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Dirac Notation
A powerful & concise formalism (also known as bra-ket / bracket notation) Two mathematical traditions: Heisenberg matrix mechanics vs. Schrdinger wave mechanics (matrices & vectors) (integrals). Computationally different but formally equivalent. Each has strengths & weaknesses. Dirac notation is a useful first step when a QM calculation is set up. (Then choose matrix or wave mechanics depending on which is computationally easier).
is a vector
it contains what is known (e.g. p=2, or x=3) if we put a function into the Ket, e.g. | it represents a system in an eigenstate (also called a state vector)
The Bra: |
is also a vector represents the final state of the system. e.g. x=3| specifies final state has position x=3. can be used in conjunction with a Ket. e.g. x=3| is the probability amplitude of at position x=3. can be squared to give a probability. e.g. |x=3||2 is the probability of finding the particle at x=3.
alternatively, a Bra can contain the variable in which to express the ket. e.g.
x = (x ) = 2 sin ( x ) = 2 sin (x )
We might equally want in terms of momentum, in which case,
e.g.
is the projection of the state onto the state . is equal to the probability amplitude that a system starting in state will end up in state .
A Ket-Bra product is sometimes referred to as an overlap integral. It is formally equivalent to the integral notation you have seen previously:
= *d
= *d
(we will see a proof of this in a few slides)
=
Hence,
Also, the Ket is the transpose of its corresponding Bra. (See maths catch-up notes: matrices section)
Ket-Bra products, | |
x x
we get
x x
to
In higher dimensions, we can think of a vector as being equal to the sum of its components in each orthogonal direction.
a,
the projection onto each of its component parts in the orthogonal (and normalised) direction vectors i and j is given by
a= i ia + j ja
i i + j j =1
Generally, when there are n discrete, orthogonal basis states, the sum of the identity operators over these states is given by
n
n
n =1
When the basis states are not discrete (e.g. position) , the sum becomes an integral:
n dx = 1
= n n
n
= n n dx
= x x dx = * ( x ) ( x )dx
Notice that here we have replaced the vertical bar with the identity operator (and summed over all basis states) once the problem is written down (i.e. the basis set is chosen) we can evaluate this integral using traditional techniques.
Hence we have shown the equivalence of a Dirac Bra-Ket projection with the overlap integral of wave mechanics
We could show the same result by thinking of | and | as linear superpositions of the eigenstates of position, x:
= x x dx
and
x' x = 0
x' x = x x = 0
Examples of Superposition
The following few slides show how superposition can be applied to QM problems. The examples themselves arent important, but the techniques are...
Particle Spin
The electron possesses an internal angular momentum called the spin. It can assume two values (up and down) in some arbitrarily chosen direction. Lets say that we specify the z direction as direction in which the spin is defined. Then the eigenstates can be given (in units of h/4) by the vectors below: spin up in the z direction:
1 S z ,up = 0 0 S z ,down = 1
These are kets because they denote the state of the system
These vectors form a complete, discrete basis set (i.e. they describe all the states that are possible).
1 0 0 = 1 0 + 0 1 = 0 1
1 2 2 0 = 1 + 0 =1 0 2 2 1 = 0 +1 = 1
What if we want to know the spin vector in a different basis, i.e. the orthogonal direction, x ? Answer: We need to translate the eigenstates into the language we want, i.e. from spin along the z axis, to spin along the x direction. To do so we can take linear combinations of the two z-axis eigenstates:
S x ,up =
1 S z ,up + S z ,down 2
) )
S x ,down =
1 S z ,up S z ,down 2
Note the factor 1/2, which is required to normalise the linear combinations, because:
Answer:
S x ,up =
1 S z ,up + S z ,down 2
S x ,down =
1 S z ,up S z ,down 2
1 2
1 2 1 2
1 0 + 0 1
1 2
1 2 1 2
1 0 0 1
Notice that these two basis states are orthogonal (dot product = 0).
Similarly, these two basis states are also orthogonal (dot product = 0).
So, and
Exercise:
Determine whether
S x ,up
is orthogonal to
S z ,up
Answer: We need to find the angle between the two vectors, so we work out the dot product:
S x ,up S z ,up =
1 2 1 2
1 = 0
1 2
1 +
1 2
0 =
1 2
= 45o
i.e. they are not orthogonal. this means that S x ,up and S z ,up are not discrete basis states
10
S x ,up =
1 2 1 2
Given this starting state, Dirac notation allows us to calculate the probabilities of getting either spin up or spin down as the result of an experiment to measure spin along the x axis:
= 1 =1
2 2
=0
i.e. every experiment will give a measurement of spin up, when measured along the x axis.
