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QM Physics 137B Formulas: by R.L. Griffith@ UCB

This document contains formulas and constants from a physics textbook. It begins by defining important physical constants like pi, the elementary charge, Planck's constant, and others. It then provides formulas for nondegenerate and degenerate perturbation theory. For nondegenerate theory, it shows the first-order correction to energy is the expectation value of the perturbation. For degenerate theory with two states, it sets up a 2x2 matrix involving the perturbation matrix elements to solve for the corrected energies. The document summarizes key equations and concepts from time-independent perturbation theory in quantum mechanics.

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Martín Figueroa
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49 views

QM Physics 137B Formulas: by R.L. Griffith@ UCB

This document contains formulas and constants from a physics textbook. It begins by defining important physical constants like pi, the elementary charge, Planck's constant, and others. It then provides formulas for nondegenerate and degenerate perturbation theory. For nondegenerate theory, it shows the first-order correction to energy is the expectation value of the perturbation. For degenerate theory with two states, it sets up a 2x2 matrix involving the perturbation matrix elements to solve for the corrected energies. The document summarizes key equations and concepts from time-independent perturbation theory in quantum mechanics.

Uploaded by

Martín Figueroa
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
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QM Physics 137B Formulas: by R.L.

Griffith@ UCB

Physical Constants
Name
Number
Number e
Eulers constant

Symbol
Value
Unit

3.14159265358979323846
e
2.71828182845904523536
 n

P
= lim
1/k ln(n) = 0.5772156649
n

k=1

e
G,
= e2 /2hc0
c
0
0

1.60217733 1019
6.67259 1011
1/137
2.99792458 108
8.854187 1012
4 107
8.9876 109

C
m3 kg1 s2

Plancks constant
Diracs constant
Bohr magneton
Bohr radius
Rydbergs constant
Proton Compton wavelength
Reduced mass of the H-atom

h
~ = h/2
B = e~/2me
a0
Ry
Cp = h/mp c
H

6.6260755 1034
1.0545727 1034
9.2741 1024
0.52918
13.595
1.3214 1015
9.1045755 1031

Js
Js
Am2

A
eV
m
kg

Stefan-Boltzmanns constant
Wiens constant
Molar gasconstant
Avogadros constant
Boltzmanns constant

kW
R
NA
k = R/NA

5.67032 108
2.8978 103
8.31441
6.0221367 1023
1.380658 1023

Wm2 K4
mK
Jmol1 K1
mol1
J/K

Electron mass
Proton mass
Neutron mass
Elementary mass unit
Nuclear magneton

me
mp
mn
mu =
N

9.1093897 1031
1.6726231 1027
1.674954 1027
1.6605656 1027
5.0508 1027

kg
kg
kg
kg
J/T

Diameter of the Sun


Mass of the Sun
Rotational period of the Sun
Radius of Earth
Mass of Earth
Rotational period of Earth
Earth orbital period
Astronomical unit
Light year
Parsec
Hubble constant

D
M
T
RA
MA
TA
Tropical year
AU
lj
pc
H

1392 106
1.989 1030
25.38
6.378 106
5.976 1024
23.96
365.24219879
1.4959787066 1011
9.4605 1015
3.0857 1016
(75 25)

m
kg
days
m
kg
hours
days
m
m
m
kms1 Mpc1

Elementary charge
Gravitational constant
Fine-structure constant
Speed of light in vacuum
Permittivity of the vacuum
Permeability of the vacuum
(40 )1

1
12
12 m( 6 C)

m/s (def)
F/m
H/m
Nm2 C2

To the lowest order (0 ) this yields H 0 n0 =


which is nothing new. To the first order
( )

Chapter 6: Time-Independent Pertubation Theory

En0 n0 ,
1

Nondegenerate Pertubation Theory


Suppose we solved the (time-independent)
Schrodinger equation for some potential (say,
the one-dimensional infinite square well):
H 0 n0 = En0 n0

H 0 n1 + H n0 = En0 n1 + En1 n0
To the second order (2 )

(1)

H 0 n2 + H n1 = En0 n2 + En1 n1 + En2 n0 (10)

obtaining a complete set of orthonormal


eigenfunctions, n0 ,
0
i = nm
hn0 |m

and so on.
First-Order Theory
Taking the inner product of equation 7 with
n0 (that is, multiplying by (n0 ) and integrating

(2)
En0 .

and the corresponding eigenvalues


now
we perturb the potential slightly. Wed like to
find new eigenfunctions and eigenvalues:
Hn = En n

hn0 |H 0 n1 i + hn0 |H n1 i

(3)

= En0 hn0 |n1 i + En1 hn0 |n0 i (11)

Pertubation theory is a systematic procedure for obtaining approximate solutions to the


perturbed problem, by building on the known
exact solutions to the unperturbed case.
To begin with we write the new Hamiltonian
as the sum of two terms
H = H 0 + H

But H 0 is hermitian, so

hn0 |H 0 n1 i = hH 0 n0 |n1 i = hEn0 n0 |n1 i


= En0 hn0 |n1 i (12)

(4)

and this cancels the first term on the right.


