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edited Nov 21 2011 at 15:02

Minhyong Kim
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On the periods in the periodic table (or Why is a noble gas stable?)

Added 22, November:

I've succeeded in making the question entirely unintelligible with all my additions.So I thought I would summarize it in the simplest form I could manage and add it to the title. The question is thereby somewhat narrower in scope than my original query, but I would be happy to have this focused version answered.

The main point is that the loose answer

(A) because the outer shell is filled

frequently heard is definitely wrong. If we take the usual definition of a shell, all the noble gases but Helium have justthe s and p subshells (corresponding to the representations $V_0\otimes S$ and $V_1\otimes S$) filled in the outermost shell, and this is not a full shell once the atom is bigger than Argon.The wikipedia article on noble gases offers an amusing formulation whereby, fora noble gas, 'the outer shell of valence electrons is considered to be "full"' (my emphasis).

All this led to my initial confusion: I thought that the term 'shell' must mean somethingelse for multi-electron systems in a manner adapted to the answer (A). Such an alternative definition does not seem to exist, and it is not at all obvious how to come up withone in a non-tautological way. So I believe the essence of what I am asking is whether or not there is

a natural mathematical explanation for the stabilityof noble gases

that is more or less independent of experimentsconfirmed by difficult computations using approximation schemes.

Anyone interested in the background and details is invited to read the incoherent paragraphs below,or to look up a proper reference like Atkin's book on physical chemistry.

Added, 21 November:

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edited Nov 20 2011 at 16:29

Minhyong Kim
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L-shell: $2s\oplus 2p$

and so on. (In case you're wondering, the representations after $V_3\otimes S=f$ are labeled consecutively in the alphabet.) In The key point is that, in this form, a shell does not necessarily consist of a grouping of subshells of similar energies when more than a few electrons are present. Rather, the conventional description of the phenomena says that more than one shell can be incomplete in an atom. For example, in the fourth row of the periodic table, starting with potassium (K) and up to copper (Cu), they say both the $M$-shell and the $N$-shell are incomplete. If this is confusing to you, I suggest you don't worry about it. I just wanted to point out that my question `what is a shell?' has a clear-cut answer in this usage. If we don't want to go against this convention, we need to stick to the version

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edited Nov 20 2011 at 16:23

Minhyong Kim
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Added, 19 21 November:

Having read some more here and there, I should make some terminological corrections, in case I mislead anyone with my ignorance. I will do so here, and leave the text below as written, in case the temporary confusion is helpful to other interested non-experts.

Firstly, as far as I can tell, the word 'orbital' does seem to refer to a wavefunction, not a representation. So the eigenfunctions in the second occurrence of the representation $V_1\otimes S$ will be called the $3p$-orbitals. That is, the individual wavefunction is an orbital, while the representation itself might be referred to as the so-and-so orbitals, in the plural. The definitive term for any given occurrence of an irreducible representation in $L^2\otimes S$ seems to be subshell.

Secondly, I finally read the wikipedia article on shells. It doesn't help much with my questions, but it does describe the convention regarding the term 'shell'. As far as I can tell, the shells are simply the direct sums of the following form:

K-shell: $1s$

L-shell $2s\oplus 2p$

M-shell: $3s \oplus 3p \oplus 3d$

N-shell: $4s\oplus 4p \oplus 4d\oplus 4f $

O-shell: $5s\oplus 5p \oplus 5d\oplus 5f\oplus 5g $

and so on. (In case you're wondering, the representations after $V_3\otimes S=f$ are labeled consecutively in the alphabet.) In this form, a shell does not necessarily consist of a grouping of subshells of similar energies. Rather, the conventional description says that more than one shell can be incomplete in an atom. For example, in the fourth row of the periodic table, starting with potassium (K) and up to copper (Cu), they say both the $M$-shell and the $N$-shell are incomplete. If this is confusing to you, I suggest you don't worry about it. I just wanted to point out that my question `what is a shell?' has a clear-cut answer in this usage. If we don't want to go against this convention, we need to stick to the version

`What determines a period?'

I'm very sorry for all the confusion.

Added, 19 November:

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edited Nov 20 2011 at 2:39

Minhyong Kim
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edited Nov 19 2011 at 15:03

Minhyong Kim
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edited Nov 19 2011 at 6:58

Minhyong Kim
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I Just saw Scott's answer as I was preparing to post this addition. There is a bit of overlap.