What is the probability of getting a result of spin up if we try to measure spin along the z-axis? To find the probability, we must evaluate the following bra-ket pair: probability amplitude of ending up in spin up along z axis, given that the starting state is spin up along the x axis To evaluate the Bra-Ket pair we take the dot product of the two state vectors
S z ,up S x ,up 1 = 0 = 1 2
1 2 1 2
= 1
1 2
+ 0
1 2
11
Similarly, the probability of getting a result of spin down along the z axis, given that the starting state is spin up along the x axis is given by
S z ,down S x ,up
1 2
Conclusions When the system starts in the state |Sx,up, every measurement of the spin in the x direction will give the same result: spin up. But measurement of spin in the z direction yields spin up in 50% of the experiments and spin down in the other 50%.
i.e Spin is well determined in the x-direction but not determined in the z direction.
NOTE: Linear superposition is NOT a mixture. We cannot regard |Sx,up as a 50/50 mix of |Sz,up & |Sz,down, because |Sz,up and |Sz,down are themselves linear superpositions of |Sx,up & |Sx,down:
S z ,up =
1 S x ,up + S x ,down 2
) )
S z ,down =
1 S x ,up S x ,down 2
If |Sx,up were a mixture of |Sz,up and |Sz,down, it would give an indefinite measurement of spin in the x-direction, despite the fact that its an eigenfunction of the x-spin operator.
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= n n
n
Projection of onto the eigenstate n i.e. the contribution that n makes to , in other words, just a number. Equivalent to cn coefficients you met with TRW. Thus,
= n cn
n
Consider a trial wave function for the particle in a box of length 1. (For the time being, lets just say we have pulled it out of a hat).
(x ) = 105 x 2 x 3
Is this trial wavefunction any good to describe any of the true eigenstates of the system? Remember that previously, we solved the particle in a box problem exactly and got the following expression for the complete basis:
13
Because a state is given by a linear combination over the entire basis (due to the completeness condition), i.e.
= n cn
n
it is possible to expand the trial eigenstate (using software) into a linear combination of the true, orthogonal, eigenstates. The first few coefficients come out as follows:
105 x 2 x 3 = 0.935
2 sin (x )
-0.351
= 0.935
-0.351
+0.0035
+...
The first coefficient is 0.935. This tells us that the trial function has a good deal of the true n=1 wavefunction in it.
However it wasnt quite right! It is an infinite expansion that includes bits of the entire basis set.
14
Thus, matrices operate on vectors to give information about the state of the system. Note that a matrix, operating on (i.e. multiplying by) a vector gives a vector as the answer.
All observables have an associated operator. A system is either in a well defined state, or it isnt.
Example:
For spin, the operators are given (in units of h/4) by:
0 1 = S x 1 0
1 0 = S z 0 1
If we apply the spin operator to a spin state vector, we get the following:
0 1 S = S x x ,up 1 0
i.e.
1 2 1 2
1 2 1 2
S S x x ,up = S x ,up
15
1 0 S S = z x ,up 0 1
1 2 1 2
1 2 1 2
= S x ,down
=a A = a A =a A A
A QM eigenvector equation
a=
expression for a.
divide by
to leave an
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When the observable is energy, the operator is known as the Hamiltonian, and the expectation values for the energy is given by
E=
If is normalized, this simplifies to give a simple expression for the expectation value for energy:
E= H
Once more, this is analogous to the integrals you have seen already. i.e.
d E = *H
We can demonstrate this equivalence by looking at the expectation value for the position of a system in a state |:
x
the position operator Lets see what happens when we expand | into the states of the position operator:
= x x x dx x = x x x dx = * ( x ) x ( x )dx
x =xx = x x x
17
S S S x ,up z x ,up =
1 2
1 2
1 0 0 1
1 2 1 2
=0
final state
initial state
The result of 0 is consistent with the idea that 50% of the time we will get spin +1 and 50% of the time we will get spin = 1 (hence giving a mean of 0).
x x = exp i 2
But de Broglies relation tells us that
p=
hence
h p
18
x =xx x p =p p p
But what about the momentum operator in coordinate space? We can use Dirac notation to help us out (surprise!)
= x p
h d x i dx
Matrix Elements
This section is based on Atkins MQM. See the book for more details...
The fundamental commutation relation of mechanics, implies that x and px are operators.
