Generating SALCS and SALC-MOs

Ryan Johnson December 6, 2010

Introduction

!v

C2

! 'v Symmetry adapted linear combinations (SALCS) are simply linear combinations of atomic orbitals (as we are used to making) but are constructed in such a way that the resulting functions transform in well dened ways under symmetry operations. In other words, z group theory provides us with a process that can be y used to generate combinations of an arbitrary basis x set (AOs in this case) that transform by a specied symmetry. The SALCs make the task of building molecular orbitals (SALC-MOs) far easier as it eliminates any combination that would have zero over- Figure 1: Dening coordinate and operation notation lap. The main principle in play is that when building for the C2v point group MOs, only SALCs of the same symmetry (A1 , B2 ,. . . ) can be combined, because mixing two dierent irreps O2s O2px O2py O2pz H1s H1s (ie. A1 + B2 ) has a necessarily zero overlap, like E O2s O2px O2py O2pz H1s H1s combining an s orbital side-on with a p. The proC2 O2s -O2px -O2py O2pz H1s H1s cess of generating SALCs can be daunting at rst, v O2s O2px -O2py O2pz H1s H1s but is tremendously powerful and provides interestv O2s -O2px O2py O2pz H1s H1s ing insight into molecular orbitals. In this handout I will (hopefully) explain this process and go through the analysis of two molecules of the C2v point group: Table 1: Complete transformation table for H2 O with H2 O and NO2 all valence orbitals in basis set

6 0 2 4

H2 O

First, lets take a look at the relatively simple water molecule. We will take all valence atomic orbitals as our basis set. These are the 2s and 2p of oxygen and the 1s orbitals of each hydrogen. I have labeled the hydrogens as H and H for clarity. Please refer to Figure 1, in which I have labeled coordinates and operations of the C2v point group. Remember that as long as you are consistent, it doesnt matter how 1

these are set up. For example, v andv could be switched without trouble. The rst step for building SALCs is to nd how the complete basis set transforms. In other words, we need to nd the irreps to which the basis set belongs. In Table 1 I have drawn up how each orbital of the molecule changes under every operation. Please take a close look at this table and convince yourself that it is true. I have also tallied up the orbitals (1 for no change, -1 for reversal, and 0 for atoms that

switch place) to get the reducible representation . This can be reduced to 3A1 + B1 + 2B2 . Try to reduce it yourself (how many A1 s does it contain. . . ) and then verify by adding together the resulting irreducible representations to recover . Now that we have determined the irreps that are spanned by this basis set we can start to write linear combinations that follow the symmetry of the group, ie the SALCs. We should notice rst that we have already found how many SALCs we need and their symmetry: 3A1 + B1 + 2B2 = 6 SALCs to nd. Notice that this is the same number as E for our . There is a reason for that. . . Now, there is a formal way to actually nd the functional form of the SALCs by using the following equation: (n) = 1 h (n) (R) Ri (1)

We have now found one of the three A1 SALCs. We now continue this process for each column and each irrep until we nd all the 6 possible SALCs. Try to nish o the table for A1 . You should nd that the other two A1 SALCs are (A1 ) = O2pz
(A1 )

(3) (4)

= H 1s + H 1s

Where (n) is the particular irrep you are interested in and h is the order of the group. R is an operation so (n) (R) is the character of a particular operation, and R is the new AO formed by operation R. The details of this formal approach are discussed in section 11.5(c) of the book (page 437). I will now show a brief example of how it is used, but I will primarily focus on an alternative method which I nd to be more intuitive, informative and easier to use. Lets say we want to nd the 3A1 s rst (ie, our (n) in Equation 1 is A1 and the values of (n) (R) are all 1, and values of R are taken from the rst column of Table 1 which are all O2s because this orbital is changed by no operation ). We then go column by column, repeating for each irrep. Lets start with the rst column of O2s orbital transformations. Applying the Equation 1, we get: (A1 ) = 1 (1) (O2s) + (1) (O2s) 4 +(1) (O2s) + (1) (O2s) which simplies to: (A1 ) = O2s

Again, this process is formal and general, and as such will always give you the correct answer, but it can be a bit tedious and making mistakes is easy, as you might recognize while trying to nd the third of the above SALCs. Note: Using this equation is exactly the kind of work cut out for a computer, and codes that do QM most certainly have something similar programmed in. I would like to show you an alternative approach that leverages what we already know about molecular orbitals (which is quite a bit!). The rst step is to break the molecule apart into fragments. It takes a little practice to see what is the best way to do this, but lets take the two hydrogens as a fragment and the oxygen atom alone as the other fragment. We can now treat each fragment separately.

