“The Best Work I’ve Ever Done”


Linus Pauling, 1931.

[An examination of Linus Pauling’s first paper on the nature of the chemical bond, published in April 1931. This is part 1 of 2.]

“It seems to me that I have introduced into my work on the chemical bond a way of thinking that might not have been introduced by anyone else, at least not for quite a while. I suppose that the complex of ideas that I originated in the period of around 1928 to 1933 – and 1931 was probably my most important paper – has had the greatest impact on chemistry.”

-Linus Pauling, 1977

One of the major film documentaries chronicling Linus Pauling’s life was produced for the long-running NOVA series in 1977. By that point, when asked to look back over the decades of significant work that he had done, Pauling still singled out his insights into the chemical bond as being his most significant contribution to chemistry.

Pauling’s initial 1931 paper in particular marked the first time that he published his revolutionary point of view related to the chemical bond, and reflecting on that period Pauling went so far as to call the article “the best work I’ve ever done.” Indeed, the paper marked the first instance in which Pauling began to spell out the ways in which the burgeoning field of quantum mechanics might be applied to fundamental questions in chemistry. And though first in a lengthy series, Pauling placed major significance on this one paper because it profoundly changed the course of his career and set into motion a period of heavy influenced on the trajectory of an entire discipline.


G.N. Lewis, ca. 1930.

While an undergraduate at Oregon Agricultural College, Pauling had been taught – and went on to teach his own students – the “hooks and eyes” theory of chemical bonding. In this model, each atom was presumed to have a certain number of hooks or eyes that determined how and to what other atoms it could connect. Though it prevailed at the time, the model was deemed to be outdated and insufficient by many of Pauling’s contemporaries, some of whom were concurrently searching for a more satisfactory replacement.

That said, “hooks and eyes” did serve as a useful precursor to the later concept of valence, because it correctly assumed that each atom possessed a concrete number of electrons to contribute to the formation of bonds with other atoms. The theory also suggested that there were rules governing how chemical bonds worked and how likely it was that two or more atoms might form a bond.

While Pauling was still a student in Oregon, he avidly read G.N. Lewis’ ideas about electron structure and also studied Irving Langmuir’s theory of valence, a tutelage that helped propel his own nascent interest in chemical bonding and atomic structure. Lewis proved to be particularly important. A chemist at the University of California, Berkeley and a future mentor of Pauling’s, Lewis proposed that eight electrons provided a maximally stable environment for a molecule, a tenet known today as the octet rule. Working from this idea, Lewis hypothesized that an atom containing, for example, seven electrons would bond more readily with an atom containing nine electrons, and that the bond that was formed consisted of the electron shared between the two atoms.

Lewis wasn’t the first to chase the nature of the chemical bond. Indeed, the problem had been under attack for a few decades. In 1911, Ernest Rutherford created the first modern atomic model, but ran into trouble because it wasn’t compatible with classical physics. Niels Bohr then updated this model. Less than twenty years after J. J. Thompson had discovered the electron, Bohr suggested that electrons orbited the nucleus in a predictable way, emitting quanta when they moved into lower orbits.


Arnold Sommerfeld, 1928.

From there, others sought to fill gaps in Bohr’s model. In 1915, Arnold Sommerfeld, a physicist with whom Pauling eventually worked, helped to devise what came to be known as the Sommerfeld-Wilson quantization rules. These guidelines provided an explanation for angular momentum by describing electron orbits as ellipses rather than perfect circles.

At the same time, Werner Heisenberg, Erwin Schrödinger and Max Planck (among others) were rapidly embracing a new way to look at physics, expanding the theory and mathematics behind involved in this innovative approach. In 1925, a year before Pauling began an influential trip to Europe, Heisenberg had authored his “Quantum Theoretical Reinterpretation of Kinematic and Mechanical Relations,” which many point to as the true beginning of quantum mechanics. Schrödinger then completed his wave function in 1926. By contrast, the Lewis and Langmuir models were part of an old system that – as soon Pauling discovered – was in the process of being discarded.


Linus Pauling at the Temple of Neptune, Paestum, Italy, during his legendary Guggenheim trip to Europe. This photo was taken by Ava Helen in April 1926.

An admirer of Sommerfeld’s work, Pauling traveled to Europe on a Guggenheim fellowship to learn as much as he could about quantum mechanics, which at the time was referred to as “new physics.” He was especially keen to learn more about Schrödinger’s equation and to dig into the ways in which the wave function might be applied to a more sophisticated understanding of the chemical bond. Though impressed by Heisenberg, Pauling gravitated toward Schrödinger because he saw more potential for practical application of the wave function, as opposed to Heisenberg’s matrix mechanics. In a note penned during his travels, Pauling wrote specifically that

I think that it is very interesting that one can see the [psi] functions of Schrödinger’s wave mechanics by means of the X-ray study of crystals. This work should be continued experimentally. I believe that much information regarding the nature of the chemical bond will result from it.