Added, 19 November.

After receiving the nice answers from Jeff and Antoine, I realized that I should sharpen the questionsomewhat more. I like Neil's formulation, but I think I am asking something much more naive.Allow me to start by providing more background for mathematicians whose knowledge is as hazyas mine. As mentioned by Jeff and Antoine, the Hamiltonian for a system of $N$ electronsmoving around a nucleus of charge $Z$ looks like

$$H=-\frac{\hbar^2}{2m}\sum_{i=1}^N \Delta_i-\sum_{i=1}^N \frac{Ze^2}{r_i}+ \sum \frac{e^2}{r_{ij}}.$$

In principle, one would like to understand the structure of discrete spectrum solutions to the eigenvalue equationOne characterizes solutions using labels called 'quantum numbers'. In general, there is an * objective label* oftendenoted $l$, the angular momentum quantum number. This comes from the fact that there isan $SO(3)\times SU(2)$ symmetry, breaking up solutions into the irreducible representation $V_l\otimes S$, mentionedearlier. All the vectors in a given irreducible representation must have the same energy level $E$, becausea basis for the space can be obtained from a highest weight vector by applying elements of $LieSO(3)$.Any given $V_l\otimes S$ is called a subshell or an orbital (I'm a bit unclear about this because the term 'orbital' is also used for the individual eigenfunctions) and is described using the (historical) labels

$$V_0\otimes S \leftrightarrow s$$$$V_1\otimes S \leftrightarrow p$$$$V_2\otimes S \leftrightarrow d$$$$V_3\otimes S \leftrightarrow f$$

The * principal quantum number* is determined as follows. We order all the orbitals by energy levels,and the $n-$th time $V_0 \times S$ occurs, we call that subspace $ns$. However, the $n$-th time that$V_1\otimes S$ occurs, we call it $(n+1)p$. In general, the $n$-th time $V_l\otimes S$ occurs,the label is $(n+l+1)$(whatever letter $l$ corresponds to). For example, the orbital $3d$ is the first occurrenceof the representation $V_2\otimes S$. When there is just one electron in a $1/r$ potential, these $n$ really labelthe order of the energy levels, and $d$ really occurs the first time in the third energy level. This is the reason forthe shift in labelling, even though this correspondence with energy levels fails for multi-electron systems.In fact, in neutral atoms with $N=Z$, the energy levels are ordered like$$1s<2s<2p<3s<3p<3d<4s<4p<5s<4d\ldots$$I hope it is clear then that the orbitals (or the subshells) are completely well-defined and have a labellingscheme that is a bit odd, but makes sense when the obvious translation is combined with history.So the real question is

What determines a shell?

Some energy-non-decreasing consecutive sequence of subshells is a shell. The shells then determine the rows of the periodic table (if we ignore the added complicationthat $Z$ is also increasing as we move right and down). Now, I was tempted to conclude that the standardconvention was a bit arbitrary. After all, the chemical similarity of the columns could possibly be explained simply by thefact that

they have the same representation of $SO(3)\times SU(2)$ at the uppermost energy level, and thesame number of electrons in this representation

without any reference to an outermost shell. This can be easily seen by the arrangement into blocks shown here . And then, unlike the $N=1$ case,the energy levels in one shell are not even the same, just rather close to each other.

Unfortunately, it is clear that

the grouping into rows represent real phenomena.

This comes out very clearly, for example, in the graph of ionization energies, with the noticeable peaksat the end of the rows immediately followed by precipitous drops. So I believe a bit of thought reduces a good deal of my original question to two parts:

Is there some reason for a big gap in ionization energy when one moves to an $s$-orbital?

Can one show that two orbitals of the same type are necessarily separated by a huge energygap, so that it is highly unlikely for them to occur in the same shell?

1 and 2 together make it natural that the dimensions we see in each shell will be of the form

2, 2+6, 2+6+10, 2+6+10+14, etc,

even in the general case. Of course, this doesn't say anything about how many times each combination islikely to occur.

In any case, I hope there is a mathematical answer to these two questions that doesn't involve a full-blown programme inhard analysis.

