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https://www.scribd.com/doc/53729235/MechanicsOfAtomMaxBorn
07/21/2013
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THE
applications of the
principles of
quantum mechanics, developed
in the second
chapter, are at
present considerably restricted, owing
to the fact that these
principles are concerned
only with
multiply
periodic systems. The first
example dealt with
by Bohr, namely,
systems consisting of a nucleus and a
single electron
(the hydrogen
atom and the similar ions He+
, Li++
,
etc.), satisfies this condition of
periodicity. In the case of other atoms the same difficulties underlie
an examination of the
periodic properties as in the case of the
many
body problem of
astronomy, and we can
proceed only by a method
of
approximation. Bohr realised that a
large number of atomic
properties, especially those which exhibit themselves in the series
spectra, may be
explained on the
hypothesis that one electron, the
"
radiating electron "
or "
series
electron/' plays a
special role in
the
stationary states under consideration. The essential feature of
these states is that this one electron is in an orbit, which, at
any
rate in
part, is far removed from the rest of the
atom, or "
core," x
and exerts
only a small reaction on the latter. We shall
always
speak, therefore, of the
stationary orbits of the
radiating electron,
since we
neglect the
changes taking place in the core. The
spectrum
of the atom
corresponds then to transitions of the
radiating electron
from one orbit to another.
This
assumption implies that the motion of the outer electron is
multiply periodic, and that, in
traversing the core, the electron
neither
gives up energy to nor receives
energy from it. Motions of
this kind are
quite special cases
according to classical
mechanics, for
the motions of the core electrons must be such that their
energy is
the same after
every period of the outer
electron, a condition which
1
German, Rumpf. The English equivalent of this word is not
completely
standardised: the alternatives
"body," "trunk," "kernel" have been used
by
different writers.
130
SYSTEMS WITH ONE RADIATING ELECTRON 131
is
evidently fulfilled
only by strictly periodic solutions of the com
plex manybody problem. Since, however, a
large number of obser
vations
may be
explained in a
surprisingly simple way by such
stationary orbits of the
radiating electron, it
appears that we are
here
dealing with some
general process, which cannot
easily be ex
plained by such
singular types of motion. We have here the same
failure of the classical mechanics as was
brought to
light by Franck's
researches on electron
impact ; the
exchange of
energy between
electron and atom, or atom core, is restricted in a manner similar
to that familiar to us in the
energy interchange between an atom
and radiation.
At
present we cannot
express this nonmechanical behaviour in
formulae. We endeavour to substitute for the atom a model which
possesses, in common with the actual atom, this characteristic
pro
perty of the absence of
energy exchange between core and electron,
and to which the
principles of the
quantum theory, developed in the
second
chapter, are
applicable. The
simplest assumption is that the
action of the core on the
radiating electron can be
represented by
a
spherically symmetrical field of force. Further
development has
shown that this
simple hypothesis suffices to
provide an
explanation
of the main characteristics of the
spectra of the first three divisions
of the
periodic table and their
subgroups. The
conception of a
single
"
radiating electron "
is, however, no
longer adequate to
explain the
spectra of the
remaining elements, but these considera
tions are
beyond the
scope of this book.1
For this reason we shall now deal with the motion of a
particle in
a central field of force. The motion in a Coulomb field of force
(such
as we have in the case of the
hydrogen atom) will be found from this
as a
special case.
So far as the calculation is concerned it is immaterial whether we
consider our
problem as a
onebody or as a
twobody problem. In
the first case we have a fixed centre of force, and the
potential of the
field of force is a function
U(r) of the distance from the centre. In the
second casewe have two masses, whose mutual
potential energy U(r)
depends only on their distance
apart ;
they move about the common
centre of
gravity. As we have shown
generally in
20, the Hamil
tonian function in
polar coordinates is
precisely the same for the
two cases, if, in the
onebody problem, the mass
p of the
moving
1
For the development of the
theory of
complex spectra, see H. N. Russel and
F. A. Saunders, Astroph. Journ.t vol. Ixi, p. 38, 1925 ; W. Pauli, jr., Zeitsch.
f.
Phys., vol. xxxi, p. 765, 1925 ; W. Heisenberg, Zeitschr.
f. Phys., vol. xxxii, p. 841,
1925; F. Hund, Zeitsch.
f. Phys., vol. xxxiii, p. 346; vol.
xxxiv, p. 296, 1925.
132
THE MECHANICS OF THE ATOM
body and its distance r from the centre are used, and if in the two
body problem /* is defined
by the
equation (2), 20,
=+,
/LC
m1 m2
'
and r is the distance between the two masses. The
following equa
tions admit then of both
interpretations.
We work with
polar coordinates r, 6, and
canonical transformation
(13), 7, which transforms
rectangular into
polar coordinates, we obtain for the kinetic
energy,
22*5
where
pr,
pe,
p^ are the momenta
conjugate with r, 0, ^ respectively.