These thoughts proved prophetic, as we will see in part 2 of this series.

Pauling returned to Pasadena in the fall of 1927, bursting with new ideas. While he was away, Caltech chemistry chief A.A. Noyes had sent word that a unique position had been created for his promising young faculty member, one that lined up nicely with Pauling’s new interests. Upon his re-arrival at Caltech, Pauling was to begin working under the title of Assistant Professor of Theoretical Chemistry and Mathematical Physics.

Although Noyes eventually dropped the physics course from the appointment, Pauling liked the idea of hybridizing his interests into one name. It was at that point that he began referring to himself as a quantum chemist.


Pauling Amidst the Titans of Quantum Mechanics: Europe, 1926

Erwin Schrödinger and Fritz London in Berlin, Germany, 1928.

[Ed. Note: Spring 2010 marks the seventy-fifth anniversary of the publication of Linus Pauling and E. Bright Wilson, Jr.’s landmark textbook, Introduction to Quantum Mechanics.  This is post 1 of 4 detailing the authoring and impact of Pauling and Wilson’s book.]

…the replacement of the old quantum theory by the quantum mechanics is not the overthrow of a dynasty through revolution, but rather the abdication of an old and feeble king in favor of his young and powerful son.

-Linus Pauling, “The Development of the Quantum Mechanics,” February 1929.

Since 1925 the John Simon Guggenheim Memorial Foundation has annually awarded fellowships to promising individuals identified as advanced professionals who have “already demonstrated exceptional capacity for productive scholarship or exceptional creative ability in the arts.”  The selection process is extremely competitive and recipients are generally esteemed in their chosen field as applicants face rigorous screening and are selected based on peer recommendation and expert review.

Since the first awards in 1925, many Nobel and Pulitzer prize winners have received Guggenheim Fellowships including, but not limited to, Ansel Adams, Aaron Copland, Martha Graham, Langston Hughes, Henry Kissinger, Paul Samuelson, Wendy Wasserstein, James Watson and, of course, Linus Pauling.

As one of the program’s earliest honorees, Pauling was awarded his first Guggenheim fellowship in 1926.  Heeding the advice of his mentors, Pauling had applied for the fellowship in hopes of pursuing an opportunity for international study.  Pauling’s advisers had long been insisting that he go to Europe to study alongside the leading experts in the budding field of quantum physics, and the Guggenheim funding provided Pauling with the opportunity to do just that.  It was this fellowship that allowed Pauling to travel abroad in order to learn from the European geniuses of quantum physics and to later become one of the early American pioneers of the new field of quantum mechanics.

Linus and Ava Helen Pauling’s apartment in Munich, Germany. 1927.

The subject of quantum mechanics constitutes the most recent step in the very old search for the general laws governing the motion of matter.

–Linus Pauling and E. Bright Wilson, Introduction to Quantum Mechanics, 1935.

The mid-1920s – the time during which Pauling was awarded the prestigious Guggenheim fellowship – was an exciting period to begin an exploration of quantum theory.  The tides were dramatically shifting in this field of study and the acceptance of the old quantum theory was rapidly declining.

Linus and Ava Helen left for Europe on March 4, 1926, arriving in Europe in the midst of what was a great quantum theory reform.  At the inception of quantum theory, physicists and chemists had attempted to apply the classical laws of physics to atomic particles in an effort to understand the motion of and interactions between nuclei and electrons.  This application was grossly flawed as the classical laws, such as Newton’s laws, were originally generated to represent macroscopic systems.   Theorists soon discovered that the classical laws did not apply to atomic systems, and that the microscopic world does not consistently align with experimental observations.

A series of breakthroughs by prominent theorists in the early- to mid-1920s accelerated the decline of the old quantum theory.  In 1924 Louis de Broglie discovered the wave-particle duality of matter, and in the process introduced the theory of wave mechanics.  Then in 1925, just one year before Pauling began his European adventure, Werner Heisenberg developed his uncertainty principle and thus began applying matrix mechanics to the quantum world.

In 1926, shortly after the Paulings arrived in Europe, Erwin Schrödinger combined de Broglie’s and Heisenberg’s findings, mathematically proving that the two approaches produce equivalent results.  Schrödinger then proceeded to develop an equation, now know as the Schrödinger Equation, that treats the electron as a wave.  (The Schrödinger Equation remains a central component of quantum mechanics today.)  The adoption of wave and matrix mechanics led to the development of a new quantum theory and the overwhelming acceptance of a burgeoning field known as quantum mechanics.

Arnold Sommerfeld and Ava Helen Pauling in Munich, Germany. 1927.

Where the old quantum theory was in disagreement with the experiment, the new mechanics ran hand-in-hand with nature and where the old quantum theory was silent, the new mechanics spoke the truth.

