The variational principle

The variational principle

Quantum mechanics 2 - Lecture 5

Igor Lukačević

UJJS, Dept. of Physics, Osijek

November 8, 2012

Igor Lukačević The variational principle

The variational principle
Contents

1 Theory

2 The ground state of helium

3 The linear variational problem

4 Literature

Igor Lukačević The variational principle

The variational principle
Theory

Contents

1 Theory

2 The ground state of helium

3 The linear variational problem

4 Literature

Igor Lukačević The variational principle

The variational principle
Theory

What is a problem we would like to solve?

To find approximate solutions of eigenvalue problem

Oφ(x) = ωφ(x)

Igor Lukačević The variational principle

The variational principle
Theory

What is a problem we would like to solve?

To find approximate solutions of eigenvalue problem

Oφ(x) = ωφ(x)

A question
Can you remember any eigenvalue problems?

Igor Lukačević The variational principle

The variational principle
Theory

What is a problem we would like to solve?

To find approximate solutions of Oφ(x) = ωφ(x).

A question
Can you remember any eigenvalue problems?

Hψα = Eα ψα , α = 0, 1, . . .
where
E0 ≤ E1 ≤ E2 ≤ · · · ≤ Eα ≤ · · · , hψα |ψβ i = δαβ

Igor Lukačević The variational principle

The variational principle
Theory

Theorem - the variational principle

Given any normalized function ψe (that satisfies the appropriate boundary
conditions), then the expectation value of the Hamiltonian represents an upper
bound to the exact ground state energy

hψ|H|
e ψi e ≥ E0 .

Igor Lukačević The variational principle

The variational principle
Theory

Theorem - the variational principle

Given any normalized function ψe (that satisfies the appropriate boundary
conditions), then the expectation value of the Hamiltonian represents an upper
bound to the exact ground state energy

hψ|H|
e ψi e ≥ E0 .

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

Igor Lukačević The variational principle

The variational principle
Theory

Theorem - the variational principle

Given any normalized function ψe (that satisfies the appropriate boundary
conditions), then the expectation value of the Hamiltonian represents an upper
bound to the exact ground state energy

hψ|H|
e ψi e ≥ E0 .

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

hψ|H|
e ψi e = E0

Igor Lukačević The variational principle

The variational principle
Theory

Proof
ψe are normalized ⇒ hψ|
e ψi
e =1

Igor Lukačević The variational principle

The variational principle
Theory

Proof
ψe are normalized ⇒ hψ|
e ψi
e =1
e = P cα |ψα i
On the other hand, (unknown) ψ form a complete set ⇒ |ψi α

Igor Lukačević The variational principle

The variational principle
Theory

Proof
ψe are normalized ⇒ hψ|
e ψi
e =1
e = P cα |ψα i
On the other hand, (unknown) ψα form a complete set ⇒ |ψi α
So,
DX X E X X
hψ|
e ψi
e = c β ψβ  cα ψα = cβ∗ cα hψβ |ψα i = |cα |2 = 1

β α αβ
| {z } α
δαβ

Igor Lukačević The variational principle

The variational principle
Theory

Proof
ψe are normalized ⇒ hψ|
e ψi
e =1
e = P cα |ψα i
On the other hand, (unknown) ψα form a complete set ⇒ |ψi α
So,
DX X E X X
hψ|
e ψi
e = c β ψβ  cα ψα = cβ∗ cα hψβ |ψα i = |cα |2 = 1

β α αβ
| {z } α
δαβ

Now
DX  X E X X
hψ|H|
e ψi e = c β ψβ  H  c α ψα = cβ∗ cα Eα hψβ |ψα i = Eα |cα |2
 