We arrive, of course, at the same
expression when we calculate from
sn2
2
the momenta :
and use them to
replace r, 9,
function
shows that r, 0,
are
separation variables. If one
puts
(2)
S=Sr(r)+Se
(0)+S/<),
the HamiltonJacobi differential
equation
splits up into three
ordinary differential
equations :
which can be solved for the derivatives of S :
SYSTEMS WITH ONE RADIATING ELECTRON 133
d$r
Of the three
integration constantsWdenotes the
energy ;
==xr2
sn2
is the
angular momentum about the
polar axis
(i.e. the line
6=0), and
is the
magnitude of the resultant
angular momentum. Since also
the direction of the
angular momentum is constant
(as in
every
system subject to internal forces
only), the orbit is
plane and the
normal to the
plane of the orbit is
parallel to the vector
representing
the
angular momentum. The inclination i of the orbital
plane to the
(r, <)plane is
given therefore
by
a>4=a, cosi.
We consider next the
general character of the motion and then
determine the
energy as a function of the action variables for the
case of a
periodic motion and, finally, we consider the
progress of the
motion in time.
The coordinate
(f> is
cyclic and
performs a rotational motion
(cf.
9). The coordinate 6
performs a libration or limitation motion in
an interval, symmetrical about
w/2, whose limits are
given by the
zero
points of the radicand in the
expression of
pe, i.e.
by
sin 0=_*=cos i,
0=ji.
a
2
Further, the character of the motion
depends essentially on the be
haviour of the radicand in the
expression for
pr,
We investigate the various
possible cases on the
supposition that
U(r) is a monotonic function of r and that the zero of
potential
energy is so chosen that it vanishes for r=oo .
134
THE MECHANICS OF THE ATOM
Case 1. In a
repulsive central field of force
U(r) is
positive. In
order that
positive values of
F(r) shall occur at all,Wmust be
posi
tive.
F(r) will then be
positive for
large values of
r, decreasing con
tinually with
continuously decreasing r ; for small values of
r, F(r)
is
certainly negative ;
F(r) has therefore
exactly one root. The
motion takes
place therefore between r=oo and a minimum value
of r.
Case 2. In an attractive central field, U(r) is
negative, and W
may be
positive or
negative. The
sign F(r) for
large values of r is
determined
by W. For
positive W, F(r) is
positive there, and there
are motions which extend to
infinity. There are no such orbits for a
negative W. In the case of W=0 the variation of U with r, and, in
certain cases, the
magnitude of a
e, is the
deciding factor. The
sign
of
F(r) for small values of r
depends on the rate at which
j U(r) 
be
comes infinite.
If, for small r, it increases more
rapidly than
1/r
2
,
1
F(r) will be
positive there, and there will be orbits which
approach
indefinitely close to the centre of force
; if
 U(r) 
becomes infinite
more
slowly than J
/r
2
there will be no such orbits ; if
 U(r) j
ap
proaches infinity as
1/r
2
, the
magnitude of a
e is the
deciding factor.
Further, there are cases
where, in addition to
paths extending to the
centre and to
infinity, orbits exist which extend between two finite
and nonzero values of
r, r
mm and r
max ; this is the case when r
min
and r
raax are consecutive zero
points of
F(r), between which F is
positive. In the case where
 U(r) 
becomes infinite more
slowly than
1/r
2
it is certain that there are values of W for which such a libra
tion sets in ; for
negativeWthere are in
fact, in this
case, no other
motions but librations.
In
many applications to atomic
physics we are
only concerned
with those motions in which the electron remains at a finite distance
from the centre and which are
periodic. Weconsider therefore in the
following only the case of attraction and take forWvalues such that
F(r) is
positive between two consecutive roots r
mm and r
max.
In this case we can
apply the methods
developed for
periodic
motions. We obtain the action
integrals
1
Mathematically expressed, this has the
following significance : the order of
magnitude of
 U(r) 
is
larger than that of
1/r2
for small values of r. The order
of
magnitude of a function
f(x) (>0) is
greater than the order of
magnitude of the
function
g(x) (>0), for small values of
x, if
/(*) and g(x) have the same order of
magnitude if the
limiting value of
jr
r is a
J\^f
finite constant.
SYSTEMS WITH ONE RADIATING ELECTRON 136
(4)
JJ/)=
With the
help of the substitution
a
1
i
a
e
the second
integral takes the form
Jn=
The evaluation of this
integral (cf. (3) and
(8), Appendix II) gives
J^M** %)
We can now
express a
e and a in terms of the action variables
In order to find the
energy as a function of the J's we should have
to solve the
equation
(6)
for W. This is
impossible without a detailed
knowledge of
U(r) ; it
is
seen, however, that W depends only on Jr and the combination
J0+J .
The two
frequencies
aw
are therefore
equal andthe
system is
degenerate. In accordance with
the fundamental
principles developed in
15, we introduce new
variables wl9 w2, w& and J
1? J2, J
3, so that w.