[x, px ] = ih
19
Mrc is shorthand for the element of matrix M that occurs in and column c.
row r
For rules of matrix algebra, see PWB maths catch up notes, or Just the Maths on the web. Briefly, for multiplication: the product AB is another matrix C
C rc = A rn B nc
n
AB BA 0
xp x p x x = ihI
I is the unit matrix: square with all diagonals = 1, and all other elements = 0
n mA
A mn
n mA
20
a diagonal matrix element is a Bra-Ket of the form (i.e. Bra and Ket refer to the same state.)
m mA
s sA c rA
s sB B c = r A c r A
invoke the completeness condition in reverse
i.e. the sum is a single matrix element (bra-ket) of the product of the operators.
Exercise
Use the completeness condition to prove that the eigenvalues of the square of a Hermitian operator are non-negative. i.e. prove that for
2 x = x x A
then x 0 if is Hermitian
n = nA m mA
2 x = x x x = x x x = x 1 = x xA
21
2 x xA A x = xA n nA x = x A
n
=
n
n xA n xA
2
write the Bra-Ket on the right the other way round (it becomes the conjugate: remember the definition of a Hermitian operator) for a complex number z, z(z*) is always positive, so the sum over n will be positive.
n = x A
n
f ) = A f (A
*
22
Real chemical problems cannot be solved analytically, so this is important! Variational method lies at the root of (amongst many other things) MO theory, i.e. by building wavefunctions from linear combinations of hydrogenic wavefunctions.
The Variation Principle: If an arbitrary wave function is used to calculate the energy, then the value calculated is never less than the true energy
If we adjust the coefficient(s) of the arbitrary wavefunction until we get the lowest energy, then those coefficients are best i.e. closest to the true wavefunction.
We may be able to lower the energy by using a more complicated trial wavefunction (e.g. a by taking a linear combination of known eigenstates of a similar problem, such as hydrogenic atomic orbitals)
23
Detour: Is it valid to split the expression for energy into a linear combination of eigenstates?
Lets expand in terms of the eigenstates, |n of the system, using the completeness condition:
E= H n n = H
n
n H
by
En En = n E
So
E= n E n
n
We have to figure out how to evaluate these integrals. if we are solving in coordinate space (x) then we can expand them, (once more, using the completeness condition)
E = x x n dxE n x x dx
n
E=
n
( x
*
x n dx En
) ( n x
x dx
E=
n
( x
n x dx En
) ( n x
x dx
24
E = cn E n
2 n
This is the result that you saw in TRWs lectures i.e. when you have a linear superposition of wavefunctions,
= c11 + c2 2 + ...
then the expectation value for the energy is equal to the square of the coefficients, multiplied by the energy of each state. i.e.
E = c1 E1 + c2 E2 + ...
2 2
Final Comments
Comparison of
with
tells us that
H = n E n
n
i.e. the Hamiltonian can be written as a sum of projection operators involving the eigenstates (i.e. energy levels)
25
Back to the Variational principle Why is the energy always greater than the true energy?
Lets revisit particle in a box Weve already seen how this system can be solved exactly, so its a good (i.e. simple!) system to demonstrate the results of the variational method. Well not actually solve the problem here rather we look at the results and then revisit the variational method later. We pick an trial wavefunction:
(x ) = ax(1 x )
Recall that the eigenfunctions of the Hamiltonian (i.e. the complete solution) for L=1 is given by
n = 2 sin (nx )
with
En =
n 2 2 2
Each measurement will give a particular energy, En, (i.e. one of the eigenvalues of the Hamiltonian).
26
Minimising the energy in the above problem gives an optimised trial wavefunction of:
( x ) = 30 x(1 x )
Which you may recall looks very much like the true E1 eigenstate of the particle in a box.
Using software to find the expansion coefficients of the true eigenfunctions gives:
c12 = 0.9987 c32=0.0014 c52 = 0.00006 c72 = 0.00001 All others are 0 (or really small)
E1 =
12 2 = 4.93 2
Note that in the real world, we dont have the exact eigenfunctions at our disposal thats precisely why were employing the variational method! Thus, this example is for illustration only
In this example, the first term in the linear expansion is by far the most important, Thus we can see that is a pretty good approximation to the first pure eigenstate, E1.
27
The Variational Theorem says that no matter how hard you try in constructing trial wavefunctions, you cant get lower than the true ground state energy.
Why?
