Mathematical 

Proceedings of 
the Cambridge Philosophical 
Society
http://journals.cambridge.org/PSP

Additional services for Mathematical 
Proceedings of the Cambridge 
Philosophical Society:

Email alerts: Click here
Subscriptions: Click here
Commercial reprints: Click here
Terms of use : Click here

The Wave Mechanics of an Atom with a 
non­Coulomb Central Field. Part III. Term 
Values and Intensities in Series in Optical 
Spectra
D. R. Hartree

Mathematical Proceedings of the Cambridge Philosophical Society / Volume 24 / 
Issue 03 / July 1928, pp 426 ­ 437
DOI: 10.1017/S0305004100015954, Published online: 24 October 2008

Link to this article: http://journals.cambridge.org/
abstract_S0305004100015954

How to cite this article:
D. R. Hartree (1928). The Wave Mechanics of an Atom with a non­
Coulomb Central Field. Part III. Term Values and Intensities in Series in 
Optical Spectra. Mathematical Proceedings of the Cambridge 
Philosophical Society, 24, pp 426­437 doi:10.1017/S0305004100015954

Request Permissions : Click here

Downloaded from http://journals.cambridge.org/PSP, IP address: 150.135.135.70 on 15 Dec 2012
426 Dr Hartree, The wave mechanics of an atom

The Wave Mechanics of an Atom with a non-Coulomb Central

Field. Part III. Term Values and Intensities in Series in Optical
Spectra. By D. R. HARTREE, Ph.D., Christ's College.
[Received 11 May, read 23 July, 1928.]
§ 1. Introduction.
In two recent papers* the writer has given an account of a
practical method of finding the characteristic values and functions
of Schrodinger's wave equations for a given non-Coulomb central
field. For terms of optical spectra the method is effectively the
following. We take the wave equation in the form
P" + [2v-e-l(l + l)/r2]P = 0 (I, 2"3)
and require the values of e for the solutions which are zero at the
origin and at r = x>. We consider the result of integrating this
equation outwards from P = 0 a t r = 0 t o a radius ro at which the
deviation from a Coulomb field is negligible, and inwards from P = 0
at r = oo to the same radius, with a given value of e; the charac-
teristic values are those values for which these two solutions join
smoothly on to one another, i.e. for which they have the same
value of T) = — P'jP at this radiusf. For a given e, the solution
zero at the origin depends on the particular atom; the solution
zero at infinity can be expressed in a form independent of any
particular atom.
For large values of the effective quantum number n, and so
small values of e, the solution zero at the origin can be treated as
a small variation on the solution for e = 0, and the value of •»/ at the
radius r0 for such a solution varies little with n, and is linear in e,
to the first order. But for the solution zero at infinity the value
of T) at r0 varies rapidly with n, however large n is J, so that the
possible values of n, and so of the quantum defect, are always well
defined. This suggests the questions, how can we determine q0,
the limiting value of the quantum defect as n-*-oo, and how does
q vary with n—in other words, what series formula for optical
spectra does the wave mechanics indicate ?
These questions involve the consideration of the solution of
(I, 23) for a Coulomb field and large, non-integral, values of n.
• Proc. Camb. Phil. Soc. vol. 24, pp. 89, 111 (1928). These papers will be
referred to as I and II. The same notation will be used here as in those papers,
with the exception that the effective quantum number will be written n instead of n*.
t Each solution contains an arbitrary multiplying constant, hence the form of
the condition for the solutions to fit.
X This solution cannot be treated as a variation on the solution for e = 0 , as for
any e, however small, e is the leading term in P"jP for r sufficiently large, and the
solution for such values of r for any eM=O is essentially different from that for e = 0.
 with a non-Coulomb central field 427
§ 2. Survey of the Problem.
It has already been pointed out by Eddington* and Sugiuraf
that the solutions of (I, 2'3) for a Coulomb field are confluent
hypergeometric functions^, and in particular that (apart from an
arbitrary multiplying constant) the solution zero at infinity is
P = Wn,l+i(2Cr/n),
as defined by Whittaker and Watson.§. In the applications to optical
spectra we are interested in the solutions of this equation for integer
values of I and positive non-integer values of n (greater than I)
which may be large, and moreover in comparing the solutions for
different n we are interested in their values at a given radius r,
not at a given value of 2Grjn, for it is at a fixed value of r that we
make the join between the solutions zero at r = 0 and at r = <x>,
and that the solution zero at r = 0 varies only slowly, and to the
first order linearly, with e. We require, therefore, the expansion
of Wn< z+j (2Gr/n) valid for small r. It will appear that
A Wn% i+i(2Cr/n) = G cos irn +. H sin irn,
where A is independent of r, and G and H are functions of r and
n which for a given r are even functions of l/«, and that this
property of the solution leads to the extended Rydberg-Ritz
optical series formula.
In the Coulomb field of a point charge 0, we have v = C/r,
e = C2/«2, and, if we take z = 2Cr/n(=2p of I) as independent
variable, (I, 2'3) becomes

