QUANTUM CVtNl R Al \OKS
ATOMIC A R C H I T E C T U R E 45
Chapter4 ( pp. M^- 5-))
ATOMIC ARCHITECTURE
T H E THOMSON ATOM
S P E C U L A T I V E IDEAS about the constitution of atoms can be found
many decades before the discovery of the electrón, but only with the
new particle did atomic models acquire a more realistic status. The
electrón was generally accepted as a building block of matter, which led
directly to the first elabórate model of the interior of the atom. Thomson's
important "plum pudding" model, consisting of electrons held in positions of
equilibria by a positive fluid, was first enunciated in his 1897 paper, but it
was indebted to work done many years earlier.
One of the important sources was the vortex atomic theory, according to
which atoms were conceived as vórtices in a perfect, all-pervading fluid.
Another source was an experiment that the American physicist Alfred M .
Mayer made in 1878. Mayer subjected equally magnetized needles floating
in water to the attractive forcé of a central electromagnet and noticed that the
needles took up equilibrium positions on concentric circles. Lord Kelvin
(then still William Thomson) immediately realized that the experiment fur-
nished a good analogy to the vortex atomic theory. The analogy was taken
up by the young J. J. Thomson in his Adams prize essay of 1883, where he
dealt in great mathematical detail with Kelvin's vortex theory. In this work,
Thomson (from now on, "Thomson" will refer to J. J.) examined theo-
retically the stability of a number of vórtices ananged at equal intervals
around the circumference of a circle. For more than seven vórtices, where
the calculations became highly complex, he referred to Mayer's magnet ex-
periment as a guide.' Thomson assumed his elementary vórtices to be of
equal strength, which not only simplified the calculations but also agreed
with his inclination toward a monistic theory of matter. There is a clear
analogy between his vortex arrangement of 1883 and his later arrangement
of electrons. Although Thomson, like most other physicists, abandoned the
vortex atomic theory about 1890, the idea continued to appeal to him. In
1890 he linked the periodic system of the elements with the vortex atomic
model and pointed out the suggestive similarity between an arrangement of
columnar vórtices and the regularity found among the chemical elements: "If
we imagine the molecules [atoms] of all elements to be made up of the same
primordial atom [elementary particle], and interpret increasing atomic weight
to indícate an increase in the number of such atoms, then, on this view, as
the number of atoms is continually increased, certain peculiarities in the
structure will recur" (Kragh 1997b, 330). Clearly, Thomson was inclined to
conceive of the atom as a composite system of primordial elements years
before the discovery of the electrón.
In his paper of Oclober 1897, Thomson suggested that the atom consists
of a large number of corpuscles (electrons), possibly held together by a cen-
tral forcé. Relying on Mayer's experiment, he indicated that the electrón
configuration was a ring structure and that such a configuration might ex-
plain the periodic system. In this first versión of the Thomson model, the
atom was pictured as just an aggregation of electrons and "holes," and so,
assuming Coulomb forces between the electrons, there was no attractive
forcé to keep the atom from exploding. Two years later, Thomson presented
a more definite hypothesis, in which he explicitly formulated what soon
carne to be known as the Thomson model of the atom: "I regard the atom as
containing a large number of smaller bodies which I will cali corpuscles. . . .
In the normal atom, this assemblage of corpuscles forms a system which is
electrically neutral. Though the individual corpuscles behave like negative
ions [charges], yet when they are assembled in a neutral atom the negative
effect is balanced by something which causes the space through which the
corpuscles are spread to act as if it had a charge of positive electricity equal
in amount to the sum of the negative charges on the corpuscles" (Kragh
1997b, 330). Thomson began developing this idea into a quantitative model
only in 1903, shortly after he had become acquainted with a somewhat simi-
lar model proposed by Lord Kelvin.
The essence of the classical Thomson atomic model, as presented in books
and anieles between 1904 and 1909, was this: For reasons of simplicity,
Thomson largely restricted his analysis to rotating rings of electrons re-
stricted in a plañe and subject to the elastic forcé from a homogeneous
sphere of positive electricity. By direct calculation, he examined the mechan-
ical stability of the equilibrium configurations, ruling out those that were not
stable. Thomson's involved stability calculations were quite similar to those
he had used in his vortex atom work more than twenty years earlier. The
complex calculations, which he supplemented with a more approximate
method for a larger number of electrons, showed that the electrons would be
arranged in a series of concentric rings in such a way that the number of
particles in a ring would increase with the ring's radius. Examples of his
1904 equilibrium configurations were 1, 8, 12, 16 for n = 37, and 1, 8, 12,
16, 19 for n = 56. Accelerating electrons will emit electromagnelic energy,
and Thomson therefore had to make sure that his atoms would not be radi-
atively unstable and collapse. Applying a formula derived by Larmor in
1897, he was able to show that the radiation decreased drastically with the
number of electrons in the rings and could therefore, for most purposes, be
ignored. The original Thomson atom was mechanically, as well as radi-
atively, stable.
