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MechanicsOfAtom-MaxBorn

MechanicsOfAtom-MaxBorn

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Published by Pradosh K. Roy
The fundamental text book on Atomic Physics by Nobel Laureate Max Born , one of the founders of Matrix Mechanics.
The fundamental text book on Atomic Physics by Nobel Laureate Max Born , one of the founders of Matrix Mechanics.

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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 many-body 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 non-mechanical 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

sub-groups. 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

one-body or as a

two-body 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 co-ordinates is

precisely the same for the

two cases, if, in the

one-body 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 co-ordinates r, 6, and

. Making use of the

canonical transformation

(13), 7, which transforms

rectangular into

polar co-ordinates, 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, . The structure of the Hamiltonian

function

shows that r, 0,

are

separation variables. If one

puts

(2)

S=Sr(r)+Se

(0)+S/<),

the Hamilton-Jacobi 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 co-ordinate

(f> is

cyclic and

performs a rotational motion

(cf.

9). The co-ordinate 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=--j-i.

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 non-zero 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

-j-r-

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=We-Wr

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

J-a

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

we

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

single-valued 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 co-ordinates

,

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 co-ordinates 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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