At the more speculative end, one might analyze a family of operators like

$$H_{\epsilon}=-\frac{\hbar^2}{2m}\sum_{i=1}^N \Delta_i-\sum_{i=1}^N\frac{Ze^2}{r_i}+\epsilon \sum \frac{e^2}{r_{ij}}.$$Is there a way to see the numbers we see occurring via the spectral flow of this family as we go from $\epsilon =0 $ to$\epsilon=1$? But maybe this is just as difficult as giving a full account of the structures using analysis.

By the way, I certainly wouldn't like to complain, but it is a bit puzzling to me why some people regard thisquestion as inappropriate for the site. Since I don't keep too well in touch with cultural trends in themathematical world, maybe I am unaware of how much things have changed since I was aPh.D. student. In those days, a programme like

Prove the stability of matter, based only on the Schroedinger equation

was regarded as an example of an importantmathematical problem motivated by atomic structure, tackled by people like Fefferman and Lieb. The questions I ask here are hopefully much easier, but still research-levelmathematics to my mind.

This question prompts me to ask something more specific about the periodic table.

That is, where do the length lengths of the periods

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asked Nov 18 2011 at 16:23

Minhyong Kim
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On the periods in the periodic table

This question prompts me to ask something more specific about the periodic table. As far as I know, the main significance of the periodic table is that

The elements in the same column have similar chemical properties.

For example, the noble gases at the far right are all pretty stable on their own. The explanation for this is that they have (in the neutral state) a full outermost shell. Now my question is

Is there an explanation, at some reasonable level of mathematical rigor, of when a new shell starts?

That is, where do the length of the periods

2, 8, 8, 18, 18, 32, 32

come from? I confess I've been puzzled by this ever since my university physics course.

Allow me to pinpoint my confusion a bit more. I understand that there are some numbers that are important in atomic structure, and these are 2, 6, 10, 14, and so on. This is because of the occurrence of the representations

$$V_l\otimes S$$

inside the Hilbert space for a single particle moving in a central potential. These are the orbitals one hears about in physical chemistry courses. Here, the $V_l$ are the representations of $SO(3)$ of odd-dimension $2l+l$, while $S$ is the standard two-dim representation of $SU(2)$. Since all the states in a single orbital have the same energy, it is natural that the breaks will occur after some collection of orbitals are all filled.

Thus, for a hydrogen atom, the successive shells have dimensions

$2n^2$

for $n=1, 2, 3, \ldots$ because the representations $V_l\otimes S$ for $l=1, 2,\ldots, n-1$ occur each with multiplicity one inside the $n$-th shell.

So if the periods in the table were of lengths

2, 8, 18, 32,

I would have vaguely assumed that the pattern of shells even in general looks like that of the hydrogen atom. But of course, among the known elements, each period length that occurs in the hydrogen atom is repeated twice, except for the first one. So a more precise question is

Is there a reasonable mathematical explanation of this `multiplicity two' of the periods?

The little I recall of discussions in standard textbooks were quite unclear. There are various rules by the name of Hund's rule, the Aufbau principle, and so on, but I couldn't gather from any of them

*Where the breaks should occur. *

What I do see is that periods end when the orbitals 1p, 2p, 3p, etc. get filled following the Aufbau principle. (Here, p is the chemist's label for $V_1\otimes S$.) So perhaps another version of the question is

Is there some reason that the p-orbitals mark the end of the periods?

To be honest, I've never understood the Aufbau principle either, because I don't know the rationale behind the principal quantum number for the larger atoms. That is, the number 4 in the orbital 4p refers to the 4-th energy level in the case of the hydrogen atom. But for larger nuclei, the $n $ in orbital '$np$' does not refer to the energy level. (This discrepancy is in fact implied by the Aufbau principle.) So what is the significance of the $n$ in general that enables them to play some role in a physical principle?

I realize this question is becoming incoherent already. Nevertheless, I would very much appreciate clarification on any sensible version of it at a level of mathematical rigor of your choice. (I am not asking for any axiomatics.) Pointers to an accessible reference would be equally welcome.

As with the earlier question, a word of explanation is in order on the decision to post this on Math Overflow. I will draw upon an analogy I read long ago in an article of George Mackey's that went something like this: Say my mother tongue is Korean. If I would really like to use English fluently, it is probably best eventually to learn from native speakers of English. On the other hand, if I would like a good translation into Korean of English literature, it is better to consult an educated Korean who knows a lot about English. Of course answers from real physicists will be very gratefully received, especially if they bear in mind that the query comes from someone who struggles against a serious language handicap.

quantum-mechanics