Lecture 5 Variational Principle

The variational principle

Quantum mechanics 2 - Lecture 5
Igor Lukacevic
UJJS, Dept. of Physics, Osijek
November 8, 2012
Igor Luka
cevi
c

Contents
Theory
The ground state of helium
The linear variational problem
Literature
Igor Luka
cevi
c

Theory
Contents
Theory
Literature
Igor Luka
cevi
c

Theory
What is a problem we would like to solve?

To find approximate solutions of eigenvalue problem
O(x) = (x)
Igor Luka
cevi
c

Theory

To find approximate solutions of eigenvalue problem
O(x) = (x)
A question
Can you remember any eigenvalue problems?
Igor Luka
cevi
c

Theory

To find approximate solutions of O(x) = (x).
A question
Can you remember any eigenvalue problems?
H = E , = 0, 1, . . .
where
E0 E1 E2 E , h | i =
Igor Luka
cevi
c

Theory
Theorem - the variational principle

Given any normalized function e (that satisfies the appropriate boundary
conditions), then the expectation value of the Hamiltonian represents an upper
bound to the exact ground state energy
e i
e E0 .
h|H|
Igor Luka
cevi
c

Theory

e i
e E0 .
h|H|
A question
What if e is a ground state w.f.?
Igor Luka
cevi
c

Theory

e i
e E0 .
h|H|
A question
What if e is a ground state w.f.?
e i
e = E0
h|H|
Igor Luka
cevi
c

Theory
Proof
e i
e =1
e are normalized h|
Igor Luka
cevi
c

Theory
Proof
e i
e =1
e are normalized h|
e = P c | i
On the other hand, (unknown) form a complete set |i
Igor Luka
cevi
c

Theory
Proof
e i
e =1
e are normalized h|
e = P c | i
So,
e i
e =
h|
DX
X
E X
X

c
|c |2 = 1
c =
c c h | i =
{z
}
|
Igor Luka
cevi
c

Theory
Proof
e i
e =1
e are normalized h|
e = P c | i
So,
e i
e =
h|
DX
X
E X
X

c =
c c h | i =
c
|c |2 = 1
|
{z
}
Now
e i
e =
h|H|
DX
X
E X
X

c H
c =
c c E h | i =
E |c |2
|
{z
}
|
{z
}
P
c H| i
| {z }
E | i
Igor Luka
cevi
c

Theory
Proof
e i
e =1
e are normalized h|
e = P c | i
So,
e i
e =
h|
DX
X
E X
X

c =
c c h | i =
c
|c |2 = 1
| {z }
Now
e i
e =
h|H|
DX
X
E X
X

c H
c =
c c E h | i =
E |c |2
{z
}
|
|
{z
}
P
c
H|
i

| {z }
E | i
But E E0 , , hence
e i
e
h|H|
E0 |c |2 = E0
Igor Luka
cevi
c
|c |2 = E0

Theory
Example: One-dimensional harmonic oscilator
a] Find the ground state energy and w.f. of one-dimensional harmonic oscilator:
H=
~2
1
+ m 2 x 2 .
2m
2
Igor Luka
cevi
c

Theory
H=
~2
1
+ m 2 x 2 .
2m
2
How to do this using the variational principle...

(i) pick a trial function which somehow resembles the exact ground state w.f.:
(x) = Ae x
r
4 2
A=
parameter
from normalization condition (do it for HW)
Igor Luka
cevi
c

Theory
H=
1
~2
+ m 2 x 2 .
2m
2

(x) = Ae x
r
4 2
A=
parameter
from normalization condition
(ii) calculate hHi = hT i + hV i
Igor Luka
cevi
c

Theory

(x) = Ae x
r
4 2
A=
parameter

~2
2m
m 2
hV i =
8
hT i =
On how to solve these kind of

integrals, see Ref. [5].
Igor Luka
cevi
c

Theory

(x) = Ae x
r
4 2
A=
parameter

~2
2m
m 2
hV i =
8
~2
m 2
hHi =
+
2m
8
hT i =
On how to solve these kind of

integrals, see Ref. [5].
Igor Luka
cevi
c

Theory
(iii) minimize hHi wrt parameter

d
m
hHi = 0 = =
d
2~
Igor Luka
cevi
c

Theory

d
m
hHi = 0 = =
d
2~
(iv) insert back into hHi and (x):
1
~
2
r
2
m m
min (x) = 4
e 2~ x
~
hHimin =
Igor Luka
cevi
c

