# To Bond Or Not To Bond, That Is The Question

Vinnie’s pushing pizza crumbs around his plate, watching them clump together.  “These molecular orbitals gotta be pretty complicated.  How do you even write them down?”

“Combinations.  There’s a bunch of different strategies, but they all go back to Laplace’s spherical harmonics.  Remember, he showed that every possible distribution around a central attractor could be described as a combination of his patterns.  Turn on a field, like from another atom, and you just change what combination is active.  Here’s a sketch of the simplest case, two hydrogen atoms — see how the charge on each one bulges toward the other?  The bulge is a combination of a spherical orbital and a dumbbell one.  The molecular orbitals are combinations of orbitals from both atoms, describing how the charges overlap, or not.”

“What’s that blue in the other direction?”

“Another possible combination.  You can combine atomic orbitals with pluses or minuses.  The difference is that the minus combination will always have an additional node in between.  Extra nodes mean higher energy, harder to activate. When the molecule’s in the lowest energy state, charge will be between the atoms where that extra node isn’t.”

“So the overlapped charge here is negative, right, and it pulls the two positive nucleusses —”

“Nuclei”

“Whatever, it pulls ’em together.  Why don’t they just merge?”

“Positive-positive repulsion counts, too.  At the equilibrium bond distance, the nuclei repel each other exactly as much as the shared charge pulls them together.”

Eddie’s still hovering by our table.  “You said that there’s this huge number of possible atomic orbitals.  Wouldn’t there be an even huger number of molecular orbitals?”

“Sure.  The trick is in figuring out which of them are lowest-energy and activated and how that relates to the molecule’s configuration.  Keep track of your model’s total energy as you move the atoms about, for instance, and you can predict the equilibrium distance where the energy is a minimum.  In principle you can calculate configuration changes as two molecules approach each other and react.”

“Looks like a lot of work.”

“For sure, Eddie.  Even a handful of atoms has lots of atomic orbitals to keep track of.  That can burn up acres of compute time.”

Vinnie pushes three crumbs into a triangle.  “You got three distances, you can figure their angles.  So you got the whole shape of the thing.”

“Right, but like Eddie said, that’s a lot of computer work.  Chemists had to come up with shortcuts.  As a matter of fact, they had the shortcuts way before the computers came along.”

“They used, like, abacuses?”

“Funny, Vinnie.  No, no math at all.  And it’s why they still show school-kids those Bohr diagrams.”

“Crazy Eights.”

“Eddie, you got games on the brain.  But yeah, eights.  Or better, quartets of pairs.  One thing I’ve not mentioned yet is that even though they’ve got the same charge, electrons are willing to pair up.”

“How come?”

“That’s the thing of it, Vinnie.  There’s a story about Richard Feynman, probably the foremost physicist of the mid-20th Century.  Someone asked him to explain the pairing-up without using math.  Feynman went into his office for a week, came back out and said he couldn’t do it.  The math demands pairing-up, but outside of the math all we can say is experiments show that’s how it works.”

“HAH, that’s the reason for the ‘two charge units per orbital’ rule!”

“Exactly, Eddie.  It’s how charge can collect in that bonding molecular orbital in the first place.  It’s also the reason that helium doesn’t form molecules at all.  Imagine two helium atoms, each with two units of charge.  Suppose they come close to each other like those hydrogens did.  Where would the charge go?”

“OK, you got two units going into that in-between space, ahh, and the other two activating that blue orbital and pulling the two atoms apart.  So that adds up to zero?”

“Uh-huh.  They just bounce off and away.”

“Cool.”

“Hey, I got a question.  Your sketch has a ball orbital combining with a dumbbell.  But they’ve got different node counts, one and two.  Can you mix things from different shells?”

“Sure, Vinnie, if there’s enough energy.  The electron pair-up can release that much.”

“Cool.”

~~ Rich Olcott

• A friend pointed out that I’m doing my best to avoid saying the word “electron.” He’s absolutely right.  At least in this series I’m taking Bohr’s side in his debate with Einstein — electrons in atoms don’t act like little billiard balls, they act like statistical averages, smeared-out ones at that.  It’s closer to reality to talk about where the charge is so that’s how I’m writing it.