Moreover, hn0 |n0 i = 1, so

where H is the pertubation. For the moment


well take to be a small number. later well
crank it up to 1, and H will be the true Hamiltonian. next we write n and En as a power
series in
n = n0 + n1 + 2 n2 + ...
En =

En0

En1

En2

+ ...

(9)

En1 = hn0 |H |n0 i

(13)

This is the fundemental result of first-order


pertubation theory; as a practical matter, it may
well be the most important equation in quantum
mechanics. It says that the first-order correction
to the energy is the expectation value of the pertubation, in the unperturbed state.
Equation 9 is the first-order correction to the
energy; to find the first-order correction to the
wave function we first rewrite equation 7

(5)
(6)

Here En1 is the first-order correction to the


nth eigenvalue, and n1 is the first-order correction to the nth eigenfunction; En2 and n2 are the
second-order corrections and so on.Plugging
equations 5 and 6 to equation 3 yields

(H 0 En0 )n1 = (H En1 )n0

(14)

Now, the unperturbed wave functions constitute a complete set, so n1 (like any other function) can be expressed as a linear combination
of them

(H 0 + H )[n0 + n1 + 2 n2 + ...]
= (En0 +En1 +En2 +...)[n0 +n1 +2 n2 +...]
(7)
or (collecting like powers of )

n1 =

(n) 0
cm
m

(15)

m6=n

H 0 n0 +(H 0 n1 +H n0 )+2 ((H 0 n2 +H n1 )+...

putting equation 11 into equation 10, and us= En0 n0 +(En0 n1 +En1 n0 )+2 (En0 n2 +En1 n1 +En2 n0 )+...ing the fact that the 0 satisfies the unperm
(8)
turbed
Schrodinger equation, we have
2

0
0

1
0
(Em
En0 )c(n)
m m = (H En )n (16)

En2 = hn0 |H |n1 i =

m6=n

0
0
c(n)
m hn |H |m i

m6=n

X h 0 |H | 1 ih 0 |H | 0 i
n
n
n
m
=
0
En0 Em

Taking the inner product with l0

(25)

m6=n

0
0 0
0
0
1
0 0
(Em
En0 )c(n)
m hl |m i = hl |H |n i+En hl |n i

or, finally

m6=n

(17)
i fl = n, the left side is zero, and we recover
Equation 9; if l 6= n, we get
(El0

(n)
En0 )cl

hpsi0l |H |n0 i

En2 =

Degenerate Pertubation Theory


Two-Fold Degeneracy
Suppose that

(18)

hpsi0l |H |n0 i
El0 En0

(19)

X hpsi0 |H | 0 i
n
0
l
m
El0 En0

(20)

H 0 a0 = E 0 a0 , H 0 b0 = E 0 b0 , ha0 |b0 i = 0
(27)
with a0 and b0 both normalized. Note that
any linear combination of these states,

so
n1 =

0 = a0 + b0

m6=n

The perturbation theory often yields suprisingly accurate energies but the wave functions
are notoriously poor.
Second-Order Energies
Proceeding as before, we take the inner product of the second order equation with n0 ;

H 0 0 = E 0 0

Hn = En n

Again, we exploit the hermicity of H 0

(22)

= 0 + 1 + 2 2 + ...
2

(31)
(32)

plugging this into the last equation, and collecting like powers of we find

(23)
H 0 0 +(H 0 +H 0 1 )+... = E 0 0 +(E 1 0 +E 0 1 )+...
(33)
0 0
0 0
But H = E , so the first term cancels;
at order 1 we have

But
0
0
c(n)
m hn |m i = 0

E = E + E + E + ...

so the first term on the left cancels the first


term on the right. Meanwhile, hn0 |n0 i = 1, and
we are left with a formula for En2

(30)

with H = H 0 + H and

hn0 |n1 i =

(29)

For the moment, lets write the good unperturbed states in generic form, keeping and
adjustable. we want to solve the Schrodinger
equation

= En0 hn0 |n2 i + En1 hn0 |n1 i + En2 hn0 |n0 i (21)

En2 = hn0 |H n1 i En1 hn0 |n1 i

(28)

is still an eigenstate of H 0 , with the same


eigenvalue E 0

hn0 |H 0 n2 i + hn0 |H n1 i

hn0 |H 0 n2 i = hH 0 n0 |n2 i = En0 hn0 |n2 i

(26)

m6=n

or
c(n)
m =

X h 0 |H | 0 i
m
n
0
En0 Em

(24)

m6=n

H 0 1 + H 0 = E 0 1 + E 1 0

(because the sum excludes m = n, and all


others are orthogonal), so

Taking the inner product with a0


3

(34)

sign (the plus sign corresponds to = 1, = 0).