The only way can give the correct result for the energy of the ground state of the particle in the box, is if our trial wavefunction was (by chance!) equal to the ground state eigenfunction itself. In which case,
c1 = 1,
cn >1 = 0
< 1, and other values, cn >1, are non zero. Thus the energy has to be greater than E1.
...but first a little diversion into Perturbation Theory, which is a different approximate method.
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= E H +V = E T
h2 2 ze 2 ze 2 e2 2 2m 1 + 2 + 4 r + 4 r + 4 r = E 0 1 0 2 0 3
For simplicity, from now on, we will omit the constant factor 1/40 from the Coulomb potential. Now lets rewrite the Hamiltonian in a slightly different way:
h 2 2 ze 2 h 2 2 ze 2 e 2 H = + r + 2m 2 r 2m 1 r 1 2 3
= H
H0
+ H'
Note that H0 is the sum of the H-like Hamiltonians for each of the two electrons:
H 0 = h0 (r1 ) + h0 (r2 )
with
2e 2 h2 2 h0 (r ) = r 2m
29
Weve already solved the Schrdinger equation for the H atom and obtained an s atomic orbital as the ground state. The 1s wavefunction of a H atom,
1s (r ) , satisfies
h0 (r )1s (r ) = E1s 1s (r )
Energy of hydrogenic 1s orbital What if we ignore the electron-electron interaction in He? (i.e. what if we ignore the Hamiltonian H ) Then the 2 electrons will then be independent of one another and we need only consider the 2 electron system with H0. We shall call this a reference Hamiltonian.
Each electron will follow its own H-like Hamiltonian h0 and occupy the 1s orbital independently. Note: here we neglect here the of the electron and implicitly assume that they are antiparallel. The Schrdinger equation for He is then
H 0 (0 ) (r1 , r2 ) = E (0 ) (0 ) (r1 , r2 )
with solution:
30
Question:
What assumption allows us to say that
Exercises
1. Using
h0 (r )1s (r ) = E1s 1s (r )
, show that
(0 )
is a solution of H 0
(r1 , r2 ) = E (0 ) (0 ) (r1 , r2 )
2. Express E(0) in terms of E1s. How can you explain this in terms of the assumed relation between the two electrons?
EH = hcRH = 13.6 eV
Express E1s in terms of EH and z.
31
zr 1 z 2 exp 1s (r ) = a a 0 0
Bohr radius
(0 )
H'
(0 )
1 z = 2 a 0
(0 ) H ' (0 ) =
5 zE H 4
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5 11 E1 E (0 ) + (0 ) H ' (0 ) = 2 z 2 z E H = E H = 74.80 eV 4 2
(Remember, we are ignoring the 1/40 here )
we can think of as the effective nuclear charge which takes into account the shielding effect of the second electron.
33
If we optimise to minimise the energy, will be less then z. This lower effective z will mean that the orbitals are bigger. We can justify this as being due to e-e repulsion. So our job is to find the minimum of the function
E ( ) = H
The integral is similar to the one we saw for perturbation theory, and the result is
5 E ( ) = 2 2 + 4 z EH 4
This quadratic equation has 1 minimum which determines the best Question: find . Is it bigger or smaller than z? How do you interpret it?
Variation
Experiment
-77.45
-78.98
IP / eV
20.40
23.05
24.58
34
Method:
1. Divide the Hamiltonian into a known, reference Hamiltonian, H0, and a small remaining part, V:
H = H0 +V
(0 ) (0 )
H 0 n
(0 )
= En n
(n = 0,1,2,...)
3. Use the solved expressions for n(0) and En to find approximate solutions to the full Schrdinger equation:
H n = En n (n = 0,1,2,...)
En = En
(0 )
(0) (0) V n + n + k n
En
(0 )
Ek
(0 )
+ ...
In the He example, we only used the first term i.e. it was first order.
Weaknesses: perturbation theory breaks down when there are degeneracies (i.e. En(0) = Ek(0)).
n =
( 0) n
+
k n
(0) V k( 0) n
En
(0 )
Ek
(0 )
k( 0 ) + ...
