19 October 1981
The Royal Swedish Academy of Sciences has decided to
award the 1981 Nobel Prize in Physics by one half jointly to
Professor Nicolaas Bloembergen, Harvard University,
USA, and Professor Arthur L. Schawlow, Stanford
University, USA, for their contribution to the development
of laser spectroscopy, and by the other half to Professor
Kai M. Siegbahn, Uppsala University, Sweden, for his contribution
to the development of high-resolution electron
spectroscopy.
This year's Nobel Prize in Physics rewards the development of two
forms of atomic spectroscopy, viz. laser spectroscopy, i.e. the
study of atomic systems using laser light, and electron
spectroscopy, i.e. the study of electrons expelled from atomic
systems by different kinds of processes.
Laser spectroscopy
Albert Einstein in 1917 showed
that there are three different kinds of radiation processes:
absorption, when radiation energy is taken up by the system;
spontaneous emission, when a system without external influences
emits radiation; and stimulated emission, when a system by means
of external influences is stimulated to emit radiation. The first
two processes have been known for a long time and form the basis
for the origin of for instance optical spectra. The existence of
stimulated emission, however, was something new at the time of
Einstein's famous work, but no practical importance of this could
be seen at that time.
In the early 1950s, scientists in both the USA and the Soviet
Union were at work in trying to make use of the stimulated
emission of atomic systems in order to amplify weak microwave
signals and to design oscillators based on such systems. This led
to the maser (Microwave Amplification by Stimulated Emission of
Radiation), first designed by Townes and his co-workers in the USA and
which at the same time had been suggested by Basov and Prokhorov in the USSR.
The idea of extending the principle of the maser to the infrared
or optical region arose in different quarters in the late 1950s.
The wholly decisive contribution in the realization of this idea
was made in 1958 by Schawlow and Townes, who then published a
work analysing the preconditions necessary for such a design,
theoretical as well as practical. Prokhorov around the same time
proposed a similar design for the generation of longer waves.
Other suggestions based on the same idea were also presented at
that time. However, it was primarily the work by Schawlow and
Townes which initiated the whole dynamic field which we now
associate with the concept of "laser" (Light Amplification by
Stimulated Emission of Radiation).
The 1964 Nobel Prize in Physics was awarded to Townes, Prokhorov
and Basov for "fundamental work in the field of quantum
electronics, which has led to the construction of oscillators and
amplifiers based on the maser-laser-principle". Subsequent
developments, however - particularly in lasers - have made this
field increasingly deserving of additional rewards.
The fundamental principle of laser - as for maser - is that an
attempt is made in one way or another to bring about a population
inversion, i.e. a system with more atoms in a higher state than a
lower, as opposed to what is obtained when the system is left to
itself without external influences. If an atom in the higher
state falls down to the lower state by the emission of a photon
(light quantum), this photon may stimulate another atom to emit a
photon of the same kind, etc. In this way a chain process may be
built up, and we obtain what is known as laser light. This light
has the particular property of being coherent, and the photons
forming part of the light beam oscillate largely in phase with
one another - as opposed to ordinary light, as from a light bulb.
The laser light may further be made extremely parallel and
monochromatic, which is the foundation of many of its areas of
application.
The first functioning laser was constructed in 1960, and since
then developments have been rapid. It is now possible to produce
laser light throughout the entire range of visible wavelengths,
as well as in portions of the infrared and ultraviolet ranges.
Thus the laser has become a next to ideal instrument of atomic
spectroscopy for studying the properties of atoms and molecules,
and a number of spectrographic methods have been developed in
recent years. Many of these methods are based on non-linear,
optical phenomena, caused by the circumstance that laser light is
so strong that the usual linear relationships no longer
apply.
One such a class of non-linear, spectrographical methods, which
have been developed and applied particularly by Schawlow and his
co-workers at Stanford university, are founded on the
circumstance that "saturation phenomena" may appear in the
absorption of the laser light because of the high intensity. This
may be utilized in so-called Doppler-free spectroscopy, where the
broadening of the spectral lines due to the motion of the atoms
(the Doppler effect) has been eliminated. This method has been
applied in the study of the simplest of all substances, hydrogen,
with extremely high precision. Thereby it has been possible to
determine one of the most fundamental of atomic constants, the
Rydberg constant, with a significantly higher degree of precision
than was previously possible, which is of the greatest importance
to our knowledge of the fundamental constants in nature in
general.
