The Music of The Spherical Harmonics

Eddie’s diner serves tasty pizza, but his music playlist’s tasty, too — heavy with small-group vocals.  We’re talking atomic structure but suddenly Vinnie surprises me.  “Whoa, she’s got a hot voice!”

“Who?”

“That girl who’s singing.”

“Which one?  That’s a quartet.”

“The alto.”

“How can you pick one voice out of that close-harmony performance?”

“By listening!  She’s the only one singing those notes.”

“You’re hearing a chaotic sound wave yet you can pick out just one sound.”

“Yeah, just her special notes.”

“Interesting thing is, atoms do that, too.  Think about, say, a uranium atom, 92 electrons attracted by the nucleus, repelled by every other electron, all dashing about in the nuclear field and getting in each other’s way.  Think that’d be a nice, orderly picture?”

“Sure not.  It’d be, like you say, chaotic.”

“But just like we can describe a messy sound wave as a combination of frequencies, we can describe that atom’s electron structure as a combination of basic patterns.”  I pull Old Reliable from its holster and bring up an image.  “Here’s something I built for a presentation.  It’s a little busy so I’ll walk you through it.”Shell levels

“Busy, uh-huh.”

“Start with those blue circles.  They look familiar?”

“Right, they’re Laplace’s spherical patterns.  You got them sorted by how many blue spaces they got.”

“Yup.  Blue represents a node, a 2-D region where the value touches or crosses zero.  There are patterns with three or more nodes, but I ran out of space and patience to draw them.  Laplace showed there’s an infinite number of candidate patterns as you add more and more nodes.  You can describe any physically reasonable distribution around the central point as some combination of his patterns.”

“Why’d you draw them on stair-steps?”

“Because each step (we call it a shell) is at a different potential energy level.  Suppose, for instance, that there’s charge in that one-node pattern.  Moving it away from the nucleus puts a node there.  That’ll cost some energy and shift charge to the two-node shell.  To exclude it from there and also from another node, say a larger spherical surface, would take even more energy, and so on.”

“How is that potential energy?”

“We’re comparing shell energy to the energy of an electron that’s far away.  It’s like gravitational potential energy, maybe the energy a space rock converts to kinetic energy as it falls to Earth.  Call the far-away energy zero.  The numbers get more and more negative as the rock or the charge get closer to the center of attraction.”

“Ah, so that’s why you’ve got minus signs in the picture.”

“Exactly.  See zero at the top of the stairs?  With a hydrogen atom, for instance, an electron would give up 13.6 electron-volts of energy to get close to the nucleus in that 1-node pattern.  Conversely, it’d take 13.6 eV to rip that charge completely away.”

“If the 13.6 is what you’re calling ‘Minimum’, why not just write ‘–13.6’ in there?”

“It’s a different number for different atoms and even ions.  Astronomers see all kinds of ions with every amount of charge so they have to keep things general in their calculations.”

“What are those fractions about?  Wait, don’t tell me, I can figure this.  Each divisor is the square of its node count.  Are those the 1/n² numbers from whosit’s formula?”

Rydberg’s.  You’re on the right track, keep going.”

“If the minimum is 13.6 eV, the diagram says that the two-node shell is … 3.4 eV down from the top and … 10.2 eV up from the bottom.  And from what we said about the hydrogen spectrum, I’ll bet that 10.2 eV jump is the first line in that, was it the Ly series, the one in the ultra-violet?”

“Bravo, Vinnie!  The Lyman series it is.  Excellent memory for detail there.”

“I noticed something else.  You carefully didn’t say we moved an electron between shells.”

“That’s an important point.  At the atomic size scale we can’t treat the electron as a particle moving around.  Lightwaves act to turn off one shell and excite another one, like your singer exciting a different note.”

“Yes, she does.”

~~ Rich Olcott

  • Thanks to the Molnars for a delightful meal, and to their dinner party guests the Jumps for instigating this post.
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Prelude to A Shell Game

Big Vinnie barrels into the office.  “Hey, Sy, word is that you’ve been trash-talking Niels Bohr.  What’s the story?”