β α αβ
| {z } α
| {z } δαβ

α cα H|ψα i
P
| {z }
Eα |ψα i

Igor Lukačević The variational principle

The variational principle
Theory

Proof
ψe are normalized ⇒ hψ|
e ψi
e =1
e = P cα |ψα i
On the other hand, (unknown) ψα form a complete set ⇒ |ψi α
So,
DX X E X X
hψ|
e ψi
e = c β ψβ  cα ψα = cβ∗ cα hψβ |ψα i = |cα |2 = 1

β α αβ
| {z } α
δαβ

Now
DX  X E X X
hψ|H|
e ψi e = c β ψβ  H  c α ψα = cβ∗ cα Eα hψβ |ψα i = Eα |cα |2
 
β α αβ
| {z } α
| {z } δαβ
H|ψ i
P
c
α α α
| {z }
Eα |ψα i

But Eα ≥ E0 , ∀α, hence

X X
hψ|H|
e ψi e ≥ E0 |cα |2 = E0 |cα |2 = E0
α α

Igor Lukačević 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:

~2 1
H=− ∆ + mω 2 x 2 .
2m 2

Igor Lukačević 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:

~2 1
H=− ∆ + mω 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.:
2
ψ(x) = Ae −αx

r α parameter
4 2α
A= from normalization condition (do it for HW)
π

Igor Lukačević 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:

~2 1
H=− ∆ + mω 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.:
2
ψ(x) = Ae −αx

r α parameter
4 2α
A= from normalization condition
π
(ii) calculate hHi = hT i + hV i

Igor Lukačević 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.:
2
ψ(x) = Ae −αx

r α parameter
4 2α
A= from normalization condition
π
(ii) calculate hHi = hT i + hV i

~2 α
hT i =
2m On how to solve these kind of
mω 2 integrals, see Ref. [5].
hV i =
8α

Igor Lukačević 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.:
2
ψ(x) = Ae −αx

r α parameter
4 2α
A= from normalization condition
π
(ii) calculate hHi = hT i + hV i

~2 α
hT i =
2m On how to solve these kind of
mω 2 integrals, see Ref. [5].
hV i =
8α
~2 α mω 2
hHi = +
2m 8α

Igor Lukačević The variational principle

The variational principle
Theory

Example: One-dimensional harmonic oscilator

(iii) minimize hHi wrt parameter α

d mω
hHi = 0 =⇒ α =
dα 2~

Igor Lukačević The variational principle

The variational principle
Theory

Example: One-dimensional harmonic oscilator

(iii) minimize hHi wrt parameter α

d mω
hHi = 0 =⇒ α =
dα 2~
(iv) insert back into hHi and ψ(x):
1
hHimin = ~ω
2
r
mω − mω 2
ψmin (x) = 4 e 2~ x
π~

Igor Lukačević The variational principle

The variational principle
Theory

Example: One-dimensional harmonic oscilator

(iii) minimize hHi wrt parameter α

d mω
hHi = 0 =⇒ α =
dα 2~
(iv) insert back into hHi and ψ(x):
1

hHimin = ~ω 

2
r exact ground state energy and w.f.
mω mω 2
ψmin (x) = 4 e− 2~ x 
π~

A question
Why did we get the exact energy and w.f.?

Igor Lukačević The variational principle

The variational principle
Theory

Example: One-dimensional harmonic oscilator

2
b] Do the same, but with trial function ψ(x) = Bxe −βx

Igor Lukačević The variational principle

The variational principle
Theory

Example: One-dimensional harmonic oscilator

2
b] Do the same, but with trial function ψ(x) = Bxe −βx
s
2  mω 3/4
(i) normalization gives B = √
π ~

Igor Lukačević The variational principle

The variational principle
Theory

Example: One-dimensional harmonic oscilator

2
b] Do the same, but with trial function ψ(x) = Bxe −βx
s
2  mω 3/4
(i) normalization gives B = √
π ~
3~3 3mω 2 1
(ii) calculate hHi = β+
2m 8 β