(this is a mixing coefficient)
35
The modification to n(0) to give n is given by other functions k(0) The mixing coefficients are proportional to the integral i.e. the bigger the overlap between k(0) n(0) the higher the mixing coefficient a.k.a. the transition matrix element
( 0) n V k( 0 )
En
(0 )
1 (0 ) Ek
This means that the coefficient is bigger when the energies are similar. i.e. nearly degenerate states mix better
Diatomic Molecules
AB
The Variational Method is versatile: any sensible trial function will do. Often a linear superposition of basis states is easiest:
( x ) = cn f n ( x )
n
coefficients taken as variational parameters Remember, the aim is to optimise the variational parameters to minimise the energy
36
For a diatomic molecule, there are two atoms, each supplying one electron to the covalent bond. Thus our linear combination of hydrogenic basis functions will look like this:
= c A A + cB B
The basis wavefunctions are normalised but at this stage, not necessarily orthogonal. i.e. the overlap integral, S is given by
S AB = B A 0
A H B
as a matrix element:
H AB
37
E AA = A H A E BB = B H B
E AB = B H A E AB = A H B
Expectation value for resonance energy of electrons delocalised across both atoms.
These matrix elements may be... calculated (as for He atom earlier) or estimated from spectroscopy or simply taken as parameters (see Hckel
theory later)
E=
c A A + cB B H c A A + cB B c A A + cB B c A A + cB B
expand Bra-Kets
extract constants
gather like terms, and notice that SAA = SBB = 1 provided that A and A are normalised
38
we must then vary the parameters cA and cB in order to minimise this energy. The minimum will occur when
E =0 c A
and
E =0 cB
E=
E H =0
in full,
E c A + 2c AcB S AB + cB c A H AA + c AcB (H AB + H BA ) + cB H BB = 0
2 2 2 2
) (
39
E c A + 2c AcB S AB + cB c A H AA + c AcB (H AB + H BA ) + cB H BB = 0
2 2 2 2
) (
) (
E ) (2c H c
A A
AA
+ 2cB H AB ) = 0
When
E = 0 this becomes: c A
(H AA E )cA + (H AB ES AB )cB = 0
Similiarly, from
E = 0 we get: cB
H AA E H ES BA BA
H AB ES AB cA 0 = H BB E cB 0
Now is a good time to review the catch-up maths notes if you havent done so already. Make sure that you can find the eigenvalues and eigenvectors of a 2x2 matrix
40
H AA E H ES BA BA
H AB ES AB H AA = H BB E H BA
H AB 1 S AB E H BB S BA 1
H AA H BA
H AB 1 S AB c A 0 E 0 S c = H BB 1 BA B
In an abstract and more general form (i.e. which is applicable to any number of electrons and not just the 2 we are looking at here), it is:
(H ES ) c = 0
This allows us to get a value for the energy, E, of the MOs, and the coefficients of the AO linear combinations.
H ES
H ES = 0
This is called the secular equation and it can be solved to give the energy, E, of the MOs.
When we have the eigenvalues, E , we can then find the atomic orbital coefficients, c, from
(H ES ) c = 0
(Actually, in our 2 electron case, it will only give a ratio for cA / cB i.e. you have to guess one number and the other can be calculated. Ultimately, normalisation will give the absolute values of cA and cB)
41
We can simplify things at this stage by choosing an orthonormal set of atomic orbitals as the basis set. Then the overlap integrals become either 1 or 0:
S AB = B A = 0 S AA = A A = 1
This means that the overlap matrix turns into the identity matrix:
S=I
Hence,
(H ES )c = 0 (H EI )c = 0
Hc Ec = 0 Hc = Ec
This is a matrix eigenvector problem which is easily solved. (Check the maths notes for how to do it by hand for a 2x2 matrix.) Reminder: this isnt the Schrdinger equation! H is a matrix of energy integrals, and not an operator matrix. c just gives the coefficients of the linear combination of atomic orbitals. For bigger matrices, this is done by diagonalisation using computers.
42
H AA H BA
H AB c A cA = E c H BB cB B
eigenvector equation
H AB c A H AA E H =0 H BB E BA cB
H AA E H BA H AB H BB E =0
(H AA E )(H BB E ) H AB H BB = 0
E 2 (H AA + H BB )E (H AA H BB H AB H BB ) = 0
E 2 (H AA + H BB )E (H AA H BB H AB H BB ) = 0
E=
1 (H AA + H BB ) 2
( H AA H BB )2 + 4a(H AA H BB H AB H BB )
We wont do it here, but you would then substitute these values for E into the equation
(H ES ) c = 0
to find c1/c2
43
Hckel MO Theory
A simple treatment of the MOs of conjugated planar hydrocarbons A series of approximations to help us solve the secular equation It is a semi-empirical method as it relies on experimental data. We consider only one pz atomic orbital per C atom involved in the delocalised system., which comes from a 2pz AO We describe the molecular orbitals as a linear combination of these 2pz atomic orbitals.