When 21 is not an integer, two solutions in ascending powers of z

are Mn _ ± (J+H (z) in the notation of Whittaker and Watson ||, and the
relation between the solution Wn, J+J which is zero at infinity and
these two solutions in ascending powers is given by Whittaker
and Watson % But for the cases in which we are interested for
the application to optical spectra, I is always a positive integer;
the solution Mn>[+i remains, but A[n,-u+i) disappears, and the
other solution in ascending powers of z also involves terms in
logs.
We will first consider the two solutions of (2"1) valid near
z = 0, with I integral, and then find the relation between them
and the solution Wn< J+J which is zero at infinity by the same
method as that used by Whittaker and Watson for the case when
I is not integral.
* A. S. Eddington, Nature, voL 120, p. 117 (1927).
t Y. Sngiora, Phil. Mag. Ser. 7, vol. 4, p. 498 (1927).
i See E. T. Whittaker and G. N. Watson, Modern Analysis, ch. 16.
§ Op.cit. § 16-12. || Op. cit. g 16-1. • 1T Op. cit. § 16-41.
428 Dr Hartree, The wave mechanics of an atom

The solutions which are valid near the origin are most con-
veniently expressed with z as independent variable, and with
e~iz as a factor multiplying a series in ascending powers of z; the
coefficient of the general series term can then be expressed most
simply, and also this form is the most suitable in which to compare
these solutions with the expansion of Wnt J+J. But in this form a
property of them as functions of n for a given r (not z), which is
important in the sequel, is masked. To establish this property we
shall first consider the solutions of the differential equation with r
as dependent variable, or rather with
a = 2Cr = nz,
to avoid the continual appearance of the factor 20; for a given
spectrum, equal values of a clearly give equal values of r, inde-
pendent of n.
§ 3. Solutions as Functions of a (or r).
The differential equation with er as independent variable is
l l + 1
d?P | f l 1 (. )]p = Q (3-D

The indicial equation has roots I + 1, — I (see I, § 3), and two inde-
pendent particular solutions are of the form *

Hi (a) = a~l [b0 + Wo- + 62ffa ...] + aG[(<r) log a ...(33).

Substituting (3"2) in the differential equation we find for the
coefficients am the recurrence formula
m>l, (a_i = 0) ...(34).
The standard solution of the form (32) will be taken as that de-
fined by ao = 1/(21 + 1)!. It is clear that the coefficients am are
then polynomials in 1/n8, so that for a given value of a (and so
of r), this solution G is an even function of 1/n.
The corresponding recurrence formulae for the coefficients bm
in the solution (33) are found to be
( 2 l l ) b b + b l 2 l(6 0)

(3-5),
0. ba+1 = -ba+~ &«_! - (21 + 1) aa0 .. .(3-6),

m (m - 21 - 1) bm = - bm-i + ^ 6m_2 - (2m -21-1) aam^^,

2 (37).
* See, for example, H. T. H. Piaggio, Differential Equation*, § 98.
 with a non-Coulomb central field 429

The coefficient b2l+1 is indeterminate, as it must be since it is the

coefficient of o^"1"1, the first power of a in the solution Gt (a-), and
the sum of Hi and an arbitrary multiple of Gi is still a solution;
equation (3'6) relates the coefficient a of the log a- term to the
coefficients bm (m < 21).
These relations (3'5)—(37) between the coefficients show that
if a (or b0) and ba+1 (the coefficient of <xm) are even functions of
1/n, then the solution H is an even function of 1/n-, for given a.
Writing* *(«) = ^

and /3n,i = -v/r(n)-•f(?i-Q + —

2/
m=o r(n + l + l-m)m\(2l+l-m)
(3-71),
it will appear most convenient to take the standard solution H aa
defined by ao= 1/(21 + 1)1, already used to define the standard
solution G, and
a=l/7r, Tr(2l + l)\b2i+1 = -1r(l)- + (2l + 2)) (g.?2)

From Stirling's approximation to the V function we havef

\ogT(n)-(n-$)logn+n~$log2Tr+Z^ 2q (2q - 1) n2^'
so, differentiating,
/2«~ 2
which is an even function of 1/n.
I have not yet been able to find a, general proof that ySn, j is an
even function of 1/n for all I, but
1 T(n + l + l) / . . .