Theory

d
m
hHi = 0 = =
d
2~
(iv) insert back into hHi and (x):
~
2
r
exact ground state energy and w.f.
2
m
m
e 2~ x
min (x) = 4
~
hHimin =
A question
Why did we get the exact energy and w.f.?
Igor Luka
cevi
c

Theory
b] Do the same, but with trial function (x) = Bxe x
Igor Luka
cevi
c

Theory

s
2 m 3/4
(i) normalization gives B =
~
Igor Luka
cevi
c

Theory

s
2 m 3/4
~
(ii) calculate hHi =
3m 2 1
3~3
+
2m
8
Igor Luka
cevi
c

Theory

s
2 m 3/4
~
3m 2 1
3~3
+
2m
8
m
(iii) minimize hHi = =
2~
Igor Luka
cevi
c

Theory

s
2 m 3/4
~
3~3
3m 2 1
+
2m
8
m
2~
(iv) get minimal values
3
~
2
s
2
2 m 3/4 m
min (x) =
xe 2~ x
~
hHimin =
Igor Luka
cevi
c

Theory

s
2 m 3/4
~
3~3
3m 2 1
+
2m
8
m
2~
(iv) get minimal values
3
~
2
s
2
2 m 3/4 m
min (x) =
xe 2~ x
~
hHimin =
Igor Luka
cevi
c
exact 1st excited state

energy and w.f.

Theory
In conclusion...
b]
trial (x) = Bxe x

2
a]
gs
trial (x) = exact
(x) = Ae x
Igor Luka
cevi
c
D
E
b]
gs
= trial (x)|exact
(x) = 0

Theory
In conclusion...
b]
trial (x) = Bxe x

2
a]
gs
trial (x) = exact
(x) = Ae x
D
E
b]
gs
= trial (x)|exact
(x) = 0
b]
Also, hHimin accounts for 1st excited state
Igor Luka
cevi
c

Theory
In conclusion...
b]
trial (x) = Bxe x

2
a]
gs
trial (x) = exact
(x) = Ae x
D
E
b]
gs
= trial (x)|exact
(x) = 0
b]
Also, hHimin accounts for 1st excited state

Corollary
If h|gs i = 0, then hHi Efes , where Efes is the energy of the 1st excited
state.
Igor Luka
cevi
c

Contents
Theory
Literature
Igor Luka
cevi
c

~2
(1 + 2 )
2m

e2
2
1
2
+
40 r1
r2
|~r1 ~r2 |
H =
A question
What does each of these terms mean?
Igor Luka
cevi
c

~2
(1 + 2 )
2m

2
e
2
1
2
+
40 r1
r2
|~r1 ~r2 |
H =
A question
What does each of these terms mean?
Igor Luka
cevi
c

~2
(1 + 2 )
2m

2
e
2
1
2
+
40 r1
r2
|~r1 ~r2 |
H =
kinetic energy of electrons 1 and 2
Igor Luka
cevi
c

~2
(1 + 2 )
2m

e2
2
1
2
40 r1
r2
|~r1 ~r2 |
H =
electrostatic attraction between the nucleus

and electrons 1 and 2
Igor Luka
cevi
c

~2
(1 + 2 )
2m

e2
2
2
1
+
40 r1
r2 |r1 r2 |
H =
electrostatic repulsion between the electrons

1 and 2
Igor Luka
cevi
c

~2
(1 + 2 )
2m

e2
2
1
2
+
40 r1
r2
|~r1 ~r2 |
H =
Our mission
to calculate the ground state energy Egs
exp
Egs
= 78.975 eV
Igor Luka
cevi
c

~2
(1 + 2 )
2m

2
e
2
1
2
+
40 r1
r2
|~r1 ~r2 |
H =
A question
Can you identify the troublesome term in H?
Igor Luka
cevi
c

