Chemical Forums
Chemistry Forums for Students => Undergraduate General Chemistry Forum => Topic started by: Chahud on July 31, 2021, 02:51:01 PM
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Hello!
I'm curious about the naming of atomic orbitals and where it came from. The letters S, P, D, and F seem pretty random without knowing the context, so I looked it up:
S = sharp
P = principal
D = diffuse
F = fundamental
These apparently describe the shape of spectral lines in alkali metals and are where the terms we're so familiar with come from.
But this isn't enough for me and there isn't any great explanation available online that I found. Why do the lines look like this and do they have anything to do with the orbitals they're named after? In other words, is there particularly something having to do with a d orbital interaction that would cause the spectral line to appear diffuse? Does anyone have an example of these spectral lines? Any other info is greatly appreciated too. Thanks.
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The designations were given to spectral lines in various alkali metals, which were grouped into series. At the time shapes of orbitals were not known - orbitals and their connection to spectroscopic transitions were discovered later. As you might guess, lines in the sharp series were, well, sharp peaks, whereas those in the diffuse series had a lot of fine structure. These two designations came from emission spectra, primarily (I believe) sodium, which was one of the first studied.
https://en.wikipedia.org/wiki/Sharp_series
https://en.wikipedia.org/wiki/Diffuse_series
The "Principal" in principal series derives from similarity(in pattern) of absorption lines of alkalis to those of corresponding hydrogen spectra (for obvious reasons, as we now know), against which many atomic spectra were usually compared as a benchmark. Since the hydrogen spectra were the ones that were first seriously analyzed, their spectral line series was known the best - so I guess the "principal" appellation for similar spectral series that appeared in the alkalis makes sense.
I'm wasn't sure where the fundamental comes from, but according to this:
https://en.wikipedia.org/wiki/Fundamental_series
It seems like it was because the discoverer thought the line pattern was much simpler than other series, perhaps because the fine structure was too small to be easily observed.
Anyway, eventually the origin of spectral lines was discovered as quantum mechanics was formulated (actually, coming up with ways to explain the spectral line patterns was a big part of that), and the orbital transitions that gave rise to the spectral lines took the names of those series....and the rest is history.