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" = #c ! i i .
i
The corresponding “bra” is " = ! ci* i where ci* is the complex conjugate of ci.
i
The ket is an abstract quantity that represents a quantum state. Often, we wish to be
more specific an explicit representation that gives us information about (for example)
spatial (position) distribution of electron density. To do this, we “project” the ket onto the
bras that are the eigenstates of position. The resulting function is called the wave
function (in the position representation). An explicit example of a set of basis wave
functions are the hydrogen ground state orbitals used to develop the states of the
diatomic molecule, linear chain, etc.:
1/ 2
2 (ri / a0 & 1 #
*i ( r ) = e '$ !
a03 % 4) "
where a0 is the Bohr radius and ri is the radial distance of the electron from the ith
nucleus.
(We will rarely actually use the explicit forms of these basis functions. Rather we make
use of their mathematical properties such as orthogonality and normalization – see
below.)
Projections – scalar products:
The coefficients in the linear combination are the projections of ! on the basis states
i , i.e. ci = i ! where the object i ! is a scalar product analogous to the “dot” product
of ordinary vectors. The scalar product of two state vectors (or the projection of one
on the other) is a sum of! products of their respective projections on the basis (again just
!
like ordinary vectors: a ! b = a x bx + a y by + a z bz ). Thus,
" ! = #" i i! .
i
If we were using explicit functions of spatial coordinates to represent the states ! and
! , we would evaluate the projection with an integral
* ! !
# " = !# (r )" (r )dV .
all space
PH575 SPRING 2012
The quantity ! " is often called the "overlap integral". It represents "how much" of one
function is "contained" in another. The overlap integral of orthogonal functions (see
below) is either zero or one.
The orthonormal property usually assumed for the basis states can be expressed in
terms of their scalar products:
j i = 1 if i = j; j i = 0 if i ! j .
State vectors ! are usually normalized: ! ! = 1 . This leads to the result that
* 2
!c c = ! c
i
i i
i
i =1
2
The quantity ci is the probability that in a measurement, an electron will be found in the
particular basis state i . The normalization condition simply expresses the fact that the
electron must be found in some basis state, thus the sum of all probabilities equals 1.
Operators
In quantum mechanics, observable physical quantities are represented by operators.
There are two cases to consider:
Case I: An operator L “operates” on a state vector ! and yields the same state
vector simply multiplied by a constant:
L ! = CL ! .
L ! = constant " # .
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The matrix elements of an operator L are expressed in terms of a particular basis set
i . They are scalar products of a basis bra j and the ket produced by the action of L
on i , i.e. j L i = L ji .
When i = j, the “diagonal” matrix element i L i = Lii is the “expectation value” of the
physical quantity represented by L in the particular basis state i . If, in addition, i is an
eigenvector of L, then Lii is just the eigenvalue CL. For example, if L is the energy
operator H and our basis states are the atomic ground states, then Hii is the energy of
an electron in the ground state of atom i.
The corresponding “bra” is " = ! ci* i where ci* is the complex conjugate of ci.
i
where a0 is the Bohr radius and ri is the radial distance of the electron from the nucleus.
Projections are really integrals. The notation means integrate over all space, in
" " "
the function ! ( r, ! , " ) into the integral and the notation 1s means insert the complex
conjugate function ! 1s* ( r, ! , " ) into the integral. Thus:
2& & $
Because we can look up the position representation of basis wave functions, we can
plug in and evaluate. But because the basis functions of the Hamiltonian are orthogonal
to one another, the integration is not necessary (but you should check that it actually
does evaluate to 1 or zero)!
! 1 2 $ 1 2 1
1s ! = 1s # 1s + 2 pz & = 1s 1s + 1s 2 pz =
" 5 5 % 5 !" # 5 !"
$ $
# 5
1 0
! 1 2 $ 1 2 2
2 pz ! = 1s # 1s + 2 pz & = 2 pz 1s + 2 pz 2 pz =
" 5 5 % 5 !"
# # $ 5 !#"# $ 5
0 1
The scalar product of two state vectors (or the projection of one on the other) is a sum
of products of their respective projections on the basis (again just like ordinary vectors:
! !
a ! b = a x bx + a y by + a z bz ). Suppose another state of the H-atom is represented by
1 1
! = 1s + 3px . Then the projection of ! onto ! is
2 2
! 1 2 $! 1 1 $
! " =# 1s + 2 pz & # 1s + 3px &
" 5 5 %" 2 2 %
1 1 2 2 1
= 1s 1s + 1s 3px + 2 pz 1s + 2 pz 3px =
10 !"# 10 !"
$ $ # 10 !"
$ $ # 10 !$"$ # 10
1 0 0 0
" ! = #" i i! .
i
Or we could evaluate the projection with the integral
! !
# " = !# * (r )" (r )dV .
all space
The quantity ! " is often called the "overlap integral". It represents "how much" of one
function is "contained" in another. The overlap integral of orthogonal functions (see
below) is either zero or one.
Operators
!! 2 2 e2
Case I: The Hamiltonian operator H =
" ! “operates” on a state vector
2m 4!" 0 r
and yields the same state vector simply multiplied by a constant. Examples are the
PH575 SPRING 2012
states 1s , 2 pz 3px
!e 2 !e 2 !e 2
H 1s = 1s ; H 2 pz = 2
2 p z ; H 3p x = 2
3px
2a0 2a0 ( 2 ) 2a0 (3)
In this case 1s , 2 pz 3px are eigenstates of the operator H, which is why we chose
them as the basis states. The eigenvalues are the energies of the respective orbitals.
!! 2 2 e2
Case II: The Hamiltonian operator H = " ! “operates” on a state vector
2m 4!" 0 r
and yields a different state vector (multiplied by some constant). Examples are ! and
!e 2
! , which are NOT eigenvalues of H. For example, H ! = " where the ket !
52a0
is found below:
! $
! 1 2 $ 'e 'e 2 2
'e2 # 1 &
H ! = H# 1s + 2 pz & = 1s + 2
2 pz = # 1s + 2 pz &
" 5 5 % 52a0 5a0 ( 2 ) 52a0 # !##"4 ##
$&
" ! %
The matrix elements of the Hamiltonian H are expressed in terms of a particular basis
set i . They are scalar products of a basis bra j and the ket produced by the action of
H on i , i.e. j H i = H ji . If the basis vectors are eigenfunctions, the matrix is diagonal.
For example:
H1s,1s = 1s H 1s = E1s 1s 1s = E1s
H1s,2s = 1s H 2s = E2s 1s 2s = E1s .0 = 0
1s ! E1 0 0 0 0 0 $
# &
2s # 0 E2 0 0 0 0 &
2 px # &
# 0 0 E2 0 0 0 &
2 py # 0 0 0 E2 0 0 &
# &
2 pz # 0 0 0 0 E2 0 &
# 0 0 0 0 0 E3 &%
3s "
The “diagonal” matrix element i L i = Lii is called the “expectation value” of the
physical quantity represented by L in the particular basis state i .
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Using the same basis states to express the Lz operator, we find the matrix is NOT
diagonal because the px and py states are not eigenfunctions of the Lz operator:
Lz 1s 2s 2 px 2 py 2 pz 3s
1s
" 0 0 0 0 0 0 %
2s
$ 0 0 0 0 0 0 '
2 px $ '
$ 0 0 0 !0 0 0 '
2 py $ 0 0 !0 0 0 0 '
$ 0 0 0 0 0 0 '
2 pz $ '
# 0 0 0 0 0 0 &
3s