 46 C H A P T E R 4
Thomson realized that his planar model atom would have to be gener-
alized to a spherical model, but saw no reason to engage in the Herculean
calculations such an extensión would require. After all, the number of elec-
trons in real atoms was unknown, so a detailed comparison with the physi-
cochemical properties of the elements was out of the question. The model
was undoubtedly the most popular atomic model in the period 1904-10,
when many physicists considered ¡t a good approximation of the real consti-
tution of the atoms. In a lecture in Góttingen in 1909, Max Born praised it as
"being like a piano excerpt from the great symphonies of luminating atoms."
Rutherford and Lorentz also considered the model to be attractive and made
use of it in their own works. The attractive features of the model were partic-
ularly related to its monistic nature, which promised a reduction of all matter
to electrons, in agreement with the electromagnetic worldview. Moreover,
Thomson's calculations provided the model with a good deal of mathemati-
cal authority, although most physicists paid little attention to the details of
the electrón configurations. When it carne to empirical credentials, however,
the model was less impressive. It was able to explain, in a qualitative and
vague manner, phenomena such as radioactivity, photoelectricity, dispersión,
the emission of light, the normal Zeeman effect, and, not least, the periodic
system. In addition, it promised to ¡Ilumínate many chemical facts and was,
for this reason, popular among many chemists. But in most cases, the expla-
nations were suggestive analogies rather than deductions based on the details
of the model.
It was evident from the very beginning that the Thomson model was prob-
lematic, both conceptually and empirically. One of the weak points was the
positive electricity, supposed to be frictionless and massless and ultimately a
manifestation of negative electrons. As Thomson wrote to Oliver Lodge in
1904, "I have always had hopes (not yet realised) of being able to do without
positive electrification as a sepárate entity, and to replace it by some property
of the corpuscles. . . . One feels, I think, that the positive electrification will
ultimately prove superfluous and it will be possible to get the effects we now
aitribute to it, from some property of the corpuscles" (Dahl 1997, 324).
Thomson never succeeded in explaining the positive electricity as an epi-
phenomenon. On the contrary, from different kinds of experimental evi-
dence, he concluded in 1906 that the number of electrons was comparable
with the atomic weight, a conclusión that was soon generally accepted. Dur-
ing the next few years, a growing body of evidence indicated that the num-
ber might be even smaller, possibly corresponding to the ordering number in
the periodic system. This was an uncomfortable conclusión, for then the
positive sphere must account for the major part of the atom's mass, which
contradicted the electromagnetic conception of mass. (The electromagnetic
inertia varíes inversely with the radius of the charge and so would be neglig-
ible for a body of atomic dimensions.) It was no wonder that Lodge called
ATOMIC A R C H I T E C T U R E 47
Thomson's estímate of the number of electrons "the most serious blow yet
dealt at the electric theory of matter."
The small number of electrons was a problem not only for the electromag-
netic view of matter, but also, and in particular, for the credibility of the
Thomson model. In 1904 Thomson did not need an exacl match between his
model atoms and those really existing, for with several thousand electrons
even in the lightest atoms, there was no way in which such a match could be
established. Around 1910. there was good reason to believe that the hydro-
gen atom contained only one electrón, the helium atom two. three, or four
electrons, and so on; this meant that Thomson's model calculations could
now be confronted with the chemical and physical properties of the real
elements. In the case of the lightest elements. it could no longer be argued
that the number of electrons was too large or that ihrec-dimensionsal calcu-
lations were not technically possible. Although Thomson proceeded as if the
problem did not exist, it was clear that the desired correspondence between
the model and the reality just did not exist.
There were other problems of a more empirical nature. In particular. Thom-
son's model was unable to explain, without artificial assumptions, the regu-
larities known from line spectra, such as Balmer's law. Indeed, most spectra
seemed to pose problems, for according to Thomson, light was emitted by
the vibrations of electrons and this required that the number of electrons
must be of the same order as the number of observed spectral Iines. How
could the tens of thousands of lines found in many metal spectra be under-
stood on the basis of the vibrations of one hundred or fewcr electrons?