is certainly an even function of 1/n, and by direct evaluation

= !4(4n«-13) (i=2),

* Cf. Whittaker and Watson, op. cit. ch. 12. Writing 7 for Euler's Constant,
we have the special values ^(1) = - 7 , <p(n+\)~-y+ S (1/m) (n integral).
+ Cf. Whittaker and Watson, op. cit. § 12-33.
430 Dr Hartree, The wave mechanics of an atom
while direct expansion of y8n> j in inverse powers of n gives
&,,, = l/4>n* +1(31 + l)/16n4 + 0 (1/n6)
for any 1>1. So for s, p, d sequences (I = 0, 1, 2) at least, if is
exactly an even function of 1/n; for higher values of I deviations
from an even function, if any, are of order 1/ri1 at most, and as n is
greater than I in all practical cases, and 6a+i is of order unity,
such deviations will be quite unimportant.
We will write Gi (<r, 1/n2), Hi (a, 1/n2) for the standard solutions
G defined by ao = (2l + l)\, and H defined by (3-72). 1/n2 is
written as an explicit argument of G and H to emphasise that
they are even functions of 1/n for a given value of a- (or r).
The function Gt (<r, 1/n2) is the only solution of (31) and so of
(2*1) which is zero at the origin, hence it must be a simple multiple
of the solution Mn> i+i of (2 - l) given by Whittaker and Watson, viz.
Mn,
M

(3-8)

-m) (vi-2l-iy.m\

Putting z = a/n and comparing the lowest term of this expression

for Mn> i+i {a/n) with that of Gt (a, 1/n2) defined by (3-2) we see
that

so that nl+1 Mn< J+J {cr/n) is an even function of 1/n, for given a;
this result is by no means obvious from the series formula for

§ 4. Limiting Forms of Solutions for 1/n2 = 0.

For l/« 2 = 0, equation (3 - l) becomes

whose solutions are expressible in Bessel functions*.

Comparing coefficients we have

using the notation adopted by Watsonf for the Bessel function of

the second kind.
* See E. Jahnke and P. Enjde, Funktionentafeln, p. 166. [Put /3=2, 7=4,
p = 2l+l in the second equation of § 13.]
t G. N. Watson, Treatise on Bessel Functions, § 3-52 (3), and § 3-54 (2).
 with a non-Coulomb central field 431
As will be seen later, these results are useful in determining
the limiting value of the quantum defect of a sequence of terms
as n-*-ao.
§ 5. The Expansion of Wn> J+J (z)for small z.
We consider now the expansion for small z of Wn, J+J (z), the
solution of (21) which is zero at infinity. We have from a formula
given by Whittaker and Watson*,

where (2-R') is the sum of the residues of

r(s)V(-s-n-l)T(-s-n
at the poles of
r(-s-n-l)r(-s-n
These poles are s = — n — l + m, m integral and > 0; for
0 ^ m ^ 21 they are simple poles, for m > 21 + 1, double poles.
Evaluating the residues, we find

n ^(-n-l + m)T(2l + l-m)

m=0 m!
_ •
m=2«+i m\(m 2l iy.
X {log Z + TJr(-n-l + m) — y}r(m + l) — yfr(m~ 21)} .
Taking the factor l/r(—n-l) inside the square bracket and
using the relations

and writing sin ir (n — I) = (—)' sin 7r«, since ^ is integral, we have

x —2 „ , ' , —
L ».=or(n + / + 1 — m m!

( )
x {log z + 7T cot irn + yjr (n +1 + 1 - m) - yjr (m + 1) - yfr (m - 2J)}
(5-3).
* Op. cit. § 16-41.
432 Dr Hartree, The wave mechanics of an atom

By comparison with the series (3"81) for Mnj+i(z), the

coefficient of cos mi in (5"3) is seen to be

If now we write

= — e~iz (nz)~l . _ _ , _ ,

r
I ( _ )m-i ^ + ^ + 1) «"

x Ji^ (?i) - ifr (n + / + 1 - m) + ^ (m + 1) + ^r (m - 20 + l/2n)

(5-4)
as definition of Mntt^^{z), (53) becomes

W
x «-'Jtf,,, ;+J (^) S m J r - +« J + 1 Jlfn> J+i (^) cos Trn (5-5).

