The variational principle

The variational principle

Quantum mechanics 2 - Lecture 5

Igor Lukacevic
UJJS, Dept. of Physics, Osijek

November 8, 2012

Igor Luka
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The variational principle

The variational principle

Contents

Theory

The ground state of helium

The linear variational problem

Literature

Igor Luka
cevi
c

The variational principle

The variational principle

Theory

Contents

Theory

The ground state of helium

The linear variational problem

Literature

Igor Luka
cevi
c

The variational principle

The variational principle

Theory

What is a problem we would like to solve?

To find approximate solutions of eigenvalue problem
O(x) = (x)

Igor Luka
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The variational principle

The variational principle

Theory

What is a problem we would like to solve?

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

Igor Luka
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The variational principle

The variational principle

Theory

What is a problem we would like to solve?

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
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The variational principle

The variational principle

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
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The variational principle

The variational principle

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|
A question
What if e is a ground state w.f.?

Igor Luka
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The variational principle

The variational principle

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

Igor Luka
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The variational principle

The variational principle

Theory

Proof
e i
e =1
e are normalized h|

Igor Luka
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The variational principle

The variational principle

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
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The variational principle

The variational principle

Theory

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

So,
e i
e =
h|

DX

X
E X
X

c 
|c |2 = 1
c =
c c h | i =
{z
}
|

Igor Luka
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The variational principle

The variational principle

Theory

Proof
e i
e =1
e are normalized h|
e = P c | i
On the other hand, (unknown) form a complete set |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
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The variational principle

The variational principle

Theory

Proof
e i
e =1
e are normalized h|
e = P c | i
On the other hand, (unknown) form a complete set |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
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|c |2 = E0

The variational principle

The variational principle

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
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The variational principle

The variational principle

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

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
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The variational principle

The variational principle

Theory

Example: One-dimensional harmonic oscilator

a] Find the ground state energy and w.f. of one-dimensional harmonic oscilator:
H=

1
~2
+ 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

(ii) calculate hHi = hT i + hV i

Igor Luka
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The variational principle

The variational principle

Theory

Example: One-dimensional harmonic oscilator

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

(ii) calculate hHi = hT i + hV i

~2
2m
m 2
hV i =
8
hT i =

On how to solve these kind of

integrals, see Ref. [5].

Igor Luka
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The variational principle

The variational principle

Theory

Example: One-dimensional harmonic oscilator

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

(ii) calculate hHi = hT i + hV i

~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
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The variational principle

The variational principle

Theory

Example: One-dimensional harmonic oscilator

(iii) minimize hHi wrt parameter

d
m
hHi = 0 = =
d
2~

Igor Luka
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The variational principle

The variational principle

Theory

Example: One-dimensional harmonic oscilator

(iii) minimize hHi wrt parameter

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
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The variational principle

The variational principle

Theory

Example: One-dimensional harmonic oscilator

(iii) minimize hHi wrt parameter

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
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The variational principle

The variational principle

Theory

Example: One-dimensional harmonic oscilator

b] Do the same, but with trial function (x) = Bxe x

Igor Luka
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The variational principle

The variational principle

Theory

Example: One-dimensional harmonic oscilator

b] Do the same, but with trial function (x) = Bxe x

s
2  m 3/4
(i) normalization gives B =
~

Igor Luka
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The variational principle

The variational principle

Theory

Example: One-dimensional harmonic oscilator

b] Do the same, but with trial function (x) = Bxe x

s
2  m 3/4
(i) normalization gives B =
~

(ii) calculate hHi =

3m 2 1
3~3
+
2m
8

Igor Luka
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The variational principle

The variational principle

Theory

Example: One-dimensional harmonic oscilator

b] Do the same, but with trial function (x) = Bxe x

s
2  m 3/4
(i) normalization gives B =
~

3m 2 1
3~3
+
2m
8
m
(iii) minimize hHi = =
2~
(ii) calculate hHi =

Igor Luka
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The variational principle