That the basis set, the 2pz atomic orbitals, are orthonormal, i.e.
S=I
(Note that if this were strictly true there would be no bonding! Neighbouring atoms will have p overlap, but much smaller than the 2p overlap) All the overlap integrals (Sij) are set to 0. All the diagonal elements of the Hamiltonian matrix are represented by a single parameter, . i.e. H11 = H22 = ... = The off diagonal elements are set to different common parameter, Hij = , but only when atoms i and j are connected. Otherwise, Hij = 0
44
Implications of setting diagonal energy elements to , and all non diagonal energy elements are 0 unless atoms are touching:
This implies that the energy is purely atomic in nature. It is consistent with a picture of bonding that is fully delocalised across the whole system and the environment of the atom can be neglected. A result is that conformational isomers such as cis- / trans- are not distinguished from one another.
This molecule has 4 carbon atoms contributing to the system, so we use four 2pz atomic orbitals. Thus we are looking for 4 MOs that are linear combinations of the 4 atomic pz orbitals:
2 = c5 A + c6B + c7C + c8D 3 = c9 A + c10B + c11C + c12D 4 = c13 A + c14B + c15C + c16D
45
Hc = Ec
4pz atomic orbitals means that the Hckel Hamiltonian is a 4x4 matrix. Thus we have...
c1 0 0 c1 c2 0 c2 E = c 0 c 3 3 0 0 c c 4 4
E 0 0 E 0 =0 E 0 E 0 0
46
If we really had to work it out by hand, the determinant of the secular equation would expand as follows:
( E )4 3 2 ( E )2 + 4 = 0
( E )
= 3 2
( 3 )
2
1
2 2
4 4
3 5 = 2 2
3 5 2 E = 2
47
We neednt stop here: we can find the eigenvectors too, i.e. the coefficients of the four AOs in each MO...
If we go to the trouble of normalising these eigenvectors, we get the following coefficients for the linear superposition of atomic pz orbitals:
c1 0.372 0.602 0.602 0.372 c2 0.602 0.372 0.372 0.602 c = 0.602 , 0.372 , 0.372 , 0.602 3 c 0.372 0.602 0.602 0.372 4
48
MO Energy levels in Butadiene calculated using Hckel approximation (as viewed down the axis of the pz-orbitals)
Now that we have the coefficients for the linear superposition, we can sketch the wavefunctions
49
Homework...
1. Calculate the Hckel MO energies and coefficients for ethylene (C2H4) 2. For the allyl cation (C3H5+), work out the Hckel MO energies and if youre up to the challenge, calculate the coefficients as well.
3. Write down the Hckel Hamiltonian for benzene and for hexatriene (C6H8). How do they differ?
1. Ethylene
Hc = Ec
c1 c1 = E c c 2 2
c1 0 E = E c2 0
50
E =0 E
( E )( E ) 2 = 0
2 2E + E 2 2 = 0
E = ( + ) E = ( )
solving, we get:
To find the coefficients for each MO, we must substitute eachvalue for E in turn into the eigenvector equation...
For E = + :
c1 c1 = ( + ) c c2 2
c1 + c2 = ( + )c1 c1 ( + )c1 = c2 c1 = c2 c1 = c2
51
For E = -
c1 c1 ( ) = c c 2 2
c1 + c2 = ( )c1 c1 ( )c1 = c2 c1 = c2 c1 = c2
1 = c1 A c1 B 2 = c1 A + c1 B
Finally, we must normalise:
where A and B are the wavefunctions for the pz atomic orbitals that form the basis.
c1 + c1 = 1
2 2 2
c1 = c1 =
1 2 1 2
1 = 2 =
1 2
A A +
1 2
B B
1 2
1 2
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2. C3H5+
Hc = Ec 0 0 c1 c1 c2 = E c2 c 3 c3
only 2 electrons, but we must consider 3 pz atomic orbitals
0 c1 0 E E c2 = 0 0 E c3 0
E 0 E =0 0 E
( E )
E E +0 =0 E 0 E 0
( E )(( E )( E ) 2 ) ( ( E ) 0 ) = 0
...then expand brackets and solve for E
53
Alternatively, use Maple (or similar) Maple syntax... at the prompt, type the following:
set linear algebra mode enter matrix, called H solve the secular determinant for e
Answers:
E = a, a + 2b, a 2b
54
eigenvalue multiplicity of this eigenvalue ditto for 2nd and 3rd eigenvalues
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0 0
55