“Nothing against Bohr, Vinnie, he was a smart guy who ran a numbers game out of C-town —”

“Which C-town, Cincy or Cleveland?”

“Copenhagen.  But he got caught short at payoff time.  Trouble is, some people still think the game’s good which it’s not.”

Hydrogen spectrum
Hydrogen spectrum, adapted from work by Caitlin Jo Ramsey
(CC BY-SA 3.0)
via Wikimedia Commons

“Which numbers game was this — policy, mutuale, bolita?”

“Rydberg.”

“Never heard of that one.”

“Rydberg was a Swedish physicist in the late 1800s.  He systemized a pile of lab and astronomy data about how hydrogen gas interacts with light.  Physicists like Lyman and Balmer showed how hydrogen’s complicated pattern (the white lines on black on this diagram) could be broken down to subsets that all have a similar shape (the colored lines).  Rydberg found a remarkably simple formula that worked for all the subsets.  Pick a line, measure its waves per meter. There’ll be a pair of numbers n1 and n2 such that the wave count is given by  Rydberg equationZ is the nuclear charge, which they’d just figured out how to measure, and R is a constant.  Funny how it just happens to be Rydberg’s initial.”

“Any numbers?”

“Small whole numbers, like 1, 2, up to 20 or so.  Each subset has the same n1 and a range of values for n2. The Lyman series, for instance, is based on n1=1, so you’ve got 1/1–1/4=3/4, 1/1–1/9=8/9, 15/16, 24/25, and so on. See how the fractions get closer together just like those lines do?”

“Nice, but why does it work out that way?”

“Excellent question, but no-one had an answer to that for 25 years until Bohr came up with his model.  Which on the one hand was genius and on the other was so bogus I can’t believe it’s still taught in schools.”

“So what did he say?”

“He suggested that an atom is structured like a solar system, planar, with electrons circling a central nucleus like little planets in their orbits. Unlike our Solar System, multiple electrons could share an orbit, chasing each other around a ring.  The 1/n² numbers are the energies of the different orbits, from n=1 outwards.  An electron in a close-in orbit would be tightly held by the nuclear electrical field; not so much for electrons further out.”

“Yeah, that sounds like what they taught us, alright.”

“Bohr then proposed that an incoming lightwave (he didn’t believe in photons) energizes an electron, moves it to a further-out orbit.  Conversely, a far-away electron can fall inward, emitting energy in the form of a lightwave.  Either way, the amount of energy in the lightwave depends only on the (1/n1²–1/n2²) energy difference between the two orbits.  The lightwave’s energy shows up in that wave number — more energy means more waves per meter and bluer light.”

“Ah, so that Ly series with n1=1 is from electrons falling all the way to the lowest-energy orbit and that’s why it’s all up in the … is that ultra-violet?”

“Yup, and you got it.  The Balmer series is the one with four lines in the visible.”

“Uhh… why wouldn’t everything just fall into the middle?”

“Bohr said each orbit would have a capacity limit, beyond which the ring would crinkle and eject surplus electrons.  He worked out limits for the first half-dozen elements but then things get fuzzy, with rings maybe colliding and swapping places.  Not satisfactory for predictions.  Worse, the physics just doesn’t work for his basic model.”No Bohr

“Really?  Bohr was a world-class physicist.”

“This was early days for atomic physics and people were still learning what to think about.  The Solar System is flat, more or less, so Bohr came up with a flat model.  But electrons repel each other.  They wouldn’t stay in a ring, they’d pop out to the corners of a regular figure like a tetrahedron or a cube.  That’d blow all his numbers.  The breaker payout, though, is his orbiting electrons must continually radiate lightwaves but don’t have an energy source for that.”

“Was he right about anything?”

“The model’s only correct notion was that lightwaves participate in shell transitions.  Schools should teach shells, not orbits.”

~~ Rich Olcott