The variational principle

Theory

Example: One-dimensional harmonic oscilator

b] Do the same, but with trial function (x) = Bxe x

s
2  m 3/4
(i) normalization gives B =
~

3~3
3m 2 1
+
2m
8
m
(iii) minimize hHi = =
2~
(iv) get minimal values
(ii) calculate hHi =

3
~
2
s
2
2  m 3/4 m

min (x) =
xe 2~ x
~

hHimin =

Igor Luka
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The variational principle

The variational principle

Theory

Example: One-dimensional harmonic oscilator

b] Do the same, but with trial function (x) = Bxe x

s
2  m 3/4
(i) normalization gives B =
~

3~3
3m 2 1
+
2m
8
m
(iii) minimize hHi = =
2~
(iv) get minimal values
(ii) calculate hHi =

3
~
2
s
2
2  m 3/4 m

min (x) =
xe 2~ x
~

hHimin =

Igor Luka
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exact 1st excited state

energy and w.f.

The variational principle

The variational principle

Theory

Example: One-dimensional harmonic oscilator

In conclusion...
b]

trial (x) = Bxe x

2
a]
gs
trial (x) = exact
(x) = Ae x

Igor Luka
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D
E
b]
gs
= trial (x)|exact
(x) = 0

The variational principle

The variational principle

Theory

Example: One-dimensional harmonic oscilator

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
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The variational principle

The variational principle

Theory

Example: One-dimensional harmonic oscilator

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
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The variational principle

The variational principle

The ground state of helium

Contents

Theory

The ground state of helium

The linear variational problem

Literature

Igor Luka
cevi
c

The variational principle

The variational principle

The ground state of helium

~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
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The variational principle

The variational principle

The ground state of helium

~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
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The variational principle

The variational principle

The ground state of helium

~2
(1 + 2 )
2m


2
e
2
1
2

+
40 r1
r2
|~r1 ~r2 |

H =

kinetic energy of electrons 1 and 2

Igor Luka
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The variational principle

The variational principle

The ground state of helium

~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
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The variational principle

The variational principle

The ground state of helium

~2
(1 + 2 )
2m


e2
2
2
1

+
40 r1
r2 |r1 r2 |

H =

electrostatic repulsion between the electrons

1 and 2

Igor Luka
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The variational principle

The variational principle

The ground state of helium

~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
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The variational principle

The variational principle

The ground state of helium

~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
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The variational principle

The variational principle

The ground state of helium

~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
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The variational principle

The variational principle

The ground state of helium

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
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The variational principle

The variational principle

The ground state of helium

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
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The variational principle

The variational principle

The ground state of helium

Now, let us account for Vee :

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

hVee i =

e2
40



Igor Luka
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23
a3

2 Z

r1 +r2

e 4 a
d~r1 d~r2
|~r1 ~r2 |

The variational principle

The variational principle

The ground state of helium

Now, let us account for Vee :

0 99K trial w.f. (is this justifiable?)
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
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The variational principle

The variational principle

The ground state of helium

Now, let us account for Vee :

0 99K trial w.f. (is this justifiable?)

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
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The variational principle

The variational principle

The ground state of helium

Now, let us account for Vee :

0 99K trial w.f. (is this justifiable?)
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
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The variational principle

The variational principle

The ground state of helium

Zeff
effective nuclear
charge
Trial w.f.
1 (~r1 ,~r2 ) =

Igor Luka
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The variational principle

3
Zeff
e Zeff
3
a

r1 +r2
a

The variational principle

The ground state of helium

Zeff
effective nuclear
charge
Trial w.f.
1 (~r1 ,~r2 ) =

2
Z3eff Zeff r1 +r
a
e
a3

Zeff - variational
parameter

Igor Luka
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The variational principle

The variational principle

The ground state of helium

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
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The variational principle

The variational principle

The ground state of helium

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 |


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

Igor Luka
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The variational principle

The variational principle

The ground state of helium

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 |


27
2
= hHi = 2Zeff
+
Zeff E1
4
Now minimizing hHi we get
min
Zeff
= 1.69

Igor Luka
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The variational principle

The variational principle

The ground state of helium

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 |


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
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The variational principle

