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VIII. Molecular Orbital Theory (7.13-14) A.

Overview/Definitions So far, we have been visualizing covalent bonds (molecular orbitals) as regions where electrons are being shared between atomic orbitals (that may or may not be hybridized). For example, to visualize the bonding in CH4, wed have a picture like this:

where the ovals around the carbon are amusingly crude approximations to sp3 orbitals. We havent talked about it much, but the assumption has been that, for example, the 1s orbital from H (with its one electron) has overlapped with one of the sp3 orbitals on C (with its one electron) to form a covalent bond (a molecular orbital). Since the Pauli Exclusion Principle is a property of electrons, if two electrons are going to be paired in the same space, they must have opposite spins. This picture that we havent talked about much is a very simplified version of valence bond theory. It pictures bonding as the result of the overlap of atomic orbitals. We wont talk about valence bond theory any more, because its really a simplified version of molecular orbital theory, which is the subject of the current section. In chapter 5, we saw that atomic orbitals (e.g. 1s, 2s, 2p, etc.) are solutions to Schrdingers equation for the hydrogen atom. Molecular orbitals are simply solutions to Schrdingers equation for molecules. Now, the big problem with Schrdingers equation is that it can be solved exactly only for systems that have one electron: the hydrogen atom being the simplest case. Therefore, the Schrdinger equation cant be solved for molecules that have more than one electron. To get around this problem, theoretical chemists and physicists have learned how to construct approximate solutions (molecular orbitals) to Schrdingers equation for molecules using atomic orbitals. In other words, atomic orbitals are combined mathematically to generate molecular orbitals, which describe the energy states available to electrons in molecules. Thats molecular orbital theory in a teeny, tiny nutshell. Without going into any kind of mathematical detail (we do that in your Junior year if you become a chemistry major), lets see what MO theory can do for us. B. A Linear Combination of Atomic Orbitals: H2 Mathematically, atomic orbitals are combined through something called a linear combination. I promised wed do this without math, so lets try and get a feel for what this is conceptually. Consider the simplest molecule, H2: you can imagine this as the mixing of two 1s atomic orbitals;

one from each hydrogen. In broad terms, there seems to be two ways to combine these atomic orbitals: either add them, or subtract them.

When the atomic orbitals are added, the result is a bonding molecular orbital (), since there is a good probability of finding the two shared electrons between the two hydrogen atoms. This sharing helps to hold the molecule together. When the atomic orbitals are subtracted, the result is an antibonding molecular orbital (*), since there is zero probability of finding the electrons in this molecular orbital between the atoms. (The blue color on the left refers to a change in sign of that atomic orbital subtracting is the same thing as adding the negative.) If electrons are in this antibonding orbital, it would help to destabilize the molecule. A more in-depth mathematical treatment would show that when atomic orbitals are combined this way, the energy of the bonding MO is lower than the energy of the original 1s atomic orbitals in the hydrogen atoms, and the energy of the antibonding MO is higher than the individual 1s orbitals on hydrogen. However, the split is generally not equal; most of the time, the antibonding orbital is higher in energy with respect to the atomic orbitals than the bonding orbital is lower. This is much easier to see with a diagram:

Notice what weve been trying to describe: the antibonding is destabilized (relative to the energy of the 1s orbital) more than the bonding orbital is stabilized. This molecular orbital picture helps to explain a lot of chemical bonding. To see why, we need to add some electrons to the diagram. Consider H2. For this molecule, each AO contains one electron:

When the two orbitals combine to create the and * MOs, the two electrons occupy the lowest energy MO: (remember the Aufbau principle?)