New experiments added to the problems of ihe Thomson atom. Thomson
explained scattering of beta particles by assuming múltiple scattering. that is,
that the observed scattering was the collective result of many individual
scatterings on atomic electrons. On this basis, he managed to account fairly
salisfactorily for experimental data. But Thomson's scattering theory failed
when confronted with the results of alpha scattering experiments. On the
other hand, these were niccly explained by Rutherford's idea of a nuclear
atom; for this reason, the alpha scattering experiments have traditionally
been regarded as the crucial test between the two theories of atomic struc-
ture. However, it would be misleading to consider the demise of the Thom-
son atom as simply the result of the Manchester alpha scattering experi-
ments. A theory is not refuted just because it fails to account for some
experiments. The refutation of Thomson's atomic theory was a gradual pro-
cess, during which anomalies accumulated and it became more and more
clear that the model could not be developed ¡tito a satisfactory state. By
1910. before Rutherford proposed his nuclear atom, the Thomson model had
run out of steam and was no longer considered attractive by most physicists.
A few, including Erich Haas in 1910 and Ludwig Fóppl in 1912, continued
to investígate the model, but the investigations were primarily malhematical
48 C H A P T E R 4
and had no relevance lo the real atoms studied by the experimentalists. In a
1910 work, Haas, an Austrian physicist, suggested relating Planck's constanl
to the dimensions of a Thomson hydrogen atom. Making use of some rather
arbitrary assumptions, he obtained formulas for Planck's constan! and Ryd-
berg's constant in terms of the size of the atom and the electron's mass and
charge. His model was the first attempt to apply quantum theory to the struc-
ture of atoms, but Haas's approach was essentially classical: He wanted to
explain the quantum of action in terms of atomic theory rather than explain
the structure of the atom by means of quantum theory.
At the second Solvay conference in 191.3, physicists listened to the swan
song of the Thomson atomic model. Thomson applied a suitably modified
model in order to explain both alpha scattering and the linear relationship
between the energy of photoelectrons and the frequency of incident light that
experiments indicated. By assuming that the charge density of the positive
sphere decreases from the center, and by making several other ad hoc as-
sumptions, he was able to obtain the photoelectric law with Planck's con-
stant expressed in terms of the electron's charge and mass. However, the
whole procedure was so ad hoc and artificial that it must have appeared to
his listeners what it was: a last attempt to save a once useful atomic model
and to avoid the nonclassical features of quantum theory. Few, if any, of the
physicists gathered in Brussels were convinced that Thomson's atom de-
served to survive.
OTHER EARLY ATOMIC MODELS
Although Thomson's model was by far the most important atomic model of
the first decade of the century, it was not the only orie. The recognition of
the electrón as a universal constituent of matter stimulated physicists to pro-
pose a variety of models, most of them short-lived and some mere specula-
tions. It was mostly in Britain that these atomic models had their origin and
were discussed. In Europe and in North America, interest in atomic structure
was limited. Common to all models was the inclusión of electrons; what
distinguished them were the proposals of how to arrange the necessary posi-
tive charge. Thomson's suggestion of placing the electrons in a sphere of
positive fluid was made independently by Kelvin in 1901. Kelvin's model
had evidently much in common with Thomson's, but it was more qualitative
and did not make use of the modern concept of the electrón. Kelvin pre-
ferred to cali his negative particles "electrions," possibly in order to distin-
guish them from the electrons of Thomson, Lorentz, and Larmor. In papers
written between 1902 and 1907, the aging Kelvin (who died in 1907 at age
83) applied his model to a variety of phenomena, including radioactivity,
which he believed was triggered by some externa! agency, perhaps ethereal
A T O M I C A R C H t T E C T U R E 49
waves. By introducing non-Coulomb forces into his model, he was able to
avoid, to his own satisfaction, the "utterly impossible" conclusión that radio-
activity was energy stored in the atoms. Kelvin's ideas were politely ignored
by other British physicists.