Igor Lukačević The variational principle

The variational principle
Theory

Example: One-dimensional harmonic oscilator

2
b] Do the same, but with trial function ψ(x) = Bxe −βx
s
2  mω 3/4
(i) normalization gives B = √
π ~
3~3 3mω 2 1
(ii) calculate hHi = β+
2m 8 β
mω
(iii) minimize hHi =⇒ β =
2~

Igor Lukačević The variational principle

The variational principle
Theory

Example: One-dimensional harmonic oscilator

2
b] Do the same, but with trial function ψ(x) = Bxe −βx
s
2  mω 3/4
(i) normalization gives B = √
π ~
3~3 3mω 2 1
(ii) calculate hHi = β+
2m 8 β
mω
(iii) minimize hHi =⇒ β =
2~
(iv) get minimal values
3
hHimin = ~ω
2
s
2  mω 3/4 − mω 2
ψmin (x) = √ xe 2~ x
π ~

Igor Lukačević The variational principle

The variational principle
Theory

Example: One-dimensional harmonic oscilator

2
b] Do the same, but with trial function ψ(x) = Bxe −βx
s
2  mω 3/4
(i) normalization gives B = √
π ~
3~3 3mω 2 1
(ii) calculate hHi = β+
2m 8 β
mω
(iii) minimize hHi =⇒ β =
2~
(iv) get minimal values
3

hHimin = ~ω 

2
s 
exact 1st excited state
2  mω 3/4 − mω 2
energy and w.f.
ψmin (x) = √ xe 2~ x 

π ~ 

Igor Lukačević The variational principle

The variational principle
Theory

Example: One-dimensional harmonic oscilator

In conclusion...
2
)
b]
ψtrial (x) = Bxe −βx D
b] gs
E
a] gs 2 =⇒ ψtrial (x)|ψexact (x) = 0
ψtrial (x) = ψexact (x) = Ae −αx

Igor Lukačević The variational principle

The variational principle
Theory

Example: One-dimensional harmonic oscilator

In conclusion...
2
)
b]
ψtrial (x) = Bxe −βx D
b] gs
E
a] gs 2 =⇒ ψtrial (x)|ψexact (x) = 0
ψtrial (x) = ψexact (x) = Ae −αx
b]
Also, hHimin accounts for 1st excited state

Igor Lukačević The variational principle

The variational principle
Theory

Example: One-dimensional harmonic oscilator

In conclusion...
2
)
b]
ψtrial (x) = Bxe −βx D
b] gs
E
a] gs 2 =⇒ ψtrial (x)|ψexact (x) = 0
ψtrial (x) = ψexact (x) = Ae −αx
b]
Also, hHimin accounts for 1st excited state

Corollary
If hψ|ψgs i = 0, then hHi ≥ Efes , where Efes is the energy of the 1st excited
state.

Igor Lukačević The variational principle

The variational principle
The ground state of helium

Contents

1 Theory

2 The ground state of helium

3 The linear variational problem

4 Literature

Igor Lukačević The variational principle

The variational principle
The ground state of helium

~2
H = − (∆1 + ∆2 )
2m
e2
 
2 2 1
− + −
4π0 r1 r2 |~r1 − ~r2 |

A question
What does each of these terms mean?

Igor Lukačević The variational principle

The variational principle
The ground state of helium

~2
H = − (∆1 + ∆2 )
2m
2
 
e 2 2 1
− + −
4π0 r1 r2 |~r1 − ~r2 |

A question
What does each of these terms mean?