Since the two electrons are now in a lower energy orbital (lower energy state), there is a net gain in stabilization, and H2 is stable. In fact, we can talk about bond order to give us a feel for the strength of the bond. Weve talked about bond order before, but never called it by name: bond order is the number of electron pairs shared between two bonded atoms. Therefore, a single bond has a bond order of 1, a double bond has a bond order of 2, and a triple bond has a bond order of 3. In actuality, the numerical value of the bond order depends greatly on the quantum-mechanical model that is being used to calculate it. However, a simpler formula is typically used for the diatomic MO diagrams were looking at here: e "e (7.2) B = b ab 2 where B is the bond order, eb is the number of electrons in bonding orbitals, and eab is the number of electrons in anti-bonding orbitals. So, in the above example, H2 has a bond order of ! 2 "0 B= =1 2 which is what youd expect for a single bond.

! How about H2? To form this molecule, wed have to add another electron, and that would have to go into the * orbital because of the Pauli exclusion principle:

Again, there is still a net stabilization because there are two electrons in the more stable MO, and only one in the antibonding MO. Indeed, H2 is stable it has a bond order of


2 "1 1 = 2 2

So, youd expect this bond to be a bit weaker than the single bond in H2.

! How about He2? Well, for each He atom, you can imagine two electrons in the 1s orbital, and when they combine, you get the same MO diagram weve been using here. However, when you put in the electrons, you get:

Now there is a net destabilization because of the filled * orbital, and sure enough, He2 doesnt exist. It has a bond order of zero. C. Other Diatomic Molecules In essence, all the models for molecular electronic structure that weve seen so far (Lewis structures, valence bond) arein a sensesimplified versions of molecular orbital theory. Since they are simplified versions, they are generally less accurate descriptions of the electronic structure of molecules, and in some cases they can be just plain wrong. write For example, if you were asked to write the Lewis structure for O2, you would probably

and get full credit for it, because it obeys the simple rules we have for writing Lewis structures. The problem with this is that its wrong. The above electronic structure suggests that all the electrons are paired either in lone pairs, a sigma bond, or a pi bond. If that was the case, O2 would be diamagnetic: it would be weakly repelled by a magnetic field. (If youre up on your physics, you know that a moving electric charge creates a magnetic field. The spin on the electrons acts in a

similar way, but if there is no net electron spin in a molecule, it wont interact with a magnetic field.)

In fact, O2 is paramagnetic: it is attracted by magnetic fields. (You can see a cool picture of this on p. 259 of McMurry and Fay.) This property of O2 could be explained if the molecule had unpaired electrons spinning in the same direction. This spin would induce a magnetic field that would interact with any external field. Again, the Lewis structure predicts no net spin since all the electrons are paired. Molecular orbital theory gives us a better description of O2. First, lets create the MO diagram in other words, build up MOs for O2 from the valence AOs on each oxygen atom. Heres what the full diagram looks like:

Notice that the 2s orbitals combine to form a bonding orbital and an antibonding * orbital just like the 1s orbitals did in H2. For the 2p orbitals its basically the same idea although it certainly looks intimidating at first. Lets break it apart and make some sense out of whats going on up there. Look at the 2pz orbitals. (The z-axis is defined to be the line connecting the two atoms in the diatomic molecule.) The 2pz orbitals are combining to form one bonding orbital that looks like antibonding * orbital that looks like , and an

. So its the same pattern as before: two AOs

combine to give two MOs, one a lower-energy bonding orbital, the other a higher-energy antibonding orbital. Look at the 2py orbitals. They are combining to give a bonding orbital that looks like and an antibonding * orbital that looks like . Again, same pattern of AOs to give MOs. The 2px orbitals interact the same way, but the orbitals are rotated 90 from those generated from the 2py. (Thats why they have the same energy its really the same thing, just turned in space.) Stare at this for awhile to really see whats going on. Okay, so we have the MO diagram for O2. To see how this accounts for its paramagnetic character, lets put in the electrons:

Notice that if we follow Hunds rule, the two red electrons should fill the * orbital as shown, with parallel spins. These are unpaired electrons, and they should generate a magnetic field that will interact with any external field, and so MO theory successfully predicts that O2 is paramagnetic. Note that the bond order between the two oxygen atoms is


8"4 =2 2