The Kelvin-Thomson model was one of the hypotheses of atomic struc-
ture that Lodge included in his 1906 book Electrons. Another was the idea
that the atom "consists of a kind of ¡nterlocked admixture of positive and
negative electricity, indivisible and inseparable into units." This was the pie-
ture of the atom favored by Lenard, according to whom the basic structures
were rapidly rotating "dynamids," a kind of eléctrica] doublets. Lenard de-
veloped the idea in several works between 1903 and 1913, but it failed to
attract the interest of other physicists. Yet another of Lodge's candidate hy-
potheses was that "the bulk of the atom may consist of a multitude of posi-
tive and negative electrons, interleaved, as it were, and holding themselves
together in a cluster by their mutual attractions" (p. 148). Although it was
generally accepted that positive electrons did not exist, in 1901 James Jeans
nonetheless proposed such a picture in order to explain the mechanism of
line spectra. As a means to circumvent the objection that no equilibrium
system exists for a system of charged particles, Jeans suggested that Cou-
lomb's law would break down at very small distances. Undisturbed by the
experimentalists' measurements of the electron's charge and mass, Jeans
considered an ideal atom in which there was an almost infinite number of
(practically massless) electrons concentrated in the atom's outer layer. The
positive electrons would then be effectively, and conveniently, hidden within
the atom. By means of these and other arbitrary assumptions, he was able to
derive spectral series resembling those observed. A somewhat similar model
was proposed by Lord Rayleigh five years later, again with the solé purpose
of calculating spectral frequencies. In all atomic models before 1913, the
emission of light was supposed to result from vibrating electrons. It is inter-
esting to note that Rayleigh, at the end of his paper, considered the possi-
bility that "the frequencies observed in the spectrum may not be frequencies
of disturbance or of oscillations in the ordinary sense at all, but rather form
an essential part of the original constitution of the atom as determined by
conditions of stability" (Conn and Turner 1965, 125). However, he did not
develop the suggestion, which later would form a crucial part of Bohr's
quantum atom.
Another type of atomic models mentioned by Lodge was the picture of the
atom as a kind of solar system, with the electrons revolving ("like aster-
oids") around a center of concentrated positive electricity. The first sugges-
tion of this kind was enunciated by the French chemist and physicist Jean
Perrin in a popular article of 1901. Perrin suggested that the model might
explain radioactivity and emission of light, but the suggestion was purely
qualitative and he paid no attention to the problem of stability of his plañe-

50 C H A P T t R 4
lary atom. The micro-macro analogy between atoms and solar or galactic
systems was popular at the time and seems to have been a main reason why
planetary atomic models received some atlention. The most elabórate at-
tempt was that of Hantaro Nagaoka, whose "Saturnian" model was published
in 1904, in the same volume of Philosophical Magazine in which Thomson's
theory appeared. Nagaoka's model was astronomically inspired, in the sense
that it closely relied on Maxwell's 1856 analysis of the stability of Saturn's
rings. The Japanese physicist assumed that the electrons were placed uni-
formly on rings moving around the attractive center of a positivo nucleus.
Like Thomson and all other model builders, Nagaoka safeguarded his con-
clusions by adding that "the actual arrangement in a chemical atom may
present complexities which are far beyond the reach of mathemalical treat-
ment" (Conn and Turncr 1965, 113) Nagaoka's calculations led to sugges-
tive spectral formulas and a qualitativc explanation of radioactivity. How-
ever, they were sevcrely criticized by George A . Schott. a British physicist,
who argued that Nagaoka's assumptions were inconsistent and that the
model could not lead lo the claimed agrcement with experimental data. The
Saturnian model disappeared from the scene and only reappeared, in an en-
tirely different dressing, with Rutherford's nuclear theory.
In 1911 John W. Nicholson, a mathematical physicist at the Cavendish
Laboratory, suggested an atomic model somewhat similar to Nagaoka's.
Nicholson's ambitious aim was to derive all the atomic weights of the chem-
ical elements from combinations of proto-atoms, which he supposcd existed
in the stars only. He considered the positive charge to be of electromagnetic
origin, henee much smaller than the electrón, and located in the center of the
atom. Rotating in spheres around the nucleus (as he callcd the central
charge) were the electrons. Contrary to most other model makers. Nicholson
attempted lo account for the structure of real atoms, albeit by using hypo-
thetical proto-atoms. Thus, in his scheme, hydrogen contained a ring of three
electrons, with the simples! proto-atom being the two-clectron system, which
he called "coronium." By means of various assumptions, he managed to
account for the atomic weights of most elements. Like Haas before him,
Nicholson introduced concepts from Planck's quantum theory in order to
explain the line spectra. He was led to an atomic explanation of Planck's
constant and the conclusión that the angular momentum of the proto-atoms
had to be a múltiple of this constant. That is, he arrived at the quantization
rule L = nhfln. This may look very similar to Bohr's rcasoning of two
ycars later, but Nicholson's model was not really a quantum theory of the
atom. It was founded on classical mechanics and electromagnetism and was
much closer to Thomson's than to Bohr's approach. Nicholson continued to
develop his theory in papers between 1911 and 1914, and it received some
positive response from other British physicists. Yet, by 1915 it was evident
that the Nicholson model belonged to the past and not to the future.