Igor Lukačević The variational principle

The variational principle
The ground state of helium

~2
H = − (∆1 + ∆2 )
2m
2
 
e 2 2 1
− + −
4π0 r1 r2 |~r1 − ~r2 |

kinetic energy of electrons 1 and 2

Igor Lukačević The variational principle

The variational principle
The ground state of helium

~2
H = − (∆1 + ∆2 )
2m
e2
 
2 2 1
− + −
4π0 r1 r2 |~r1 − ~r2 |

electrostatic attraction between the nucleus

and electrons 1 and 2

Igor Lukačević The variational principle

The variational principle
The ground state of helium

~2
H = − (∆1 + ∆2 )
2m
e2
 
2 2 1
− + −
4π0 r1 r2 |r̃1 − r̃2 |

electrostatic repulsion between the electrons

1 and 2

Igor Lukačević The variational principle

The variational principle
The ground state of helium

~2
H = − (∆1 + ∆2 )
2m
e2
 
2 2 1
− + −
4π0 r1 r2 |~r1 − ~r2 |

Our mission to calculate the ground state energy Egs

exp
Egs = −78.975 eV

Igor Lukačević The variational principle

The variational principle
The ground state of helium

~2
H = − (∆1 + ∆2 )
2m
2
 
e 2 2 1
− + −
4π0 r1 r2 |~r1 − ~r2 |

A question
Can you identify the troublesome term in H?

Igor Lukačević The variational principle

The variational principle
The ground state of helium

~2
H = − (∆1 + ∆2 )
2m
2
 
e 2 2 1
− + −
4π0 r1 r2 |~r1 − ~r2 |

A question
Can you identify the troublesome term in H?

e2 1
Vee =
4π0 |~r1 − ~r2 |

Igor Lukačević 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 ψ looks like and what’s the
energy?

Igor Lukačević 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 ψ looks like and what’s the
energy?
H = H1 + H2
23 −2 r1 +r 2
ψ0 (~r1 ,~r2 ) = ψ100 (~r1 )ψ100 (~r2 ) = e a
a3 π
E0 = 8E1 = −109 eV

Igor Lukačević The variational principle

The variational principle
The ground state of helium

Now, let us account for Vee :

ψ0 99K trial w.f. (is this justifiable?)
hHi = 8E1 + hVee i
2 Z r1 +r2
e2 23 e −4 a
 
hVee i = d~r1 d~r2
4π0 a3 π |~r1 − ~r2 |

Igor Lukačević The variational principle

The variational principle
The ground state of helium

Now, let us account for Vee :

ψ0 99K trial w.f. (is this justifiable?)
hHi = 8E1 + hVee i
2 Z r1 +r2
e2 23 e −4 a
 
hVee i = d~r1 d~r2
4π0 a3 π |~r1 − ~r2 |

A question
What do you expect for hVee i and why?

Igor Lukačević The variational principle

The variational principle
The ground state of helium

Now, let us account for Vee :

ψ0 99K trial w.f. (is this justifiable?) HW

hHi = 8E1 + hVee i Calculate
2 Z r +r
hVee i using
−4 1 a 2
e2 23
 
e Refs. [2] and
hVee i = d~r1 d~r2 = 34 eV
4π0 a3 π |~r1 − ~r2 | [5].

Igor Lukačević The variational principle

The variational principle
The ground state of helium

Now, let us account for Vee :

ψ0 99K trial w.f. (is this justifiable?)
hHi = 8E1 + hVee i
2 Z r1 +r2
e2 23 e −4 a
 
hVee i = d~r1 d~r2 = 34 eV
4π0 a3 π |~r1 − ~r2 |

hHi = −109 eV + 34 eV = −75 eV

exp
Egs = −79 eV
Rel. error 5.1%

Igor Lukačević The variational principle

The variational principle
The ground state of helium

Zeff effective nuclear

charge
Trial w.f.
3
Zeff r1 +r2
ψ1 (~r1 ,~r2 ) = 3
e −Zeff a
a π

Igor Lukačević The variational principle

The variational principle
The ground state of helium

Zeff effective nuclear

charge
Trial w.f.
Z3eff −Zeff r1 +r2
ψ1 (~r1 ,~r2 ) = e a
a3 π
Zeff - variational
parameter

Igor Lukačević The variational principle

The variational principle
The ground state of helium

Let us rewrite the Hamiltonian:

