Doublethink and angular momentum — why chemists must be adept at it

Chemists really should know lots and lots about angular momentum which is intimately involved in 3 of the 4 quantum numbers needed to describe atomic electronic structure. Despite this, I never really understood what was going until taking the QM course, and digging into chapters 10 and 11 of Giancoli’s physics book (pp. 248 -310 4th Edition).

Quick, what is the angular momemtum of a single particle (say a planet) moving around a central object (say the sun)? Well, its magnitude is the current speed of the particle times its mass, but what is its direction? There must be a direction since angular momentum is a vector. The (unintuitive to me) answer is that the angular momemtum vector points upward (resp. downward) from the plane of motion of the planet around the center of mass of the sun planet system, if the planet is moving counterclockwise (resp. clockwise) according to the right hand rule. On the other hand, the momentum of a particle moving in a straight line is just its mass times its velocity vector (e.g. in the same direction).

Why the difference? This unintuitive answer makes sense if, instead of a single point mass, you consider the rotation of a solid (e.g. rigid) object around an axis. All the velocity vectors of the object at a given time either point in different directions, or if they point in the same direction have different magnitudes. Since the object is solid, points farther away from the axis are moving faster. The only sensible thing to do is point the angular momentum vector along the axis of rotation (it’s the only thing which has a constant direction).

Mathematically, this is fairly simple to do (but only in 3 dimensions). The vector from the axis of rotation to the planet (call it r), and the vector of instantaneous linear velocity of the planet (call it v) do not point in the same direction, so they define a plane (if they do point in the same direction the planet is either hurtling into the sun or speeding directly away, hence not rotating). In 3 dimensions, there is a unique direction at 90 degrees to the plane. The vector cross product of r and v gives a vector pointing in this direction (to get a unique vector, you must use the right or the left hand rule). Nicely, the larger r and v, the larger the angular momentum vector (which makes sense). In more than 3 dimensions there isn’t a unique direction away from a plane, which is why the cross product doesn’t work there (although there are mathematical analogies to it).

This also explains why I never understood momentum (angular or otherwise) till now. It’s very easy to conflate linear momentum with force and I did. Get hit by a speeding bullet and you feel a force in the same direction as the bullet — actually the force you feel is what you’ve done to the bullet to change its momentum (force is basically defined as anything that changes momentum).

So the angular momentum of an object is never in the direction of its instantaneous linear velocity. But why should chemists care about angular momentum? Solid state physicists, particle physicists etc. etc. get along just fine without it pretty much, although quantum mechanics is just as crucial for them. The answer is simply because the electrons in a stable atom hang around the nucleus and do not wander off to infinity. This means that their trajectories must continually bend around the nucleus, giving each trajectory an angular momentum.

Did I say trajectory? This is where the doublethink comes in. Trajectory is a notion of the classical world we experience. Consider any atomic orbital containing a node (e.g. everything but a 1 s orbital). Zeno would have had a field day with them. Nodes are surfaces in space where the electron is never to be found. They separate the various lobes of the orbital from each other. How does the electron get from one lobe to the other by a trajectory? We do know that the electron is in all the lobes because a series of measurements will find the electron in each lobe of the orbital (but only in one lobe per measurement). The electron can’t make the trip, because there is no trip possible. Goodbye to the classical notion of trajectory, and with it the classical notion of angular momentum.

But the classical notions of trajectory and angular momentum still help you think about what’s going on (assuming anything IS in fact going on down there between measurements). We know quite a lot about angular momentum in atoms. Why? Because the angular momentum operators of QM commute with the Hamiltonian operator of QM, meaning that they have a common set of eigenfunctions, hence a common set of eigenvalues (e.g. energies). We can measure these energies (really the differences between them — that’s what a spectrum really is) and quantum mechanics predicts this better than anything else.

Further doublethink — a moving charge creates a magnetic field, and a magnetic field affects a moving charge, so placing a moving charge in a magnetic field should alter its energy. This accounts for the Zeeman effect (the splitting of spectral lines in a magnetic field). Trajectories help you understand this (even if they can’t really exist in the confines of the atom).

The course is finishing up (sob !) with 3 lectures on nuclear magnetic resonance. More about the high powered doublethink required to comprehend this in a future post.

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