A T O M I C A R C H I T E C T U R E 51
RUTHERFORD'S N U C L E A R A T O M
During his fertile years in Montreal from 1898 to 1907, Emest Rutherford
was not particularly interested in atomic models. To the extent he expressed
an interest, he was generally in favor of Thomson's theory, which he found
useful in understanding radioactive phenomena. It was only in 1910 that
Rutherford turned seriously to atomic theory, primarily as a result of his
deep interest in the behavior and nature of alpha particles. In 1908 he had
deftnitely shown the alpha particle to be identical with a doubly charged
helium ion. In the same year Hans Geiger, a Germán physicist working with
Rutherford in Manchester, reponed preliminary results of the scattering of
alpha particles on metal foils. Geiger noted an appreciable scattering; the
following year, he investigated the matter more thoroughly in collaboration
with Emest Marsden, then a twenty-year-old undergraduate. They found that
heavier metáis were far more effective as reflectors than light ones and that a
thin platinum foil reflected (that is, scattered more than 90°) one of every
8,000 of the alpha particles slriking it. When Rutherford learned about the
results, he reportedly considered it "the most incredible event that has ever
happened to me in my life. . . . almost as incredible as if you fired a tífteen-
inch shell at a piece of tissue paper and it carne back and hit you." Ruther-
ford made this often-quoted remark in 1936, but it cannot have been the way
he reacted in 1909-10. The remark makes sense from the perspective of the
almost empty nuclear atom, but Rutherford had no such idea in 1909, when
he still thought of the atom as a Thomson-like plenum. At any rate, the
experiments induced Rutherford to investígate the scattering of alpha parti-
cles and compare the results with Thomson's theory of the scattering of beta
particles. This theory, according to which the beta electrons were multiply
scattered through small angles by the atomic electrons, seemed to agree
nicely with experiments that implied that the number of electrons was about
three times the atomic weight.
According to Thomson, the alpha particle was of atomic dimensions and
contained about ten electrons. Rutherford, on the other hand, believed that
the alpha particle must be considered a point particle, like the electrón. Be-
cause the alpha particle was a helium atom deprived of two electrons, this
view implied, in effect, a nuclear model of the helium atom. Rutherford
reached this important conclusión before he developed his scattering theory,
which relied on his idea of pointlike alpha particles. The theory that Ruther-
ford presented in 1911 had its experimental basis in the Geiger-Marsden
observations of large-angle scattering, which Rutherford found were incom-
patible with Thomson's theory of múltiple electrón scattering. In order to
produce the observed deflections of more than 90°, scattering had to take
place in a single encounter between the alpha particle and a highly charged
and concentrated mass. Rutherford therefore suggested that the atom con-
52 CHAPTER 4
ATOMIC A R C H I T E C T U R E 53
sisted of a massive charge Ze surrounded by a cloud of opposite electricity.
the electrons were of no importance in the scattering, this was just an arbi-
Since the results of his calculations were independent of the sign of the
trary picture. "The question of the stability of the atom proposed need not be
charge, the nucleus could just as well be a concentration of electrons em-
considered at this stage," he wrote, "for this will obviously depend upon the
bedded in a positive fluid, not unlike a special case of the Thomson atom. In
minute structure of the atom, and on the motion of the constituent charged
Rutherford's words: "Consider an atom which contains a charge ±Ne at its
parts" (Conn and Turner 1965, 138). Rutherford did not suggest a planetary
centre surrounded by a sphere of electrification containing a charge +Ne
atom in 1911, and his model was therefore completely impotent when it
supposed uniformly distributed throughout a sphere of radius / ? . . . . for con-
carne to chemical questions such as binding and the periodic table. Ñor was
venience, the sign [of the central charge] will be assumed to be positive"
it any better when it carne to physical questions, such as spectral regularities
(Conn and Turner 1965, 138). Based on his nuclear picture of the atom,
and dispersión. The defining feature of Rutherford's model, the atomic nu-
Rutherford derived the famous scattering formula, which gives the depen-
cleus, was not even new, for nuclear models had already been proposed.
dence of the scattering probability (cross section) on the scattering angle,
Nicholson, who independently suggested his own nuclear model, considered
energy of the incoming alpha particles, and the thickness and charge of the
Rutherford's to be merely "a revival of a suggestion of Nagaoka of a simple
scattering material.