–Linus Pauling, February 1929

Pauling began his work in Munich at Arnold Sommerfeld‘s Institute for Theoretical Physics, a scholarly environment described by biographer Thomas Hager as “a new wave-mechanical universe for Pauling.”  It was this atmosphere that opened the door for Pauling to leave his mark as a pioneer of quantum mechanics.

In the fall of 1926, Pauling began applying the new quantum mechanics to the calculation of light refraction, diamagnetic susceptibility, and the atomic size of large, complex atoms.  Through these types of applications, Pauling developed his valence-bond theory, in the process making significant advancements in the new field of quantum mechanics and expanding our understanding of the chemical bond.

Linus Pauling and the Birth of Quantum Mechanics

Linus and Ava Helen Pauling in Munich, with Walter Heitler (left) and Fritz London (right), 1927.

Linus and Ava Helen Pauling in Munich, with Walter Heitler (left) and Fritz London (right), 1927.

My year in Munich was very productive. I not only got a very good grasp of quantum mechanics — by attending Sommerfeld’s lectures on the subject, as well as other lectures by him and other people in the University, and also by my own study of published papers — but in addition I was able to begin attacking many problems dealing with the nature of the chemical bond by applying quantum mechanics to these problems.”
– Linus Pauling, 1992

In the spring of 1926, funded by a Guggenheim Fellowship, Linus and Ava Helen Pauling embarked on their first trip to Europe, scientific tourists beginning a journey that would revolutionize modern chemistry and physics.

The Paulings travelled through the continent, stopping at the famed institutes of modern science in Munich, Göttingen, and Zurich, among others, and meeting with scientific giants including Arnold Sommerfeld, Max Born and Erwin Schrödinger. It was at this time that quantum mechanics, the branch of science devoted to the study of the atom’s physics, was being revolutionized by the ideas of Schrödinger and Werner Heisenberg. It wasn’t until Pauling left Germany for Switzerland however, that he was introduced to a ground-breaking idea – the combination of Schrödinger’s wave mechanics with the study of structural chemistry.

In Zurich, the German researchers Walter Heitler and Fritz London explained to Pauling the concept of “electron resonance” as developed by Heisenberg. At its core, the theory suggested that electrons could be attracted to one another, to the point where they would eventually switch back and forth between two given atoms. This exchange of electrons would, in turn, release energy, in the process drawing the two atoms together and creating a chemical bond. This revolutionary concept agreed with certain known principles of the hydrogen atom – the atom on which Heitler and London were conducting their calculations – and appeared to support the Pauli exclusion principle which, as Pauling later put it, “states that no two electrons in the universe can be in exactly the same state.”

After his return to Caltech in September of 1927, Pauling worked on several projects, including his first published book and a class on the Heitler-London work. In the process of defining his research program as a young member of the Caltech faculty, Pauling decided that, rather than continuing to dabble in theoretical physics, he would instead return to his roots in chemistry. With that, he set out to combine what he had learned in Europe with his continuing interests in structural chemistry.

He began his work on the chemical bond, figuring calculations and comparing his results to existing experimental data. He affirmed that Heitler and London’s work meshed comfortably with G. N. Lewis‘ theory of the shared electron pair and he published articles on the subject, in the process introducing many chemists to the notion of using quantum mechanics as a tool for the study of non-physics problems. In early 1928, he suggested that quantum mechanics could answer the question of carbon bonding – a revolutionary idea at the time. Unfortunately, while the preliminary mathematics were promising, the sheer mathematical computing power required did not exist for Pauling to fully solve the problem.

In 1930 M.I.T. physicist John C. Slater succeeded in simplifying Schrödinger’s mathematical description of the types of changes experienced by any quantum system over time — an important mathematical model known as the Schrödinger Wave Equation. By slightly restructuring Slater’s set of simplified equations, Pauling was able to utilize the concept of wave functions to describe new orbitals that matched the known traits of the carbon-tetrahedron bond. Not only did these new methods allow Pauling to calculate the data for basic tetrahedral bonds, they also provided stable footing for detailing the precise structures of a series of complex molecules. This was the genesis of valence-bond theory — a hugely important marriage of quantum physics and structural chemistry.

In early 1931, Pauling released a paper detailing six rules, later known as “Pauling’s Rules,” that dictated the basic principles governing the molecular structure of any given molecule. He presented his findings in the simplest language possible, avoiding complex mathematics in order to make the concepts accessible to his fellow chemists. This paper, of course, was titled “The Nature of the Chemical Bond” and would serve as the basis for his immensely popular textbook of the same name.

In 1954 Pauling won the Nobel Prize in Chemistry “For research into the nature of the chemical bond and its application to the elucidation of complex substances.” The award was granted in recognition of the work that began during his first trip to Europe and blossomed in the decade that followed. Pauling’s innovative application of quantum mechanics had resulted in his receipt of the highest possible scientific honor and the subsequent worldwide recognition of his talents.

Learn more about this story by visiting the website “Linus Pauling and the Nature of the Chemical Bond: A Documentary History.”