~2
(1 + 2 )
2m

2
e
2
1
2
+
40 r1
r2
|~r1 ~r2 |
H =
A question
Can you identify the troublesome term in H?
Vee =
e2
1
40 |~r1 ~r2 |
Igor Luka
cevi
c

For start, let us ignore Vee

A question
Can you guess what happens then with H, how looks like and whats the
energy?
Igor Luka
cevi
c

For start, let us ignore Vee

A question
Can you guess what happens then with H, how looks like and whats the
energy?
H = H1 + H2
0 (~r1 ,~r2 ) = 100 (~r1 )100 (~r2 ) =
2
23 2 r1 +r
a
e
a3
E0 = 8E1 = 109 eV
Igor Luka
cevi
c

Now, let us account for Vee :

0 99K trial w.f. (is this justifiable?)
hHi = 8E1 + hVee i

hVee i =
e2
40

Igor Luka
cevi
c
23
a3
2 Z
r1 +r2
e 4 a
d~r1 d~r2
|~r1 ~r2 |


hHi = 8E1 + hVee i

hVee i =
e2
40

23
a3
2 Z
r1 +r2
e 4 a
d~r1 d~r2
|~r1 ~r2 |
A question
What do you expect for hVee i and why?
Igor Luka
cevi
c


HW
hHi = 8E1 + hVee i
Calculate
hVee i using
Refs. [2] and
[5].

hVee i =
e2
40

23
a3
2 Z
r +r
4 1 a 2
e
d~r1 d~r2 = 34 eV
|~r1 ~r2 |
Igor Luka
cevi
c


hHi = 8E1 + hVee i

hVee i =
e2
40

23
a3
2 Z
r1 +r2
e 4 a
d~r1 d~r2 = 34 eV
|~r1 ~r2 |
hHi = 109 eV + 34 eV = 75 eV
exp
Egs
= 79 eV
Rel. error 5.1%
Igor Luka
cevi
c

Zeff
effective nuclear
charge
Trial w.f.
1 (~r1 ,~r2 ) =
Igor Luka
cevi
c
3
Zeff
e Zeff
3
a
r1 +r2
a

Zeff
effective nuclear
charge
Trial w.f.
1 (~r1 ,~r2 ) =
2
Z3eff Zeff r1 +r
a
e
a3
Zeff - variational
parameter
Igor Luka
cevi
c

Let us rewrite the Hamiltonian:

~2
e2
Zeff
e2
Zeff 2
1
Zeff
Zeff 2
H=
(1 + 2 )
+
+
+
2m
40
r1
r2
40
r1
r2
|~r1 ~r2 |
Igor Luka
cevi
c


~2
e2
Zeff
e2
Zeff 2
1
Zeff
Zeff 2
H=
(1 + 2 )
+
+
+
2m
40
r1
r2
40
r1
r2
|~r1 ~r2 |

27
2
= hHi = 2Zeff
+
Zeff E1
4
For calculation details, see Ref. [2].
Igor Luka
cevi
c


~2
e2
Zeff
e2
Zeff 2
1
Zeff
Zeff 2
H=
(1 + 2 )
+
+
+
2m
40
r1
r2
40
r1
r2
|~r1 ~r2 |

27
2
= hHi = 2Zeff
+
Zeff E1
4
Now minimizing hHi we get
min
Zeff
= 1.69
Igor Luka
cevi
c


~2
e2
Zeff
e2
Zeff 2
1
Zeff
Zeff 2
H=
(1 + 2 )
+
+
+
2m
40
r1
r2
40
r1
r2
|~r1 ~r2 |

27
2
= hHi = 2Zeff
+
Zeff E1
4
Now minimizing hHi we get
min
Zeff
= 1.69
Which gives
hHimin = Emin = 77.5 eV ,
Egs Emin
= 1.87%
Egs
Note:
For more precise results see E. A. Hylleraas, Z. Phys. 65, 209 (1930) or C. L. Pekeris,
Phys. Rev. 115, 1216 (1959).
Igor Luka
cevi
c