~2 e2 e2
   
Zeff Zeff Zeff − 2 Zeff − 2 1
H=− (∆1 + ∆2 )− + + + −
2m 4π0 r1 r2 4π0 r1 r2 |~r1 − ~r2 |

Igor Lukačević The variational principle

The variational principle
The ground state of helium

Let us rewrite the Hamiltonian:

~2 e2 e2
   
Zeff Zeff Zeff − 2 Zeff − 2 1
H=− (∆1 + ∆2 )− + + + −
2m 4π0 r1 r2 4π0 r1 r2 |~r1 − ~r2 |
 
2 27
=⇒ hHi = −2Zeff + Zeff E1
4

For calculation details, see Ref. [2].

Igor Lukačević The variational principle

The variational principle
The ground state of helium

Let us rewrite the Hamiltonian:

~2 e2 e2
   
Zeff Zeff Zeff − 2 Zeff − 2 1
H=− (∆1 + ∆2 )− + + + −
2m 4π0 r1 r2 4π0 r1 r2 |~r1 − ~r2 |
 
2 27
=⇒ hHi = −2Zeff + Zeff E1
4
Now minimizing hHi we get
min
Zeff = 1.69

Igor Lukačević The variational principle

The variational principle
The ground state of helium

Let us rewrite the Hamiltonian:

~2 e2 e2
   
Zeff Zeff Zeff − 2 Zeff − 2 1
H=− (∆1 + ∆2 )− + + + −
2m 4π0 r1 r2 4π0 r1 r2 |~r1 − ~r2 |
 
2 27
=⇒ hHi = −2Zeff + Zeff E1
4
Now minimizing hHi we get
min
Zeff = 1.69
Which gives
Egs − Emin
hHimin = Emin = −77.5 eV , = 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 Lukačević The variational principle

The variational principle
The linear variational problem

Contents

1 Theory

2 The ground state of helium

3 The linear variational problem

4 Literature

Igor Lukačević The variational principle

The variational principle
The linear variational problem

ψe normalized trial function depends on α1 , α2 . . .

hψ|H|ψi
e e very complex function of α1 , α2 . . .

Igor Lukačević The variational principle

The variational principle
The linear variational problem

ψe normalized trial function depends on α1 , α2 . . .

hψ|H|
e ψie very complex function of α1 , α2 . . .
Suppose
N
X
|ψi
e = ci |ψi i , hψi |ψj i = δij
i=1

Igor Lukačević The variational principle

The variational principle
The linear variational problem

ψe normalized trial function depends on α1 , α2 . . .

hψ|H|
e ψie very complex function of α1 , α2 . . .
Suppose
N
X
|ψi
e = ci |ψi i , hψi |ψj i = δij
i=1

=⇒ (H)ij = Hij = hψi |H|ψj i matrix representation in basis {|ψi i}

Igor Lukačević The variational principle

The variational principle
The linear variational problem

ψe normalized trial function depends on α1 , α2 . . .

hψ|H|ψi
e e very complex function of α1 , α2 . . .
Suppose
N
X
|ψi
e = ci |ψi i , hψi |ψj i = δij
i=1

=⇒ (H)ij = Hij = hψi |H|ψj i matrix representation in basis {|ψi i}


H hermitian
⇒ H symmetric
{|ψi i} real

Igor Lukačević The variational principle

The variational principle
The linear variational problem

ψe normalized trial function depends on α1 , α2 . . .

hψ|H|
e ψie very complex function of α1 , α2 . . .
Suppose
N
X
|ψi
e = ci |ψi i , hψi |ψj i = δij
i=1

=⇒ (H)ij = Hij = hψi |H|ψj i matrix representation in basis {|ψi i}


H hermitian
⇒ H symmetric
{|ψi i} real
X
ψe normalized ⇒ ci2 = 1
i

Igor Lukačević The variational principle

The variational principle
The linear variational problem

ψe normalized trial function depends on α1 , α2 . . .

