is given in terms of spheri al harmoni s and a 1D radial equation:
1 d2 χnl (r) l (l + 1)
− + V (r) + χnl (r) = Eχnl (r) (1.10)
2 dr 2 2r 2
where the substitution
χnl (r) = rRnl (r) (1.11)
is used both to simplify the equation and ease its interpretation. Remember
that the probability of nding the parti le in a small volume d3 r is
P r → r + d3 r = |ψ (r)|2 d3 r
2 2
= |ψ (r)| r dr · sin (θ) dθdφ (1.12)
= |χ (r)|2 dr · Ylm
2 (θ, φ) sin (θ) dθdφ
and so we see that the normalisation of χnl and Ylm an be hosen su h that
Z ∞
|χ (r)|2 dr = 1 (1.13)
0
d2 χ l (l + 1)
2
= χ (1.15)
dr r2
whi h gives a non-divergent solution as
χ (r → 0) ∼ r l+1 (1.16)
l
⇒ Rl (r → 0) ∼ r
1.1. REVISION OF THE SCHRÖDINGER EQUATION 11
R21
0.1
5 10
r/a0
R20
0.4 5
10
r/a0
R10
1.0
5 10
r/a0
Figure 1.2: Sket h of rst three radial eigenfun tions for the hydrogen atom.
d2 χ
= −2Eχ (r) (1.17)
dr 2
whi h gives two lasses of solution:
√
χ (r) ∼ e− √2|E|r E < 0 (bound states)
(1.18)
χ (r) ∼ e±i 2Er E > 0 (continuum)
dy
= f (y (x) , x) (1.19)
dx
Se ond-order equations of the general form
d2 y
= f (y (x) , x) (1.20)
dx2
an be transformed into a pair of oupled rst-order equations using
dy
= z (x)
dx
dz
= f (y (x) , x) (1.21)
dx
and then solved using the same te hniques.
Most methods then pro eed to use an approximation to the derivative,
su h as the forward dieren e :
dy y (x + δx) − y (x)
≈ (1.22)
dx δx
the ba kwards dieren e :
dy y (x) − y (x − δx)
≈ (1.23)
dx δx
or the entred dieren e :
dy y (x + δx) − y (x − δx)
≈ (1.24)
dx 2δx
A straightforwards implementation of this approa h results in the Euler
method :
y(x)
x1 x2 x3 x4 x
Figure 1.3: Illustration of Euler's method - the derivative at ea h point xn
is extrapolated over the whole step length h to form the next point.
k1 = f (xn , yn ) h
h k1
k2 = f xn + , yn + h (1.26)
2 2
yn+1 = yn + k2 + O h3
y(x)
x1 x2 x3 x4 x
Figure 1.4: Se ond-order Runga-Kutta method - the derivative at the start
of the step is used to nd a point half-way a ross the interval h and this
midpoint value is then used to improve the al ulation of the nal point at
the end of the step. The lled ir les represent nal values whi h are of
interest, whilst open ir les are intermediate values ki whi h are dis arded
at the end of ea h step.
k1 = f (xn , yn ) h
h k1
k2 = f xn + , yn + h
2 2
h k2
k3 = f xn + , yn + h (1.27)
2 2
k4 = f (xn + h, yn + k3 ) h
k1 k2 k3 k4
yn+1 = yn + + + + + O h5
6 3 3 6
A signi ant advantage of the Runge-Kutta method is that it an be
used with a variable step size: at ea h step, an estimate of the error in
the solution an be made, and the step size redu ed if the error is larger
than some pres ribed toleran e, or the step size may be in reased if a larger
error an be a epted. In this way, more attention is paid to those regions
where the solution is rapidly varying, whilst not paying an unne essarily high
pri e of using an unne essarily small step size where the fun tion is slowly
hanging. This variable step size is a hieved by evaluating yn+1 twi e, on e
1.2. REVISION OF SOLVING ORDINARY DIFFERENTIAL EQUATIONS NUMERICALLY15
h
using a step size of h and then again using a step size of
2 . If the dieren e
in yn+1 for the two dierent step sizes is ∆, then it an be shown that for the
′
fourth order method, the required step size h to keep the pres ribed error
to within δ is given by
1
′ 15 δ 5
h = h (1.28)
16 ∆
′
as the error term is O h5 . That is, if h < h we must repeat the urrent
′ ′
step with the smaller step size, whilst if h ≥ h we may use h as the new
step size for the next step. There is, of ourse, some freedom in how to
hoose δ depending on the type of problem being solved - this may either be
an absolute error, a fra tional error, or an a umulated fra tional error sin e
the start of the al ulation.
The fourth-order Runge-Kutta method, with variable step size, is perhaps
the most widely used and trusted general purpose method for integrating
ordinary dierential equations. It has the advantage of being a self-starting
method, that is, does not require knowledge of previous values to omplete
ea h step. However, it does not exploit any parti ular properties of the
S hrödinger equation, and so in this instan e there may be more spe ialised
integration methods that an outperform it. We shall now onsider one su h
method.
The Numerov method is a spe ialised method for solving a restri ted set of
dierential equations - those that an be written in the form:
d2 y
= f (x) y (x) (1.29)
dx2
whi h in ludes the time independent S hrödinger equation. The method
exploits the spe ial stru ture of this equation to produ e a method that has
fth-order a ura y but only requires two fun tion evaluations per step!
d2 y
We an derive the method by expanding both y (x ± h) and
dx2 x±h
in
z (x + h) = 2z (x) − z (x − h) + h2 f (x) y (x) + O h6 (1.30)
where
h2
z (x) = 1 − f (x) y (x) (1.31)
12
16 CHAPTER 1. TIME INDEPENDENT SCHRÖDINGER EQUATION
The advantage of this method is that it has an error O h6 whi h is
an order of magnitude better than 4th-order Runge-Kutta and only requires
two (rather than four) fun tion evaluations per step. Hen e it is the pre-
ferred method for solving the S hrödinger equation. However, it does have a
drawba k in that it is not self-starting due to the z (x − h) term - that is, it
requires another method to generate the rst step, whereupon the Numerov
method an be used. This feature of the method will also give problems if
there are any dis ontinuities in the potential whereas the single-step Runga-
Kutta method will be OK.
1.2.3 Singularities
∞
X
χ (r) = as r s+l+1 (1.32)
s=0
from whi h it an be shown that
2 d (rVef f )
as = rVef f as−1 + − E as−2 (1.33)
s (s + 2l + 1) dr
1.2.5 Errors
In general, when solving any dierential equation numeri ally, there will be
two dominant sour es of error:
this is aused by the trun ation of the Taylor series and represents
the fundamental limit to the a ura y of a given algorithm. In
general the error in a solution aused by trun ation error an be
redu ed by using a smaller step size h.
• rounding error
• Rounding error will dominate if the step size is made too small.