Whats more, the answers
ha0 |H 0 1 i + ha0 |H 0 i
= E 0 ha0 | 1 i + E 1 ha0 | 0 i

(35)

1
1
E+
= Waa = ha0 |H |a0 i, E
= Wbb = hb0 |H |b0 i
(43)
Theorem: Let A be a hermitian operator
that commutes with H 0 and H . If a0 and b0
(the degenerate eigenfunctions of H 0 ) are also
eigenfunctions of A, with distinct eigenvalues,

Because H 0 is hermitian, the first term on


the left cancels with the first term on the right.
Putting in equation 28 and exploiting the orthonormality condition (Equation 27), we obtain
ha0 |H a0 i + ha0 |H b0 i = E 1

(36)

Aa0 = a0 , Ab0 = vb0 , and 6= v

then Wab = 0 (and hence a0 and b0 are good


states to use in pertubation theory).
Proof: By assumption, [A, H ]=0, so

or, more compactly


Waa + Wab = E 1

(44)

(37)

where

ha0 |[A, H ]b0 i = 0

Wij hi0 |H |j0 i, (i, j = a, b)

= ha0 |AH b0 i ha0 |H Ab0 i

(38)

= hAa0 |H b0 i ha0 |H vb0 i

Similarly, the inner product with b0 yields


Wba + Wbb = E

= ( v)ha0 |H b0 i
= ( v)Wab

(39)

Notice that the W s are (in principle) known


they are just the matrix elements of H , with
respect to the unperturbed wave functions a0
and b0 . Multiplying Equation 39 by Wab , and
using Equation 37 to eliminate Wab , we find

But 6= v, so Wab = 0. QED


Higher-Order degeneracy
In the previous section I assumed the degeneracy was two-fold, but it is easy to see how the
method generalizes. Rewrite Equations 37 and
39 in matrix form

[Wab Wba (E 1 Waa )(E 1 Wbb )] = 0 (40)

 
 


Waa Wab
= E1
Wba Wbb

if is not zero, Equation 40 yields an equation


for E 1

(45)

Evidently the E 1 s are nothing but the eigenvalues of the W -matrix; Equation 41 is the characteristic equation for this matrix, and good
linear combinations of the perturbed states are
the eigenvectors of W.
In the case of n-fold degeneracy, we look for
eigenvalues of the n n matrix

(E 1 )2 E 1 (Waa +Wbb )+(Waa Wbb Wab Wba ) = 0


(41)
Invoking the quadratic formula, and noting

(from Equation 38) that Wab = Wab


, we conclude that

Wij = hi0 |H |j0 i


i
p
1h
Waa + Wbb (Waa Wbb )2 + 4|Wab |2
2
(42)
This is the fundemental result of degenerate
pertubation theory; the two roots correspond to
the two perturbed energies.
But what if is zero? In that case = 1,
Equation 37 says Wab = 0, and Equation 39
gives E 1 = Wbb . This is actually included in
the general result (Equation 42), with the minus

(46)

In the language of linear algebra, finding the


good unperturbed wave functions amounts to
constructing a basis in the degenerate subsapce
that diagonalizes the matrix W.
The Fine structure of Hydrogen
In our study of the hydrogen atom we took
the Hamiltonian to be

1
E
=

H=
4

~2 2
e2 1

2m
40 r

(47)

But this is not quite the whole story. we have


learned how to correct for the motion of the nucleus; Just replace m by the reduced mass. More
significan is the so-called fine structure, which
is actually due to two distinct mechanisms: a
relativistic correction, and spin-orbit coupling. Compare to the Bohr energies, fine structure is a tiny pertubation smaller by a factor of
2 , where

e2
1

4~c
137.036

(48)

is the famous fine structure constant.


Smaller still (by another factor of ) is the
Lamb shift, associated with the quantization
of the electric field, and smaller by yet another
order of magnitude is the hyperfine structure,
which is due to the magnetic interaction between
dipole moments of the electron and proton.

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