Saturnian system of the atom, involving only a single positive nucleus"
Rutherford's nuclear atom is justly recognized as a landmark in the history
(Heilbron 1968, 303). Incidenlally, Rutherford originally wrote of a "central
of physics. An observer in 1911 or 1912, however, would never have
charge"; the word "nucleus" seems to have been used first by Nicholson.
thought so. When the model was introduced in the spring of 1911, it was
The fale of Rutherford's atomic model changed in 1913, when Geiger and
met with indifference and scarcely considered to be a theory of the constitu-
Marsden published new data on the scattering of alpha particles, including a
tion of the atom. The new conception of the atom was not mentioned in the
total count of 100,000 scintillations. Their data were in excellent agreement
proceedings of the 1911 Solvay Congress (where Rutherford participated),
with Rutherford's scattering formula and afforded "strong evidence of the
ñor was it widely discussed in the physics journals. Not even Rutherford
correctness of the underlying assumptions that an atom contains a strong
himself seemed to have considered the nuclear atom to be of great impor-
charge at the centre of dimensions, small compared with the diameter of the
tance. For example, in his 1913 textbook on radioactivity, titled Radioactive
atom" (Stehle 1994, 221). Still, this was only a confirmation of Rutherford's
Substances and their Radiations, only 1 percent of the book's 700 pages
atomic model seen as a scattering theory, not of other aspects of the model.
dealt with the new discovery and its implications. The nucleus was small but
The Geiger-Marsden results were as irrelevant for the electronic configura-
not, according to Rutherford, pointlike. On the contrary, Rutherford pictured
tions as Rutherford's model was silent about them. A n atomic theory would
it as a highly complex body held together by what would become known as
be considered really convincing only if it included the electrón system. After
nuclear forces: "Practically the whole charge and mass of the atom are con-
all, it was this part of the atom that was responsible for the large majority of
centrated at the centre, and are probably confined within a sphere of radius
the atomic phenomena that could be tested experimentally. This important
not greater than 1 0 " cm. No doubt the positively charged centre of the
1 2

aspect, absent from the work of the Manchester physicists, was supplied in
atom is a complicated system in movement, consisting in part of charged
an unexpected way by a young Danish physicist who turned Rutherford's
helium and hydrogeri atoms. It would appear as if the positively charged
picture of the nuclear atom into a proper theory of the nuclear atom.
atoms of matter attract one another at very small distances for otherwise it is
difficult to see how the component parts at the centre are held together" (p.
620).
A QUANTUM THEORY OF ATOMIC STRUCTURE
There were good reasons for the initial lack of interest in the nuclear
atom, for Rutherford presented his theory as primarily a scattering theory
Niels Bohr was not originally interested in atomic theory. He wrote his doc-
and only secondarily as an atomic theory. As a scattering theory, it was
toral dissertation on the electrón theory of metáis and found that this theory,
moderately successful, but its experimental support was limited and indirect;
as developed by Lorentz, J. J. Thomson, and others, was unsatisfactory both
and as an atomic theory, it was incomplete and might even look hopelessly
ui its details and in its principies. "The cause of failure is very likely this:
ad hoc. Rutherford had argued from scattering data that the atom's mass was
that the electromagnetic theory does not agree with the real conditions in
concentrated in a tiny nucleus, but he could offer no suggestions of how the
matter," he wrote in his 1911 thesis, published only in Danish. Bohr sug-
electrons were arranged. For reasons of simplicity, he assumed the negative
gested that nonmechanical constraints, or what he called "forces in nature of
electricity to form a homogeneous atmosphere around the nucleus, but since
a kind completely different from the usual mechanical sort," had to be intro-
54 CHAPTER 4 A T O M I C A R C H I T E C T U R E
duced in order to bring the electrón theory of metáis into agreement with the
infernal structure of atoms. But in 1911 he did not consider atomic structure
and had no clear idea of the kind of constraint or hypothesis needed. He
spent the academic year 1911-12 in England, first with J. J. Thomson in
Cambridge and then with Rutherford in Manchester, at first continuing his
studies of the electrón theory of metáis but soon concentrating on the new
picture of the alom that Rutherford had proposed and that Bohr found highly
attractive. He realized that the nuclear atom needed to be completed with an
electronic structure and that this would require some nonmechanical hypoth-
esis in order to make the atom stable. Bohr's thinking resulted in the "Man-
chester memorándum," a document from the summer of 1912 in which he
communicated his ideas to Rutherford. In this memorándum Bohr suggested
that the atom would be mechanically stabilized if the kinetic energy of the
orbiting electrons were confined to be proportional to their frequencies of
rotation. As the constant of proportionality, he chose a quantity cióse to
Planck's constant. At this point, Bohr was concerned with mechanical, not
electrodynamic, stability.