2.1

H2 Fragment

We already know exactly what this molecules orbitals looks like; there is a bonding orbital in which both s orbitals are combined with like sign and an anti-bonding orbital in which they are opposite sign. These are shown in Figure 2. Now we want to try to label these orbitals by their symmetry. Lets take the bonding orbital st. We see that no operation will change this orbital, therefore, we can label it A1 right away. When we turn to the anti-bonding orbital, we see that the C2 and v will both change the sign while the other two operations will not. Looking at the character table we see that this is how B2 behaves and so we say this orbital spans the B2 irrep. We can cross o these two SALCs from our list now and turn to the other (2) fragment; oxygen. 2

Hydrogen fragment molecular orbitals

First four occupied SALC-MOs of H2 O

(A1 ) = O2s + H 1s + H 1s

(A1 ) = O2py + H 1s H 1s

Figure 2: Molecular orbitals of H2

(A1 ) = O2pz + H 1s + H 1s

( B1 ) = O 2p x

2.2

Oxygen Fragment
Figure 3: First four molecular orbitals of the water molecule, and the corresponding SALC-MO functions.

O2pz and the H1s + H1s SALCs to form a pair of A1 bonding and anti-bonding molecular orbitals. In Figure 3, I have drawn some of these molecular orbitals. See if you can draw the remaining combinations. Dont forget the corresponding anti-bonding orbitals! Try to draw them in a molecular orbital diagram as we did with diatoms by putting each fragment on the (A1 ) = O2pz sides and the molecular orbitals in the middle. This (A1 ) is a useful way to organize everything. We can not = O2s tell the exact order of the MOs from group theory (A1 ) = H 1s + H 1s alone, but you can use your intuition to get pretty close. Remember that the more nodes it has, the (B1 ) = O2px higher the energy. Make sure to draw these MOs! (B2 ) = H 1s H 1s Water is a convenient way to learn how to make (B2 ) = O2py SALCs because of its relative simplicity, but the method is exactly the same for other more complex These are also the same SALCs that we would nd molecules. Lets now turn our attention to NO in 2 by going through the formal process, which is fairly order to step gradually up the diculty. easy to convince yourself of, simply by inspecting Table 1.

True, this is not much of a fragment but we want to go through and label the orbitals in the same way we did for the hydrogen MOs. In this case it is quite simple because we can take advantage of the far right columns of the character table which tell us that the pz orbital transforms as A1 , the px as B1 , py as B2 , and by inspection we see that the s orbital is also A1 . We have now found every irrep that we predicted by decomposing . And we can write the appropriate functional form of the SALCs easily as follows:

3
2.3 H2 O SALC-MOs

NO2

We are now ready to build our SALC-MOs. This is For this molecule we are not going to use all of the simply done by combining every SALCs of like symmetry just as we combine atomic orbitals to form valence electrons as we did with water. We will drop molecular orbitals. For example we can combine the the O2s orbitals in order to have it match exactly 3