Contents
Theory
Literature
Igor Luka
cevi
c

e
normalized trial function
depends on 1 , 2 . . .
e
e
h|H|i
very complex function of 1 , 2 . . .
Igor Luka
cevi
c

e
e i
e
h|H|
Suppose
e =
|i
N
X
ci |i i ,
hi |j i = ij
i=1
Igor Luka
cevi
c

e
e i
e
h|H|
Suppose
e =
|i
N
X
ci |i i ,
hi |j i = ij
i=1
= (H)ij = Hij = hi |H|j i
matrix representation in basis {|i i}
Igor Luka
cevi
c

e
e
e
h|H|i
Suppose
e =
|i
N
X
ci |i i ,
hi |j i = ij
i=1
H hermitian
{|i i} real
Igor Luka
cevi
c

H symmetric

e
e i
e
h|H|
Suppose
e =
|i
N
X
ci |i i ,
hi |j i = ij
i=1
H hermitian
{|i i} real
e normalized

H symmetric
ci2 = 1
Igor Luka
cevi
c

e
e i
e
h|H|
Suppose
e =
|i
N
X
ci |i i ,
hi |j i = ij
i=1
H hermitian
{|i i} real
e normalized

H symmetric
ci2 = 1
the expectation value depends on cij :

e i
e =
= h|H|
cij Hij
ij
Igor Luka
cevi
c

e normalized
ci2 = 1

e i
e =
= h|H|
cij Hij
ij
Unfortunately,
e
e = 0 , k = 1, 2, . . . , N
h|H|i
ck
is unsolvable for ck are mutually dependent.
Igor Luka
cevi
c

e normalized
ci2 = 1

e i
e =
= h|H|
cij Hij
ij
Unfortunately,
e
e = 0 , k = 1, 2, . . . , N
h|H|i
ck
Lagranges method of undetermined multipliers

e i
e E h|
e i
e 1
L(c1 , . . . , cN , E ) = h|H|
!
=
X
ij
Igor Luka
cevi
c
ci cj Hij E
ci2

Unfortunately,
e
e = 0 , k = 1, 2, . . . , N
h|H|i
ck
Lagranges method of undetermined multipliers

e i
e E h|
e i
e 1
L(c1 , . . . , cN , E ) = h|H|
!
=
ci cj Hij E
ij
ci2 1
e i
e and L are minimal for same ck
h|H|
Igor Luka
cevi
c

Let us now choose c1 , c2 , . . . , cN1 as independent

X 2
cN is given by
ci = 1
i
Igor Luka
cevi
c


X 2
cN is given by
ci = 1
i
Then we have
L
= 0,
ck
k = 1, 2, . . . , N 1
but not necessarily

L
=0
cN
Igor Luka
cevi
c


X 2
cN is given by
ci = 1
i
Then we have
L
= 0,
ck
k = 1, 2, . . . , N 1
but not necessarily

L
=0
cN
But we still have undetermined multiplier E , so now we choose it so that
L
= 0,
ck
k = 1, 2, . . . , N 1, N
Igor Luka
cevi
c


X 2
cN is given by
ci = 1
i
Then we have
L
= 0,
ck
k = 1, 2, . . . , N 1
but not necessarily

L
=0
cN
L
= 0,
ck
k = 1, 2, . . . , N 1, N
On the other hand

X
X
L
=
cj Hkj +
ci Hik 2Eck
ck
j
i
Igor Luka
cevi
c

Then we have
L
= 0,
ck
k = 1, 2, . . . , N 1
but not necessarily

L
=0
cN
L
= 0,
ck
k = 1, 2, . . . , N 1, N
On the other hand

X
X
L
=
cj Hkj +
ci Hik 2Eck
ck
j
i
|
{z
}
equal, since Hij =Hji
So,
X
Hij cj Eci = 0
Igor Luka
cevi
c

Or in matrix form
Hc = E c
A question
What represents this equation?
Igor Luka
cevi
c

Or in matrix form
Hc = E c
Hc = E c ,
= 0, 1, . . . , N 1 ,
(c ) c =
X
i
Igor Luka
cevi
c
ci ci =

Or in matrix form
Hc = E c
Hc = E c ,
= 0, 1, . . . , N 1 ,
(c ) c =
X
i
E = E , Ci = ci = HC = EC
Igor Luka
cevi
c
ci ci =