In the Manchester memorándum, Bohr dealt with electrón configurations,
molecules, and atomic volumes, but not with spectra. "I do not at al! deal
with the question of calculation of the frequencies corresponding to the lines
in the visible spectrum," he wrote to Rutherford on January 31, 1913, con-
trasting his theory with that of Nicholson (Bohr 1963, xxxvii). Shortly there-
after, he was asked by a colleague in Copenhagen how his ideas related to
Balmcr's formula of the hydrogen lines, which Bohr, surprisingly enough,
seems to have been unacquainted with or had forgotten about. The question
was an eye-opener, and Bohr immediately realized how his ideas could be
extended to give an explanation of the discrete spectra. His great paper, "On
the Constitution of Atoms and Molecules," appeared in three parts in Philo-
sophical Magazine in the summer and fall of 1913. The hydrogen atom was
the focus of the first part, where he introduced his famous postulates,
namely: (I) the notion of stationary states, where ordinary mechanics is valid
but electrodynamics invalid; and (2) the assumption that radiation is emitted
or absorbed when the atom passes between different stationary states. The
transition process could not be understood classically, Bohr pointed out, "but
appears to be necessary in order lo account for experimental facts." Most
remarkably, inspired by Planck's theory, Bohr assumed that the frequency of
light (v) did not relate directly to the frequencies of the orbiting electrons but
was given by the energy difference between two stationary states by the
cquation E¡ — E¡ = hv. From this basic assumption, Bohr was able to
derive the Balmer formula for the frequencies of the hydrogen spectrum in a
way well known from introductory physics textbooks. The derivation did not
merely reproduce a known empirical law, but also resulted in an expression
of the Rydberg constant in terms of microphysical constants of nature,
55
namely, the charge and mass of the electrón and Planck's constant. Bohr's
result was v = Rc(\ln — l/m ), where R = 2Z vrme*/h and n and m are
2 2 2 3
integral quantum numbers characterizing the stationary states; Z is the nu-
clear charge, 1 for hydrogen. In the summer of 1913, lines in accordance
with the formula were known for n = 2 (Balmer series) and n = 3 (Paschen
series); Bohr predicted the existence of further lines corresponding to n = I
and n larger than 4, "series respectively in the extreme ultraviolet and the
extreme ultra-red, which are not observed, but the existence of which may
be expected." His confidence was justified when Theodore Lyman in 1914
reponed lines in agreement with n. = 1. The ionizalion potential of a hydro-
gen atom in its ground state (n = 1) followed directly from the Balmer
expression. Bohr obtained a valué of about 13 volts, which he compared
with J. J. Thomson's experimental estímate of 11 volts. (Later and more
precise measurements gave complete agreement with Bohr's valué.) For the
radius of a hydrogen atom in its ground state, later known as the Bohr ra-
dius, he obtained 0.55 angstrom, the right order of magnitude for an atom.
Perhaps the most impressive confirmation of Bohr's theory of one-elec-
tron atoms was his demonstraron that the "Pickering lines" found in stellar
spectra and usually attributed to hydrogen were in fact due to singly charged
helium ions. These lines satisfied the Balmer-like expression v = R[l/2 — 2
l/(m + 1/2) ] which, if caused by hydrogen, would contradict Bohr's the-
2
ory, áccording to which half-quantum states were inadmissible. Bohr lurned
the threat into a triumph by simply rewriting the expression as v = 4R[V4 2
— i/(2m + l ) ] and attributing it to the H e ion. His prediction that the
2 +
Pickering lines must appear in discharge tubes with puré helium was quickly
confirmed by spectroscopists. However, the agreement between the mea-
sured wavelengths and those predicted by Bohr was not perfect and áccord-
ing to Alfred Fowler, a British spectroscopist, the small discrepancy was
large enough to question the validity of the theory. Bohr's reply, published in
Nature in the fall of 1913, was another brilliant example of what the philoso-
pher Imre Lakatos has called monster-adjustment—turning a counterexam-
ple into an example. Bohr pointed out that the quantity ra in the expression
for R should really be the reduced mass, mMI(m + M), with M being the
nuclear mass, and with this correction the discrepancy vanished.
Bohr derived the Balmer formula in more than one way, including a first
application of what later became known as the correspondence principie.