3 is constant. We
arrange at the same time that, in the case of the Coulomb field of
force, where v
r=v
& v^ that the variable w2 shall also be constant.
We write, therefore, in accordance with
(8), 7
136
THE MECHANICS OF THE ATOM
Wl=Wr
Jl=Jr+J0+J
(7)
W2=WeWr
J2
=J0+J,
W3=w*We J3=J
,
The
equation (6) contains then
only Jx and J2, and we derive the
energyWin the form
(8)
W=W(J,, J2).
For the
stationary motions we have, provided there is no further
degeneration (e.g. no Coulomb field), the two
quantum conditions :
n is called the
principal quantum number and k the
subsidiary quan
tum number.1
The action variables have the
following physical significance : J2
is
1/27T times the total
angular momentum, J
3 is
l/2ir times its com
ponent in the direction of the
polar axis.
It is obvious that Ja cannot be zero. Also J2=0 would
signify a
motion on a
straight line
through the centre of
force, a "
pendulum
motion "
; in
physical applications, where the centre of force is the
atomic nucleus, this case must of course be excluded.
In order to find the
physical significance of the
angle variables,
we calculate them with the
help of the transformation
equations
as
If we introduce the
J^'s in the
equation (3) we obtain
47rV2
T 2
v
'

3
JrO o
.
*
sin2
6
1
and for the
angle variables I
putting v
l= =
]
:
1
k is also called the azimuthal
quantum number. This term arises from the
fact that it can also be
put in the form
where is the azimuth of the
moving point in the orbital
plane.
SYSTEMS WITH ONE RADIATING ELECTRON 137
r
c
*
7
(10)
r
1
2
"J
Ja
sin2
fl
The two
integrals in dO
may be evaluated. We have
(10/)
dO
.
cos 6
;_~=sin"1
r+const.
'
T 2
.
Jo
sin2
(9
sm^
and
(10")
sin2
6
V'.
= r
:
Jsin
2
cos i dO
/
cos2
!
V ""sin2
!
J2
2
sin2
J V *
sin2
=sin*1
(cot i cot
0) +const.
It will be seen from
fig. 11
that, apart from the
arbitrary constant
of
integration, the
integral (10') is
the
angular distance
if/ of the
moving
point from the line of nodes,
measured on the orbital
plane, and
the
integral (10") is the
projection
of this
angular separation on the
(r, <)plane. By subtraction of this
projection from
get the
longi
tude of the line of nodes. The third
of our
equations (10) states, there
fore, that, apart from an
arbitrary
additive
constant, the
longitude of the node is 27rt0
3.
According to
the second of the
equations (10), 2irw
z is the
angular distance of
FIG. 11.
138
THE MECHANICS OF THE ATOM
the
moving point from the node, measured on the orbital
plane, in
creased
by a function of r :
, J
1? J2)
For
given Jj and J
2, F2 is a
singlevalued function of r, for, during
a libration of
r,
Jprrfr increases
by Jj ; the
partial derivative with
respect to J2 assumes, therefore, its old value once more.
Apart from
an additive constant, 27rw
2 is
consequently the
angular distance of a
point of the
path with a
given r from the line of
nodes, measured on
the orbital
plane, and therefore, apart from a constant, the
angular
distance of the
perihelion (rmm) from the line of nodes.
Finally, again
apart from an additive constant, 277^ is what astronomers call the
"
mean
anomaly," namely, the
angular distance from
perihelion of a
point imagined to rotate
uniformly and to
pass through perihelion
simultaneously with the actual
moving point.
Since we have a
system subjected only to internal forces, and the
motion takes
place in a
plane, the
angle variablew2, associated with
the total
angular momentum, occurs in the Fourier
representation of
the electric moment with the factor 1
only (as was shown
gener
ally in
17). We can see this also
directly, from the nature of the
expressions for the
angle variables. These are :
^1=
fi(r, Ji, J2)
w2
lf J
2)
w
3=const.,
or, if we solve for
r, i/r,
r=
^(wl9 Ji, J2)
lfj
=2TTW
2 +(l>2(Wv J
1? J2).
If we transform to the
rectangular coordinates
,
r],
, where is
perpendicular to the orbital
plane, we find for the
components of the
electric moment p expressions of the form
(11')
P^=.
According, then, to the
correspondence principle, the number k, of
the
quantum numbers n and k introduced
by (9), can alter
by 1
only, while n can in
general change by arbitrary amounts.
The orbit is best
expressed in terms of the coordinates r and
*//.
From the first
equation (10) we
get
SYSTEMS WITH ONE RADIATING ELECTRON 139
dw
UL
,dr.
Also since the
angular momentum is Jz/27r
we eliminate dt and derive the differential
equation of the orbit
(12)
27T
dr~
477V2
Since the motion consists of a
libration of
r, combined with a
uniform rotation of the
perihelion,
the form of the orbit is that of a
rosette
(cf. fig. 12).
FIG. 12.
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