William

Rowan Hamilton 18051865

American child prodigy

Zeran Colburn

"He used to carry on long trains of algebraic and arithme8cal calcula8ons in his mind, during which he was unconscious of the earthly necessity of ea8ng..." William Edwin Hamilton (his elder son)

Rowan and son

Who would not rather have the fame of Archimedes than that of his conqueror Marcellus?

First US Airmail Flight, Lafaye>e, Indiana in 1859

1868 Map of Lafaye>e, Indiana

Grant St.

1878 Map of Chauncey showing Purdue University

Northwestern

University Competed in 1874 Hall

Purdue University was founded in 1869. Classes started in 1874. The rst degree was a Bachelor of Science in Chemistry awarded in 1875.

1862 Rail-Road and Military Map of the US

Josiah Willard Gibbs

1839 - 1903

One of the principal objects of theoreWcal research in any department of knowledge is to nd the point of view from which the subject appears in the greatest simplicity.

Max Karl Ernst Ludwig Planck 1858 - 1947

1878

1901

Science cannot solve the ulWmate mystery of nature. And that is because, in the last analysis, we ourselves are a part of the mystery that we are trying to solve.

From the Preface to Gibbs StaWsWcal Mechanics (1901)

Black Body Spectrum

Ultraviolet Catastrophe is avoided if electro-magneIc vibraIons are quanIzed, = h , and the same is true for molecular vibraIons!

Heat CapaciWes of Gases and Solids

Classical predic8on: U = a T Heat Capacity: Cv =(dU/dT)v = a Expect CV to be T-independent
Diamond

Low T Energy

High T
Boltzmann distribuWon

The observed temperature dependence implies that molecular vibraIons (and rotaIons) are quanIzed, just like photons! = h

InacWve

AcWve

Albert Einstein 1879- 1955

1893

1904

1921

The most incomprehensible think about the world is that it is comprehensible.

Albert Einsteins RelaWvity and E=mc2 (1905)

m = E/c2
Atom velocity

Photoelectric Eect

Einsteins ExplanaWon of the Photoelectric Eect (1905)

photon energy Plancks Constant

= h

Frequency of light

Einsteins ExplanaWon of Brownian MoWon (1905)

Movie Animation

Mean-squared displacement Radius Viscosity Time

All of these quan88es are experimentally measurable

Proved that molecules really exist Determined Avogadros number, NA

What Happened in Lubeck in 1895?

A shouting match between the atomist and the energist

Wilhelm Ostwald

Ludwig Boltzmann

Which was which? Who won the day?

Personal Accounts of the Lubeck Conference

Georg Helm (speaker, wrote to his wife):
The great ac8vity lies behind me. I believe that the lecture was a success, it was applauded and praised; but during the discussion there was a s8 ght. Boltzmann commenced with friendly apprecia8ve remarks and [then] began to inveigh against Ostwalds and my workOstwald and Boltzmann came to heavy blowsThe mee8ng lasted from 9 un8l a]er 12The hall was more than half full, so that a few hundred persons experienced the whole business

Arnold Sommerfeld (audience member):

The champion of energe8cs was Helm; behind him stood Ostwald and behind both of them the philosophy of Mach (who was not present in person). The baale between Boltzmann and Ostwald was much like the duel of a bull and a supple bullghter. However, this 8me the bull defeated the toreador in spite of all his agility. The arguments of Boltzmann struck through. We young mathema8cians were all on Boltzmanns side

Ostwald (recounted years later):

Boltzmann (Gas Theory, Part II, 1898):

At the discussion [in Lubeck] I found myself before a closed antagonism. My only supporter and gh8ng companion was Georg Helm. But he was removed from me because of his aversion to a realis8c concep8on of energyIt was the rst 8me that I personally found myself confronted by such a unanimous band of downright adversaries

(in his book wriaen in 1909):

[Boltzmann is] the man who excelled all of us in acumen and clarity of his ideas.

When the rst part of Gas Theory was being printed [in 1895] It was just at this 8me that aaacks on the theory of gases began to increase. I am convinced that these aaacks are merely based on misunderstanding, and that the role of gas theory in science has not yet been played outIn my opinion it would be a great tragedy for science if the theory of gases were temporarily thrown into oblivion because of a momentary hos8le ahtude toward it, as was for example the wave theory because of Newtons authorityI am conscious of being only an individual weakly struggling against the stream of 8me.

Why did Einstein Write to Ostwald?