Bohr noted that for large quantum numbers, there was almost no difference
between the frequency of rotation before and after the emission of a quan-
tum; "and áccording to ordinary electrodynamics we should therefore expect
that the ratio between the frequency or radiation and the frequency of revo-
lution also is nearly equal to 1" (Bohr 1963, 13). In an address before the
Physical Society in Copenhagen in December 1913, Bohr emphasized that
although, in general, there was no connection between classical frequencies
 ATOMIC A R C H I T E C T U R E 57
56 CHAPTKR 4

proved faets,'' as Cari Oseen expressed it in his presentaron specch in Stock-

of revolulion and the frequencies found quantum-theoretically, "[o]n one
holm. Ironically, Franck and Hertz did not originally relate their experiments
point, however, we may expect a conncction with the ordinary conceptions,
to Bohr's theory and, when they first did so, they argued that their measure-
namely, that it will be possible to calcúlate the emission of slow clectromag-
ments could not be explained by the theory. Franck and Hertz measured
netic oscillations on the basis of classical electrodynamics" (Jammer 1966,
what they believed was the ionization potcntial to 4.9 volts, but in 1915
110). This was the genn of the correspondencc principie, which would play
Bohr argued that they had misinterpreted their results and not measured an
a pivotal role in the later development of atomic theory and its transforma-
ionization potential at all, but the encrgy difference between stationary states
lion into quantum mechanics (see chapter 11).
in mercury atoms. It was only after Bohr's intervention that Franck and
Bohr's theory was not simply a theory of one-electron atoms, but was
Hertz realized that they unknowingly had provided strong support for Bohr's
planned much more ambitiously. In the second and third part of the trilogy,
atomic theory.
Bohr applied his theory to chemical atoms larger than hydrogen, and also to
The red line of the hydrogen spectrum has a doublet structure, as first
molecules. He suggcsted electrón arrangements for the lighter elements and
shown by Michelson and Edward Morley as early as 1887. Although by
believed that his models provided the periodic system with its first reliable
1913 the finc-structure splitting had been measured severa! times, Bohr
explanation. Moreover, he extended his work to simple molecules, picturing
seems to have been unaware of this phenomenon, for which there was no
the covalent bond in the hydrogen molccule as two electrons revolving in the
room in his theory. But once again an apparent anomaly was turned into a
same orbit betwcen the two hydrogen nuclei. This part of his work was
confirmation. although this time it required a major extensión of the theory.
much less successful and made relatively little impact. Yet it is noleworthy,
The extensión was made by Arnold Sommerfeld in Munich who, in 1915-
for it was the first time that definite atomic models were proposed for real
16, introduced the special theory of rclativity in the mechanics of the Bohr
atoms. The covalent bond turned out to be outside the reach of Bohr's quan-
atom. In this way, he was led to a two-quantum atom in which the electronic
tum theory of atoms, but in 1913 he had no reason to think so. On the
orbits were desenbed by a principal and an azimuthal quantum number, and
contrary, there werc indications that chemistry would soon be reduced to a
an energy expression that depended on both quantum numbers. According to
branch of Bohr's new physics. For cxample, Bohr calculated the heat of
Sommerfeld's more sophisticated theory, there were many more stationary
formation of molecular hydrogen to 60 kcal per mole, in qualitative but
states than in Bohr's 1913 theory, and this made an explanation of the fine
cerlainly not quantitative agreement with the 130 kcal per mole determined
structure possible. Sommerfeld derived a valué of the fine structure separa-
experimentally by Irving Langmuir. When Langmuir revised the experimen-
tion, which was completely confirmed by experiments made by Friedrich
tal valué to 76 kcal per mole shortly afterward, and Bohr recalculated the
Paschen at the University of Tübingen in 1916. The remarkable agreement
theoretical valué to 63 kcal per mole, it seemed that the hydrogen molecule
between theory and experiment was considered a great success of the Bohr-
was nearly explained. But this was far from from the case.
Sommerfeld theory and also of the theory of relativity. In fact, the relation-
The strength of Bohr's theory was not its theoretical foundation, which to
ship between theory and experiment was rather obscure because the theory
many seemed unconvincing and even bizarre, but its experimental confirma-
allowed calculation only of frequencies but not of intensities; however, al-
tion over a wide range of phenomena. For example, in 1913-14 the young
though the success was questioned by a few physicists in Germany, to the
British physicist Henry Moseley studied the characteristic x-rays emitted by
majority of physicists the work of Sommerfeld and Paschen looked like a
different elements and showed that the square root of the frequencies related
striking confirmation of Bohr's quantum theory of atoms.
proportionally to the atomic number. The Moseley diagram quickly became
an important tool for determining an element's place in the periodic table,
and it also became an important confirmation of Bohr's theory. Moseley's
mechanism of x-ray emission rested on Bohr's theory and in a series of
works starting in 1914, Walther Kossel in Munich further explained x-ray
spectra in full accordance with the theory. Another important confirmation
was the experiments with electrón bombardment of mercury vapor that
James Franck and Gustav Hertz made in Góttingen between 1913 and 1916.
It was soon realized that the experiments brilliantly confirmed Bohr's theory.
In 1925, the two physicists were awarded the Nobel prize for having verified
Bohr's hypotheses and thereby transformed them into "experimentally