OK - let me put it a bit more precisely:
I'm asking about the orbital and spin angular momenta of electrons in, for example, low density gaseous states.
Textbooks glibly mention electrons being in states |n,l,m,s>
But how, observationally, do we come to know what m(l) and m(s) are for the states between which we observe spectral lines?
Suppose I excite some sodium vapour, and as Wikipedia states:
http://en.wikipedia.org/wiki/Sodium
"One notable atomic spectral line of sodium vapor is the so-called D-line, which may be observed directly as the sodium flame-test line (see Applications) and also the major light output of low-pressure sodium lamps (these produce an unnatural yellow, rather than the peach-colored glow of high pressure lamps). The D-line is one of the classified Fraunhofer lines observed in the visible spectrum of the sun's electromagnetic radiation. Sodium vapor in the upper layers of the sun creates a dark line in the emitted spectrum of electromagnetic radiation by absorbing visible light in a band of wavelengths around 589.5 nm. This wavelength corresponds to transitions in atomic sodium in which the valence-electron transitions from a 3p to 3s electronic state. Closer examination of the visible spectrum of atomic sodium reveals that the D-line actually consists of two lines called the D1 and D2 lines at 589.6 nm and 589.0 nm, respectively. This fine structure results from a spin-orbit interaction of the valence electron in the 3p electronic state. The spin-orbit interaction couples the spin angular momentum and orbital angular momentum of a 3p electron to form two states that are respectively notated as 3p(2p0,1/2) and 3p(2p0,3/2) in the LS coupling scheme. The 3s state of the electron gives rise to a single state which is notated as 3s(2S1 / 2) in the LS coupling scheme. The D1-line results from an electronic transition between 3s(2S1 / 2) lower state and 3p(2p0,1/2) upper state. The D2-line results from an electronic transition between 3s(2S1 / 2) lower state and 3p(2p0,3/2) upper state. Even closer examination of the visible spectrum of atomic sodium would reveal that the D-line actually consists of a lot more than two lines. These lines are associated with hyperfine structure of the 3p upper states and 3s lower states. Many different transitions involving visible light near 589.5 nm may occur between the different upper and lower hyperfine levels.[8][9]"
(see original in Wiki to see the term symbols displayed correctly).
Now, how precisely do we come to be able to state that a transition is between any of the above two states - ie to identify the states' various quantum numbers including the angular momenta?
As posed in my original question - the only way I can see this being achieved is if one first *calculates* the structure of the spectrum and thus the associated n,l,m,s, values, and then one assigns the observed spectral lines to those theoretically identified states. So one never actually observes the m(l) and m(s) values, but as mentioned in the first post, one infers them.
Or is there some other way to do this?