N2s E C2 v v N2s N2s N2s N2s

N2px N2px -N2px N2px -N2px

N2py N2py -N2py -N2py N2py

N2pz N2pz N2pz N2pz N2pz

O2px O2px -O2px O2px -O2px

O2py O2py -O2py -O2py O2py

O2pz O2pz O2pz O2pz O2pz

O2px O2px -O2px O2px -O2px

O2py O2py -O2py -O2py -O2py

O2pz O2pz O2pz O2pz O2pz

10 0 2 4

Table 2: Complete transformation table for NO2

Symmetry labels for O2 fragment
B2

orbitals (using the coordinate system dened in FIGURE 1). In Figure 3.1 I have drawn and labeled all molecular orbitals by the representation that they span. We can then collect them written in their functional form as a list of the SALCs for this fragment. Note: The coordinates are not the same as we learned them, in which we denoted the internuclear axis as z. The internuclear axis is the y axis in this coordinate system. On the right of the following SALCs I have included the names of the orbitals as we are familiar with them for the simple O2 molecule. The SALCs are:

A1

B1

A1

B2

A2

problem 11.15 in Atkins book. So, our basis set will contain the N2s, N2ps and the O2ps only. I will continue to use the fragment approach, but I highly recommend you verify the SALCs we nd by using Table 2 and Equation 1. A natural choice for fragments are those analogous to our water fragments; the two oxygen atoms as one fragment and the nitrogen atom as the other. As with water, I have started by nding all possible transformations of our basis set, which are collected in Table 2. The reducible rep, , that is formed is then reduced to 4A1 + A2 + 2B1 + 3 B2 . Make sure to verify this in order to practice reducing representations. Just as before, we now turn to each fragment in turn and write SALCs based on how the fragments transform.

(A1 ) = O2py + O 2py = 3z (A1 ) = O2pz + O 2pz = 1x (B1 ) = O2px + O 2px = 1y

(B2 ) = O2py O 2py = 4z (B2 ) = O2pz O 2pz = 2x (A2 ) = O2px O 2px = 2y

3.1

O2 Fragment

3.2

Nitrogen Atom Fragment

O2 is another molecule that we know the molecular orbitals for and we can take the MO diagram that we have generated for it previously and apply it directly to this problem (with the exception of the O2s orbitals, which we have dropped). Our task is now to label each orbital by its symmetry. For example, we can see that the 3 which are formed by the O2py 4

We have essentially already solved this atom fragment in the water example and even that was a fairly trivial task because we took advantage of the far right columns of the character table. What was a oxygen atom in water is a nitrogen atom now, but the results are the same. These are written below, nishing out the list of SALCS for the NO2 molecule.

 (A1 ) = N 2pz (A1 ) = N 2s (B1 ) = N 2px (B2 ) = N 2py I will leave you to combine the SALCs of like symmetry to generate the SALC-MOs for this molecule. This is done exactly as we did before; forming linear combinations resulting in both bonding and antibonding orbitals for every combination of like symmetry between fragments. You may be wondering what to do with the single A2 SALC formed from the O2 fragment. There is no other SALC with which it can combine so it remains the exact same (and at the same energy), and is call a non-bonding orbital. In fact, try to see what happens if you tried to combine it with another SALC. (You should nd that there can not be any overlap with any other SALC)

Planar ethylene (H2 CCH2 ) could be broken into a CC fragment and two H2 fragments, or a single H4 fragment. The later could even be constructed rst by the two H2 ones! I hope you are starting to get the idea that this is an extremely exible and powerful method. You may have noticed how nicely the number of SALCs predicted by was always exactly found. This is true no matter how you break the molecule apart and recombine it again. Please play with other molecules and discover for yourself!

Other Molecules

So how do we make the next step to look at more complicated molecules? You can always go through the formal process as outlined above and discussed in detail in the book. Equation 1 will always provide the correct list of SALCs, but is in some way a black box with a crank sticking out; put the AOs in, turn the crank and collect the SALCs as they tumble out the bottom. I personally prefer the fragment approach for molecules of any complexity because it appeals to our intuition and exposes the inner workings of the process. The trick is to recognize that you can break molecules into as many fragments as you want, and progressively build them up, piece by piece, until you have reconstructed the molecule. For example, NH3 could be treated with three fragments. First combine a single hydrogen fragment with the remaining molecular hydrogen fragment, and then combine the resulting three hydrogen SALCs with the nitrogen. As I mentioned above, with a little practice you will be able to quickly see useful ways to break apart the molecule and easy ways to recombine it. 5