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35-1
Hydrogen Atom and Non-Euclidean
Geometry1
V.A. Fock
Received on 3 April 1935
of Leningrad State University, and on March 23, 1935 at the Session of the USSR
Academy of Sciences in Moscow.
x1 = r, x2 = r, x3 = r, x4 = r (11)
This function can be called the Greens function of the third kind because
it satisfies the boundary condition on the sphere surface
G
+G=0 at r0 = 1. (15)
r0
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Z
1 u
u(x1 , x2 , x3 , x4 ) = u+ 0 Gd0 . (16)
2 2 r r0 =1
Putting these expressions into (16) and using (13) and (14) for r0 = 1,
one gets
Z
n n (0 , 0 , 0 )
rn1 n (, , ) = d0 . (19)
2 2 1 2r cos + r2
This equation is valid also for r = 1 and in this case can be reduced to
(8); the parameter is equal to integer n
Zme2
= = n, (n = 1, 2, 3, . . .), (20)
h 2mE
top has been given by Hund [F. Hund, G ottinger Nachr., M.-Phys. Kl., 1927, 465].
(V. Fock)
where l and m have the usual meaning of azimuthal and magnetic quan-
tum numbers and Ylm (, ) is a standard spherical function normalized
by the condition
Z Z 2
1
sin d | lm (, ) |2 d = 1. (22)
4 0 0
If we set
Ml2 = n2 (n2 1) . . . (n2 l2 ), (23)
then the function normalized according to
Z
2 2
l (n, ) sin2 d = 1 (24)
0
or as a derivative
sin n
0 (n, ) = . (26)
sin
Note that these formulae give the determination of the function l (n, )
also valid for complex n (continuous spectrum). The function l satisfies
the following relations:
dl p
+ l cot l = n2 (l + 1)2 l+1 ; (27a)
d
dl p
+ (l + 1) cot l = n2 1) l1 , (27b)
d
d2 l dl l(l + 1)
+ 2 cot l + (n2 1)l = 0. (28)
d2 d sin2
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3. Let us turn now to the derivation of the addition theorem for four-
dimensional spherical functions. Equation (19) is an identity relative to
r. If we expand the integrand as a power series in r,
X
1 sin k
2
= rk1 , (29)
1 2r cos + r sin
k=1
and compare the coefficients in the right- and left-hand sides of (19), we
get Z
n sin k 0
n (0 , 0 , 0 ) d = kn n (, , ). (30)
2 2 sin
But the quantity n sin n
sin as a function of , , is a four-dimensional
spherical function that can be expanded in series of functions nlm (0 ,
0 , 0 ). The expansion coefficients are determined by relation (30) (at
k = n). Thus, we arrive at the addition theorem
n1
X X l
sin n
n = nlm (, , )nlm (0 , 0 , 0 ). (31)
sin
l=0 m=l
If we substitute here relation (21) and use the well-known addition the-
orem for three-dimensional spherical functions, then we can rewrite (31)
in the form
sin n X
n = l (n, )l (n, 0 )(2l + 1)Pl (cos ), (32)
sin
l=o
Zs. Phys. 74, 216, 1932] derived a differential equation [see (9g) and (10b) of his pa-
per], which can be easily reduced to that for the four-dimensional spherical functions
in stereographic projection. [With the kind permission of E. Hylleraas, we correct
here the following misprints in his works: in the last term of equation (9f) as well as
of (9g) the magnitude E must have a factor 4]. (V. Fock)
sponds to the interval 2mE < p < . In this case, the Schrodinger
equation can be written as a system of two integral equations connecting
the values of the desirable functions on both sheets of the hyperboloid.
We can give the following geometrical interpretation of our results.
In the momentum space in the case of a discrete spectrum, there is the
Riemann geometry with the constant positive curvature and in the case
of a continuous spectrum there is the Lobachevskii geometry with the
constant negative curvature.
The geometrical interpretation of the Schrodinger equation for a con-
tinuous spectrum is less descriptive than that for the case of a discrete
spectrum. Therefore, it is reasonable first to obtain the formulae for the
point spectrum and only in the final result take the principal quantum
number to be imaginary. This can be done because l (n, ) are analyt-
ical functions of n and , which for the complex values of n and differ
from those for a discrete spectrum by constant factors only.5
5. Now let us list briefly the problems to which the presented theory of
hydrogen-like atoms can be applied.6 In many applications, e.g., in the
theory of the Compton effect by bounded electrons [2, 3] as well as in the
theory of inelastic electron collisions by atoms [4], in the mathematical
sense the problem is reduced to the following. The projection norm [5] of
the given function on the subspace of the Hilbert space, characterized
by the principal quantum number n, needs to be found. In other words,
one needs to find the sum
Z X Z
2
N = |Pn | d = | nlm d |2 . (33)
l,m
In calculation of this expression, the main difficulty is to sum over l,
especially for the cases when the level belongs to the continuous spectrum
(imaginary n) and the sum is of an infinite number of terms. Sometimes
it is possible to reduce the sum to the integral by using the parabolic
5 See [1] V.A. Fock, Basic quantum mechanics (Nachala kvantovoj mekhaniki),
Leningrad, Kubuch, 1932,162 (in Russian), eqs. (16) and (17); eq. (17) should be
corrected, namely, factor 2 should be omitted. (V. Fock)
6 We propose to treat these problems in a separate paper in more detail; it will be
The expressions of the type (34) arise, e.g., in the calculation of the
so-called atomic form-factors. Here the operator L in the momentum
representation is of the form
L = ek p ; L(p) = (p k). (35)
By relation (7) we can express the function nlm through the four-
dimensional spherical functions. Since the mean-square momentum p0
By substituting this expression into (37) and using the addition theorem
(31), we get
8p5n sin n
%n (p0 , p) = n . (39)
2 (p2 + p2n )2 (p02 + p2n )2 sin
8p5n
%n (p, p) = . (40)
2 (p2
+ p2n )4
The integral Z
4 %n (p, p)p2 dp = n2 (41)
7. The success of Bohrs scheme for the Mendeleev periodic system and
good applicability of the Rietz formula for energy levels show that the
assumption that the atomic electrons are in the Coulomb field can give
a satisfactory approximation.
Therefore, it is interesting to consider the following simplified variant
of the Bohr model of an atom. The atomic electrons are subdivided on
large layers; all electrons with the same principal quantum number n
belong to the large n-layer. Electrons of the large n-layer are described
by hydrogen-like functions with the effective nuclear charge Zn .
Instead of Zn , one can also introduce the mean-square momentum
pn connected with Zn by
a
Zn = npn (a is the hydrogen radius). (42)
h
Under these assumptions, one can express the atomic energy as a func-
tion of the nuclear charge and parameters pn and then determine these
parameters from a variational principle. Here one needs to take into
account the following. Although our wave functions of electrons belong-
ing to the same large n-layer are orthogonal to each other, they are not
orthogonal to the wave functions of other large layers. Therefore, in this
where Tn0 (x) is a derivative of the Chebyshev polynomial with the mini-
mum deviation from zero
Tn (x) = cos (n arccos x) (48)
and Pn0 is a derivative of the Legendre polynomial Pn (x). Obviously, for
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References