hψ|H|
e ψie very complex function of α1 , α2 . . .
Suppose
N
X
|ψi
e = ci |ψi i , hψi |ψj i = δij
i=1

=⇒ (H)ij = Hij = hψi |H|ψj i matrix representation in basis {|ψi i}


H hermitian
⇒ H symmetric
{|ψi i} real
X
ψe normalized ⇒ ci2 = 1
i
the expectation value depends on cij :
X
=⇒ hψ|H|
e ψi e = cij Hij
ij

Igor Lukačević The variational principle

The variational principle
The linear variational problem

X
ψe normalized ⇒ ci2 = 1
i
the expectation value depends on cij :
X
=⇒ hψ|H|
e ψi e = cij Hij
ij

Unfortunately,
∂ e
hψ|H|ψi
e = 0 , k = 1, 2, . . . , N
∂ck
is unsolvable for ck are mutually dependent.

Igor Lukačević The variational principle

The variational principle
The linear variational problem

X
ψe normalized ⇒ ci2 = 1
i
the expectation value depends on cij :
X
=⇒ hψ|H|
e ψi e = cij Hij
ij

Unfortunately,
∂ e
hψ|H|ψi
e = 0 , k = 1, 2, . . . , N
∂ck
is unsolvable for ck are mutually dependent.

Lagrange’s method of undetermined multipliers

 
L(c1 , . . . , cN , E ) = hψ|H|
e ψi e − E hψ| e −1
e ψi
!
X X
= ci cj Hij − E ci2 −1
ij i

Igor Lukačević The variational principle

The variational principle
The linear variational problem

Unfortunately,
∂ e
hψ|H|ψi
e = 0 , k = 1, 2, . . . , N
∂ck
is unsolvable for ck are mutually dependent.

Lagrange’s method of undetermined multipliers

 
L(c1 , . . . , cN , E ) = hψ|H|
e ψi e − E hψ| e −1
e ψi
!
X X
= ci cj Hij − E ci2 − 1
ij i

hψ|H|
e ψi e and L are minimal for same ck

Igor Lukačević The variational principle

The variational principle
The linear variational problem

Let us now choose c1 , c2 , . . . , cN−1 as independent

X 2
⇒ cN is given by ci = 1
i

Igor Lukačević The variational principle

The variational principle
The linear variational problem

Let us now choose c1 , c2 , . . . , cN−1 as independent

X 2
⇒ cN is given by ci = 1
i

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

Igor Lukačević The variational principle

The variational principle
The linear variational problem

Let us now choose c1 , c2 , . . . , cN−1 as independent

X 2
⇒ cN is given by ci = 1
i

Then we have
∂L
= 0, k = 1, 2, . . . , N − 1
∂ck
but not necessarily
∂L
=0
∂cN
But we still have undetermined multiplier E , so now we choose it so that
∂L
= 0, k = 1, 2, . . . , N − 1, N
∂ck

Igor Lukačević The variational principle

The variational principle
The linear variational problem

Let us now choose c1 , c2 , . . . , cN−1 as independent

X 2
⇒ cN is given by ci = 1
i

Then we have
∂L
= 0, k = 1, 2, . . . , N − 1
∂ck
but not necessarily
∂L
=0
∂cN
But we still have undetermined multiplier E , so now we choose it so that
∂L
= 0, k = 1, 2, . . . , N − 1, N
∂ck
On the other hand
∂L X X
= cj Hkj + ci Hik − 2Eck
∂ck j i

Igor Lukačević The variational principle

The variational principle
The linear variational problem

Then we have
∂L
= 0, k = 1, 2, . . . , N − 1
∂ck
but not necessarily
∂L
=0
∂cN
But we still have undetermined multiplier E , so now we choose it so that
∂L
= 0, k = 1, 2, . . . , N − 1, N
∂ck
On the other hand
∂L X X
= cj Hkj + ci Hik −2Eck
∂ck j i
| {z }
equal, since Hij =Hji

So, X
Hij cj − Eci = 0
j

Igor Lukačević The variational principle

The variational principle
The linear variational problem

Or in matrix form
Hc = E c

A question
What represents this equation?