The variational principle

The linear variational problem

Contents

Theory

The ground state of helium

The linear variational problem

Literature

Igor Luka
cevi
c

The variational principle

The variational principle

The linear variational problem

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

Igor Luka
cevi
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The variational principle

The variational principle

The linear variational problem

e
normalized trial function
depends on 1 , 2 . . .
e i
e
very complex function of 1 , 2 . . .
h|H|
Suppose
e =
|i

N
X

ci |i i ,

hi |j i = ij

i=1

Igor Luka
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The variational principle

The variational principle

The linear variational problem

e
normalized trial function
depends on 1 , 2 . . .
e i
e
very complex function of 1 , 2 . . .
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
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The variational principle

The variational principle

The linear variational problem

e
normalized trial function
depends on 1 , 2 . . .
e
e
h|H|i
very complex function of 1 , 2 . . .
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}

H hermitian
{|i i} real

Igor Luka
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H symmetric

The variational principle

The variational principle

The linear variational problem

e
normalized trial function
depends on 1 , 2 . . .
e i
e
h|H|
very complex function of 1 , 2 . . .
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}

H hermitian
{|i i} real
e normalized


H symmetric

ci2 = 1

Igor Luka
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The variational principle

The variational principle

The linear variational problem

e
normalized trial function
depends on 1 , 2 . . .
e i
e
very complex function of 1 , 2 . . .
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}

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
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The variational principle

The variational principle

The linear variational problem

e normalized

ci2 = 1

the expectation value depends on cij :

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
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The variational principle

The variational principle

The linear variational problem

e normalized

ci2 = 1

the expectation value depends on cij :

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.
Lagranges method of undetermined multipliers


e i
e E h|
e i
e 1
L(c1 , . . . , cN , E ) = h|H|
!
=

X
ij

Igor Luka
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ci cj Hij E

ci2

The variational principle

The variational principle

The linear variational problem

Unfortunately,
e
e = 0 , k = 1, 2, . . . , N
h|H|i
ck
is unsolvable for ck are mutually dependent.
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
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The variational principle

The variational principle

The linear variational problem

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

X 2
cN is given by
ci = 1
i

Igor Luka
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The variational principle

The variational principle

The linear variational problem

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

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
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The variational principle

The variational principle

The linear variational problem

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

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
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The variational principle

The variational principle

The linear variational problem

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

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

On the other hand

X
X
L
=
cj Hkj +
ci Hik 2Eck
ck
j
i

Igor Luka
cevi
c

The variational principle

The variational principle

The linear variational problem

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

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

The variational principle

The variational principle

The linear variational problem

Or in matrix form
Hc = E c

A question
What represents this equation?

Igor Luka
cevi
c

The variational principle

The variational principle

The linear variational problem

Or in matrix form
Hc = E c

Hc = E c ,

= 0, 1, . . . , N 1 ,

(c ) c =

X
i

Igor Luka
cevi
c

The variational principle

ci ci =

The variational principle

The linear variational problem

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

The variational principle

ci ci =

The variational principle

The linear variational problem

Or in matrix form
Hc = E c

Hc = E c ,

= 0, 1, . . . , N 1 ,

(c ) c =

X
i

E = E , Ci = ci = HC = EC
Solving gives N orthonormal solutions
|e i =

N
X

ci |i i ,

= 0, 1, . . . , N 1

i=1

Igor Luka
cevi
c

The variational principle

ci ci =

The variational principle

The linear variational problem

Or in matrix form
Hc = E c

Hc = E c ,

= 0, 1, . . . , N 1 ,

(c ) c =

X
i

E = E , Ci = ci = HC = EC
Solving gives N orthonormal solutions
|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

The variational principle

ci ci =

The variational principle

The linear variational problem

HC = EC
Solving gives N orthonormal solutions
|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

The variational principle

The variational principle

The linear variational problem

HC = EC
Solving gives N orthonormal solutions
|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

The variational principle

The variational principle

The linear variational problem

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

The variational principle

The variational principle

Literature

Contents

Theory

The ground state of helium

The linear variational problem

Literature

Igor Luka
cevi
c

The variational principle

The variational principle

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

The variational principle