Another class of non-linear, optical methods of spectroscopy is
based on the mixing of two or more light waves. This type of
phenomenon was demonstrated shortly after the laser was
introduced, and the theory for it was comprehensively explored
around the same time by Nicolaas Bloembergen and his co-workers.
Of particular interest is four-wave mixing where three coherent
light waves act together in generating a fourth light wave. By
this method it is possible to generate laser light far outside
the visible range, in both the infrared and the ultraviolet
directions. The method has thus drastically extended the range of
wavelengths accessible to laser spectroscopy studies. A special
form of four-wave mixing is known as "CARS" (Coherent Anti-Stokes
Raman Scattering), which has been applied in studies of widely
differing kinds - all the way from optimization of combustion
processes in motorcar engines to the study of element transport
in biological tissues.
Electron spectroscopy
When a substance is irradiated with ultraviolet light of X-rays
it may be made to emit electrons. This photo-electric effect, as
it is known, was first observed by Heinrich Hertz in the 1880s.
The correct explanation was given in 1905 by Albert Einstein
using the quantum hypothesis introduced by Max Planck five years earlier. The
energy of the emitted electrons is equal to the photon energy of
the incident light, minus the energy with which the electron is
bound to the sample. By using monochromatic light - for which all
photons have the same energy - it is thus possible through
studying the emitted electrons to get valuable information on the
electron structure of the sample being examined. This method
began to be applied already in the 1910s, primarly by H. Robinson
in Britain. However, it turned out that the spectra obtained gave
little information on the material investigated, chiefly because
the electrons are exposed to larger or smaller energy losses
through collisions on their way out of the material. The method
thus did not become of major importance at that period. Instead
an alternative method was developed for studying the interior of
atoms, viz. X-ray spectroscopy, where the radiation is studied
which is emitted when an electron moves from one inner energy
level to another.
Interest in the serious study of photo-electrons did not revive
until the 1950s. The decisive step at that time was taken when
Kai Siegbahn together with his co-workers Carl Nordling and
Evelyn Sokolowski began to analyse photo-electrons with the aid
of a high-resolution, double-focusing spectrometer, which was
originally designed for the precision study of electrons emitted
in the radioactive decay of some atomic nuclei, the so-called
beta decay. The electron spectra contained - in addition to the
broad lines observed previously - a number of strong and
extremely narrow lines which had not been observed before, These
came from electrons which had left the sample without energy
loss. Because the energy losses are quantized - i.e. the
electrons may on their way out give off energy to the sample only
in specific amounts - the probability is considerable that no
energy loss occurs. In order to discover these sharp lines,
however, the resolution of the instrument must be sufficiently
high, which was not the case in earlier experiments. Through this
discovery, the way had been prepared for a new form of
spectroscopy.
This new form of electron spectroscopy could now compete in
earnest nest with the X-ray spectroscopy technique, and Siegbahn,
Nordling and Sokolowski during several years in the late 1950s
made a systematic study of the electron energies binding of
different elements, a study which is still the major source of
information.
At a closer study of the electron energies it was found that
these for one and the same atom were to a small extent dependent
on the molecule or the crystal to which the atom was bound, a
chemical shift. Similar shifts had already been observed in X-ray
spectra, but these shifts were considerably more difficult to
interpret. The chemical shifts are caused by different electron
densities in the vicinity of the atoms. In the development of
electron spectroscopy, a practically useful analytical method had
been obtained with which it was possible to study not only which
atoms are included in a sample but also in which chemical
environment these atoms exist. At this time the concept of "ESCA"
(Electron Spectroscopy for Chemical Analysis) was created for
this method.
After the introductory stage the electron spectroscopy has
developed rapidly. This development has been greatly influenced
by the efforts of Siegbahn and his co-workers. Commercial
electron spectrometers have already been available for some
years, and electron spectroscopy is now applied in various forms
at hundreds of laboratories throughout the world. The method has
found several important fields of application, for instance in
the study of surface-chemistry processes such as catalysis and
corrosion.