Or in matrix form
Hc = E c
Hc = E c ,
= 0, 1, . . . , N 1 ,
(c ) c =
X
i
Solving gives N orthonormal solutions
|e i =
N
X
ci |i i ,
= 0, 1, . . . , N 1
i=1
Igor Luka
cevi
c
ci ci =

Or in matrix form
Hc = E c
Hc = E c ,
= 0, 1, . . . , N 1 ,
(c ) c =
X
i
|e i =
N
X
ci |i i ,
= 0, 1, . . . , N 1
i=1
What about E s:
he |H|e i = E
Igor Luka
cevi
c
ci ci =

HC = EC
|e i =
N
X
ci |i i ,
= 0, 1, . . . , N 1
i=1
What about E s:
he |H|e i = E
For example,
E0 = he0 |H|e0 i E0
A question
Whats the meaning of other E s?
Igor Luka
cevi
c

HC = EC
|e i =
N
X
ci |i i ,
= 0, 1, . . . , N 1
i=1
What about E s:
he |H|e i = E
For example,
E0 = he0 |H|e0 i E0
A question
Whats the meaning of other E s? E E , = 1, 2, . . .
Igor Luka
cevi
c

In conclusion
Solving the matrix eigenvalue problem
HC = EC ,
by diagonalization, is equivalent to the variational principle in a subspace
spanned by {|i i , i = 1, 2, . . . , N}.
Igor Luka
cevi
c

Literature
Contents
Theory
Literature
Igor Luka
cevi
c

Literature
Literature
A. Szabo, N. Ostlund, Modern Quantum Chemistry, Introduction to

Advanced Electronic Structure theory, Dover Publications, New York,
1996.
D. J. Griffiths, Introduction to Quantum Mechanics, 2nd ed., Pearson

Education, Inc., Upper Saddle River, NJ, 2005.
I. Supek, Teorijska fizika i struktura materije, II. dio, Skolska

knjiga,
Zagreb, 1989.
Y. Peleg, R. Pnini, E. Zaarur, Shaums Outline of Theory and Problems of

Quantum Mechanics, McGraw-Hill, 1998.
I. N. Bronstejn, K. A. Semendjajev, Matematicki prirucnik, Tehnicka

knjiga, Zagreb, 1991.
Igor Luka
cevi
c

Lecture 5 Variational Principle

Diunggah oleh

Informasi Dokumen

Deskripsi Asli:

Hak Cipta

Format Tersedia

Bagikan dokumen Ini

Bagikan atau Tanam Dokumen

Opsi Berbagi

Apakah menurut Anda dokumen ini bermanfaat?

Apakah konten ini tidak pantas?

Hak Cipta:

Format Tersedia

Lecture 5 Variational Principle

Diunggah oleh

Hak Cipta:

Format Tersedia

The variational principle

The variational principle

The variational principle

The variational principle

The ground state of helium

The linear variational problem

The variational principle

The variational principle

The ground state of helium

The linear variational problem

The variational principle

The variational principle

What is a problem we would like to solve?

The variational principle

The variational principle

What is a problem we would like to solve?

The variational principle

The variational principle

What is a problem we would like to solve?

The variational principle

The variational principle

Theorem - the variational principle

The variational principle

The variational principle

Theorem - the variational principle

The variational principle

The variational principle

Theorem - the variational principle

The variational principle

The variational principle

The variational principle

The variational principle

The variational principle

The variational principle

The variational principle

The variational principle

The variational principle

The variational principle

The variational principle

The variational principle

Example: One-dimensional harmonic oscilator

The variational principle

The variational principle

Example: One-dimensional harmonic oscilator

How to do this using the variational principle...

The variational principle

The variational principle

Example: One-dimensional harmonic oscilator

How to do this using the variational principle...

(ii) calculate hHi = hT i + hV i

The variational principle

The variational principle

Example: One-dimensional harmonic oscilator

How to do this using the variational principle...

(ii) calculate hHi = hT i + hV i

On how to solve these kind of

The variational principle

The variational principle

Example: One-dimensional harmonic oscilator

(ii) calculate hHi = hT i + hV i

On how to solve these kind of

The variational principle

The variational principle