This gives the required expansion of Wn< * + i (z) for small values
of z. Since Wn, i+i and Mn< i+ j are both solutions of equation (21),
and their coefficients in (5'5) are independent of z, Mnj+^ must
also be a solution.
If we now put z = ajn in order to find the behaviour of
Wn< i+i (ff/w) with n for given a (or r), we have from (3*9)
n^Mn,l+k(a/n)l(2l + 1)1 = Gt (a, 1/n8).
Also Mn, i+i(<r/n) is a solution of equation (2"1), so must be a sum
of multiples of Oi{a, 1/n?) and Hi(<r, 1/ra2). These multiples can
be found by comparing the coefficients a of [Gi(a; 1/n2) log <r] and
ba+1 of <rl+1 in n~lMn, j+J(o-/n) defined by (54) with those adopted
for the standard solutions G and H.
 with a non-Coulomb central field 433
We have immediately a = (2^ + 1)!, and if we multiply the
first term in the square bracket on the right of (5-4) by the factor
a~le~"l2n outside, the coefficient of <rl+1 in the product is
! ,iy
- m) m! W

n2!+1 rto f
r ( « + I + 1 - n») ml (21 +1 - m )

i - (X
W
Adding the contributions from other terms on the right of (5'4)
and comparing with the definition of /3n> j_ we see that the co-
efficient 52j+i of <rt+1 in n~lMn> i+± (<r/n) is altogether

W = ^ («) - log » - ^ - * <2* + 2) - * (1) - /8B>J.

This value for b^+i and the value a = (21 + 1)! are just IT (21 + 1)!
times those chosen to define Hi (a, 1/n2), so that
n~lMn, ,+j (<x/n) = 7T (21 + l)!5i(<r, l/«2),
and using (3-73), (55) becomes

= (?j (<r, l/«2) cos 7rn + Hi (<T, 1/W2) sin TTW

This gives the solution zero at infinity in the form required
for deriving the optical series formula. For a given radius r,
the coefficients of sin -rrn and cos irn are seen to be even functions
of 1/n, exactly for 1 = 0, 1, 2, and for all practical purposes, if not
exactly for other values of I.
The case n — I integral is specifically excluded from the
definition of W by an integral from which (51) is derived, but it
is included in this result (56), for when n is integral, comparison
of the series for W and M, which then terminate, gives

and (5"5) reduces to this for n integral.