Einstein (leaer to Ostwald, 1901): Einsteins Father (leaer to Ostwald, 1901):
Esteemed Herr Professor! Because your book on general chemistry inspired me to write the enclosed ar8cle, I am taking the liberty of sending you a copy of it. On this occasion permit me also to inquire whether you might have use for a mathema8cal physicist familiar with absolute measurements...because I am without means, and only a posi8on of this kind would oer me the possibility of addi8onal educa8on. Respeckully yours, Albert Einstein (gives the address of his parents) Esteemed Herr Professor! Please forgive a father who is so bold as to turn to you in the interest of his son. I shall start by telling you that my son Albert is 22 years old, that he studied at the Zurich Polytechnikum for 4 years, and that he passed his diploma examina8ons in math and phys with ying colors last summer. Since then, he has been trying unsuccessfully to obtain a posi8on as an Assistant, which would enable him to con8nue his educa8on in theore8cal & experimental physics. All those in posi8on to give a judgment in the maaer, praise his talents; in any case, I can assure you that he is extraordinarily studious and diligent and clings with great love to his science. My son therefore feels profoundly unhappy with his present lack of posi8on, and his idea that he has gone o the tracks with his career & is now out of touch gets more and more entrenched each day. In addi8on, he is oppressed by the thought that he is a burden on us, people of modest means. Since it is you...whom my son seems to admire and esteem more than any other scholar currently ac8ve in physics...[I make] the humble request to read his paper...and to write him, if possible, a few words of encouragement, so that he might recover his joy in living and working

Three weeks later he wrote again:

Esteemed Herr Professor! A few weeks ago I took the liberty of sending you from Zurich a short paper which I published in Wiedemann's Annalen. Because your judgment of it maaers very much to me, and I am not sure whether I included my address in the leaer, I am taking the liberty of sending you my address hereby. Respeckully...

Ostwald Accepts the Atomic Hypothesis

I am now convinced that we have recently become possessed of experimental evidence of the discrete or grained nature of maaer, which the atomic hypothesis sought in vain for hundreds and thousands of years. The isola8on and coun8ng of gas ions, on the one hand, which have crowned with success the long and brilliant researches of J. J. Thomson, and, on the other, the agreement of the Brownian movements with the requirements of the kine8c hypothesis, established by many inves8gators and most conclusively by J. Perrin, jus8fy the most cau8ous scien8st in now speaking of the experimental proof of the atomic nature of maaer. The atomic hypothesis is thus raised to the posi8on of a scien8cally well-founded theory, and can claim its place in a text-book intended as an introduc8on to the present state of our knowledge in General Chemistry.

From the preface to Outlines of General Chemistry by W. Ostwald (1912). Boltzmanns and Einsteins theore8cal contribu8ons are acknowledged on p. 485.

Einsteins Miracle Year (1905)

Relativity E=mc2 Light Particles Brownian Motion

Ostwalds Nobel Prize (1909)

Ostwald: Nobel Prize in Chemistry
"in recogni8on of his work on catalysis and for his inves8ga8ons into the fundamental principles governing chemical equilibria and rates of reac8on"

The first person that Ostwald nominated for a Nobel Prize was Albert Einstein Einstein: Nobel Prize in Physics 1921
"for his services to Theore8cal Physics, and especially for his discovery of the law of the photoelectric eect"

Line Spectra of Atoms and Molecules

RotaWon of CO2

VibraWons of a Nano-Ice-Cube

Molecules appear to have quanIzed energies!

Niels Henrik David Bohr (1885-1962)

In 1912 Neils wrote to his brother, Harald: Things are going rather well, for I believe I have found out a few things; but, to be sure, I have not been so quick to work them out as I was stupid to think.

Energies of Photons and Molecules

Figure 1.2 in Understanding Physical Chemistry

Wave-ParIcle Duality

Albert Einstein

Louis de Broglie

Energy

Momentum

= h = hc/
Frequency Plancks Constant

p = h/
Wavelength

DiracIon of Waves

Thomas Young's sketch of two-slit dirac8on 1803.

DiracIon of Electrons

Discovered accidentally by Davisson and Germer 1927 at Bell Labs

Molecular DiracIon
He and H2 by Rocksalt

Einstein 1913 During the year that Stern spent as Einsteins rst postdoctoral associate Experimental Data of Oao Stern 1930 1943

Stern

Irwin Schroedinger

Developed Wave EquaIon Which Predicts QuanIzaIon of Atomic & Molecular Energies

VibraIonal Normal Modes of a String

2-D VibraIonal Normal Modes

More 2-D VibraIonal Normal Modes

3-D Normal Modes

y x

StaIsIcally Independent ProbabiliIes MulIply P( ) = P( ) P( ) = 1/2 x 1/2 = 1/4 P( ) = P( ) P( ) = 1/6 x 1/6 = 1/36

2 x = 1 mv x P( x + y + z ) = P( x )P( y )P( z ) 2 Molecular 2 KineIc y = 1 mv y 2 2 1 So, P( ) e c i Energies = mv z 2 z i c( x + y + z ) P( x + y z ) e + e c x e c x e c z P( x )P( y )P( z )

Barometric DistribuIon of Atmospheric Density

Height, h
!(h)

Denisty, !

!0

Use, ideal gas law and gravitaIonal potenIal energy

To obtain,

= mgh
So,

mgh / kB T / kB T P( ) =e =e 0

1/kB T

 = h

Eq. 1.24 in UPC = 1/kBT or 1/RT