Igor Lukačević The variational principle

The variational principle
The linear variational problem

Or in matrix form
Hc = E c
X
α
⇒ Hc = Eα c , α
α = 0, 1, . . . , N − 1 , (cα )† cβ = ciα ciβ = δαβ
i

Igor Lukačević The variational principle

The variational principle
The linear variational problem

Or in matrix form
Hc = E c
X
α
⇒ Hc = Eα c , α
α = 0, 1, . . . , N − 1 , (cα )† cβ = ciα ciβ = δαβ
i

Eαβ = Eα δαβ , Ciα = ciα =⇒ HC = EC

Igor Lukačević The variational principle

The variational principle
The linear variational problem

Or in matrix form
Hc = E c
X
α
⇒ Hc = Eα c , α
α = 0, 1, . . . , N − 1 , (cα )† cβ = ciα ciβ = δαβ
i

Eαβ = Eα δαβ , Ciα = ciα =⇒ HC = EC

Solving gives N orthonormal solutions
N
X
|ψeα i = ciα |ψi i , α = 0, 1, . . . , N − 1
i=1

Igor Lukačević The variational principle

The variational principle
The linear variational problem

Or in matrix form
Hc = E c
X
α
⇒ Hc = Eα c , α
α = 0, 1, . . . , N − 1 , (cα )† cβ = ciα ciβ = δαβ
i

Eαβ = Eα δαβ , Ciα = ciα =⇒ HC = EC

Solving gives N orthonormal solutions
N
X
|ψeα i = ciα |ψi i , α = 0, 1, . . . , N − 1
i=1

What about E ’s:

hψeβ |H|ψeα i = Eα δαβ

Igor Lukačević The variational principle

The variational principle
The linear variational problem

HC = EC
Solving gives N orthonormal solutions
N
X
|ψeα i = ciα |ψi i , α = 0, 1, . . . , N − 1
i=1

What about E ’s:

hψeβ |H|ψeα i = Eα δαβ
For example,
E0 = hψe0 |H|ψe0 i ≥ E0

A question
What’s the meaning of other E ’s?

Igor Lukačević The variational principle

The variational principle
The linear variational problem

HC = EC
Solving gives N orthonormal solutions
N
X
|ψeα i = ciα |ψi i , α = 0, 1, . . . , N − 1
i=1

What about E ’s:

hψeβ |H|ψeα i = Eα δαβ
For example,
E0 = hψe0 |H|ψe0 i ≥ E0

A question
What’s the meaning of other E ’s? Eα ≥ Eα , α = 1, 2, . . .

Igor Lukačević 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 {|ψi i , i = 1, 2, . . . , N}.

Igor Lukačević The variational principle

The variational principle
Literature

Contents

1 Theory

2 The ground state of helium

3 The linear variational problem

4 Literature

Igor Lukačević The variational principle

The variational principle
Literature

Literature

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

Advanced Electronic Structure theory, Dover Publications, New York,
1996.
2 D. J. Griffiths, Introduction to Quantum Mechanics, 2nd ed., Pearson
Education, Inc., Upper Saddle River, NJ, 2005.
3 I. Supek, Teorijska fizika i struktura materije, II. dio, Školska knjiga,
Zagreb, 1989.
4 Y. Peleg, R. Pnini, E. Zaarur, Shaum’s Outline of Theory and Problems of
Quantum Mechanics, McGraw-Hill, 1998.
5 I. N. Bronštejn, K. A. Semendjajev, Matematički priručnik, Tehnička
knjiga, Zagreb, 1991.

Igor Lukačević The variational principle