434 Dr Hartree, The wave mechanics of an atom
§ 6. The Extended Ritz Series Formula.
Thus for the solution of the wave equation zero at infinity,
the value of 77 = — P'jP at a given radius* depends on the effective
quantum number in this way:
_ P' _ 0' cos irn + H' sin vn
V (
~~~P Gcoairn+Hsimrn ''
where for a given radius 0, H, Q', H' are even functions of 1/n.
For the values of n corresponding to characteristic values of
the wave equation, this must be equal to the value of 77 for the
solution zero at the origin; if P, P' refer to this solution, the
value of n is given in (6'1). Now by definition of the quantum
defect q, n + q is the principal quantum number n which is an
integer. So from (6'1)
(G'P - QP') cos irq + (HP - HP') sin -nq = 0
(6-2).
This equation determines the fractional part of q—the integral
part depends on the definition of n.
The limiting quantum defect q0 is founded by inserting values of
P,G,Ha.n& their differential coefficients for l/n 2 =0 (or e = C2/n2=0).
For G and H the expressions in terms of Bessel functions (§ 4)
may be useful, as the quantities required have already been
tabulated or can easily be evaluated from the recurrence formulae,
for the Bessel functions.
Consider now the variation of q along a sequence of terms.
We consider the solution, zero at the origin, for any given z as a
variation (see I, § 4) on the solution for e = 0; this is legitimate
(see § 1) and gives P and P' as power series in e. Also, for a given
r, 0 and H are power series in 1/n2, i.e. in e (since e = CP/n2).
Hence q obtained by the solution of (6'2) is a power series in e,
and this leads directly to the extended Ritz formula for series in
optical spectra,

It will be noted that this derivation of the Ritz formula

depends essentially on the coefficients of 2sin nn and cos irn in (5'6)
being expressible in power series in 1/n , for given r. This does
not appear obvious from the expression (5"3) forl W; in fact, at a
first glance, one would say that in (5*5)-both n~ M given by (54)
and nt+1 M given by (3-8) involved also odd powers of 1/n; if this
were so, it would lead to a series formula in which q was expressed
as a power series in e*; the preliminary investigation of § 3
appears necessary in order to establish the absence of these odd
powers of 1/n.
* Dashes denote differentiation with respect to r.
 with a non-Coulomb central field 435
§ 7. Applications of the Expansions.
In several applications of the wave mechanics it is necessary
to know for small r the solution of the wave equation zero at
infinity, e.g. in the determination of term values or quantum
defects and of intensities in line spectra.
The most satisfactory way of evaluating this solution seems to
be to calculate the functions 0 and H and use (5-6); the evalua-
tion of 0 and H would probably be best done from the series (see
§ 3) out to about a = 2, or perhaps further, followed by numerical
integration (for a suitable method see I, § 9). This would not
have to be done for many values of n, since for a given r (or <r),
6 and H vary slowly with n; the greater part of the variation of
the solution at a given radius comes from the variation of the
circular functions in (5'6).
If the solution zero at infinity is found by direct integration
inwards (see I, §§ 5, 6), it is necessary to know the solutions at
intervals of n of 0 1 or closer in order to be able to interpolate
satisfactorily. This involves 9 numerical integrations and use of
recurrence formulae (I, § 6) which, though analytically simple, are
very tedious to use in practical work, especially if the solutions for
n — I greater than 4 or 5 are required, and are not very satis-
factory in practice on account of the difficulty of keeping an
adequate check on the work; besides, the recurrence formulae
relate the values of the various solutions at equal values of z,
whereas the values usually required are those at equal values of r.
The method here suggested should be altogether much more
satisfactory; it is applicable to any n, however large, and the
interpolation for any value of n would almost certainly be very
easy.
If this method were used, it would probably be advisable to
take the arbitrary constant in P so that

()
= Gt (2CV, 1/n2) cos irn + Hi (2Cr, 1/n.2) sin irn
(7-2).
Then, for given quantum defect, P as a function of r is nearly
independent of n (apart from a possible change of sign for all r).
The normalisation integral JP2dr will be required in some
applications, e.g. in the calculation of intensities.
From the asymptotic formula* for W, it follows that with the
arbitrary constant in P so defined,

* See Whittaker and Watson, op. cit. § 16-3.

436 Dr Hartree, The wave mechanics of an atom
for large r. Now it was shown in (I, § 7) that if the arbitrary
constant is chosen such that
{) <rCrln (7-4),
then, neglecting the contribution to the normalisation integral
from the range of r where the deviation from a Coulomb field is
large,
(C/n) (a P*dr = 2~2»»r (n + I + 1) T(n - I).
Jo
The definition (7*1) gives a value of | P | bigger by a factor

as can be seen by comparing (7'3) and (7'4), and so a normalisation

integral bigger by a factor which is the square of this. Thus with
the arbitrary constant in P defined by (7 - l)

§ 8. Asymptotic Variation of Intensity in Optical Series.

As a simple application, we may derive the law I ~ l/n3 for the
variation of intensity / in a series in an optical spectrum.
Let suffixes A and B refer to the two states concerned in.the
transition. Then for a transition between states of given lA, lB,
giving a line of frequency v, we have*
IcCV (81)
JYJaVJPjdr -
If now A refers to the final state of an emission transition, PA
is the same function for r for all the lines of a series; also with
the arbitrary constant determined by (7"1), PB = const. + 0 (l/n2)
for a given r (apart from a factor + 1), and PA has become
negligibly small before the differences between the different PA's
become large (except possibly for the first line or two of the series).
Thus the numerator (8"1) differs by terms of order l/n.2 from a con-
stant for a simple series, and
I/p* - [JPjfdr]-1 ~ l/n3 (8-2)
by (7'5). It must be emphasised that n here is the effective quantum
number; the law is likely to hold more closely for the earlier
* The square of the matrix amplitude for the transition is [cf. Sugiura, loc. cit.
equation (4)] [\rPAPBdrfl (P^drjP^dr multiplied by an absolute constant and
by a factor depending on lA and IB, arising from the dependence of the wave
functions on direction of the radius r. The factor v4 arises from the relation
between doublet amplitude and intensity of emitted radiation.
 with a non-Coulomb central field 437
lines of a series when it is taken so rather than as the principal
quantum number, though asymptotically these5 are equivalent.
Deviations from this simple law are of order 1/n .
Since the transition frequency v differs from the frequency of
the series limit by terms- of order 1/n2, we have I ~ 1/n3 to the
same approximation as (8 2), but it seems probable that deviations
from this law would be larger than those from (8'2), for the early
lines of a series.
§ 9. Summary.
An expansion valid near the origin is found for the wave
solution of the wave equation in a Coulomb field for terms of non-
integral principal quantum number n. It is shown that, apart from
a factor independent of r, this is of the form G cos irn + H sin irn,
where, for given r, G and H are even functions of 1/n. The ex-
tended Ritz formula for a sequence of terms in optical spectra
follows. The law I/vl oc 1/n3 for the variation of intensity in a
series with the effective quantum number of the variable term is
also derived from this result.
I wish to express my thanks to Mr R. H. Fowler for his advice
at several points in the course of this work.

VOL. XXIV. PART III. 29