Looks aren't everything... (Let's take a spin).

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Transcription:

Looks aren't everything... (Let's take a spin).

Bohr correctly deduced the energies for the hydrogen atom, but he didn t know about the Schrödinger Eq. and he didn t know about wavefunctions. So his picture of the hydrogen atom was wrong... Bohr and Einstein in Leiden, 1925. http://upload.wikimedia.org/wikipedia/commons/thumb/d/d5/niels_bohr_albert_einstein_by_ehrenfest.jpg/414px- Niels_Bohr_Albert_Einstein_by_Ehrenfest.jpg

Rutherford s experiment... gold foil alpha particle radioactive source fluorescent screen

historical descriptions of the atom... Ernest Rutherford (1909) a central, positive, nucleus J.J. Thompson (1897) plum pudding model http://en.wikipedia.org/wiki/ Niels Bohr (1913) electrons in discrete orbits, correlated with energy and angular momentum

Hydrogen atom quantum numbers n = 1, 2, 3... hcr = 13.60 ev State vectors are labeled with the quantum number n... AND three more: l, ml, ms

Hydrogen atom quantum numbers n is called the principal quantum number. n = 1, 2, 3... l is called the orbital angular momentum quantum number. l = 0, 1, 2...(n-1) = s, p, d, f... ml is called the magnetic quantum number. ml = l, l-1,...-l : a total of 2l + 1 ms is called the spin magnetic quantum number. ms= 1/2, -1/2 - we'll deal with this one later.

The quantum states of a hydrogen atom:

ψ(r,θ, φ)...the wavefunctions for the hydrogen atom,, are three-dimensional. We use spherical polar coordinates to express this wavefunction...

Hydrogen atom wavefunctions The three dimensional H atom wavefunction can be defined by the three quantum numbers n, l, and ml:

Hydrogen atom wavefunctions The three dimensional H atom wavefunction can be defined by the three quantum numbers n, l, and ml: Rn,l(r) is the radial component of the wavefunction. Rn,l depends on the two quantum numbers n and l.

Hydrogen atom wavefunctions The three dimensional H atom wavefunction can be defined by the three quantum numbers n, l, and ml: Yl,ml(θ,ϕ) is the angular component of the wavefunction. Yl,ml depends on the two quantum numbers l and ml.

Hydrogen atom wavefunctions note: THREE quantum numbers here: n, l, ml.

...let s look at the first one: n=1, l=0, ml=0. 150 1s = 100> ψ( r,θ,φ) = 1 4π 1/ 2 2 Z a 0 3 / 2 exp Zr a 0 three dimensional probability densities

...let s look at the first one: n=1, l=0, ml=0. 151 1s = 100> ψ( r,θ,φ) = 1 4π 1/ 2 2 Z a 0 3 / 2 exp Zr a 0...electron density does not depend on θ,ϕ. orbital is spherically symmetric. We call it an s-orbital.

2s = 200> ψ( r,θ,φ) = 1 4π 1/ 2 1 Z 2 2 a 0 3 / 2 2 Zr a 0 exp Zr 2a 0 All of the s orbitals are spherically symmetric.

2s = 200> ψ( r,θ,φ) = 1 4π 1/ 2 1 Z 2 2 a 0 3 / 2 2 Zr a 0 exp Zr 2a 0 radial nodes radial nodes: n=1 has 0 n=2 has 1 n=3 has 2 etc.

For l=1, we have three ml values: -1, 0, 1 note: THREE quantum numbers here: n, l, ml. we take linear combinations the ml wavefunctions -1, 0, 1 to get these p wavefunctions

p orbital probability density plots we take linear combinations the ml wavefunctions -1, 0, 1 to get these p wavefunctions

For l=2, we have five ml values: -2, -1, 0, 1, 2 note: THREE quantum numbers here: n, l, ml. we take linear combinations of the ml wavefunctions -2, -1, 0, 1, 2 to get these d wavefunctions

d orbital probability density plots we take linear combinations of the ml wavefunctions -2, -1, 0, 1, 2 to get these d wavefunctions

Looks aren't everything... (Let's take a spin).

Hydrogen atom quantum numbers n is called the principal quantum number. n = 1, 2, 3... l is called the orbital angular momentum quantum number. l = 0, 1, 2...(n-1) = s, p, d, f... ml is called the magnetic quantum number. ml = l, l-1,...-l : a total of 2l + 1 ms is called the spin magnetic quantum number. ms= 1/2, -1/2

Hydrogen atom quantum numbers n is called the principal quantum number. n = 1, 2, 3... l is called the orbital angular momentum quantum number. l = 0, 1, 2...(n-1) = s, p, d, f... ml is called the magnetic quantum number. ml = l, l-1,...-l : a total of 2l + 1 ms is called the spin magnetic quantum number. ms= 1/2, -1/2 : a total of 2s + 1 implying that s =?

Hydrogen atom quantum numbers n is called the principal quantum number. n = 1, 2, 3... l is called the orbital angular momentum quantum number. l = 0, 1, 2...(n-1) = s, p, d, f... ml is called the magnetic quantum number. ml = l, l-1,...-l : a total of 2l + 1 ms is called the spin magnetic quantum number. ms= 1/2, -1/2 : a total of 2s + 1 implying that s = 1/2 Since s is always 1/2, we don't list it in ψ.

The Zeeman Effect ml is called the magnetic quantum number. ms is called the spin magnetic quantum number. What does magnetism have to do with atomic structure? Pieter Zeeman 1865-1943

The Zeeman Effect The Zeeman effect is the splitting of a spectral line into several components in the presence of a static magnetic field. 1902 Nobel Prize in Physics In 1896, three years after submitting his thesis on the Kerr effect, he disobeyed the direct orders of his supervisor and used laboratory equipment to measure the splitting of spectral lines by a strong magnetic field. He was fired for his efforts, but revenge later on was sweet: he won the 1902 Nobel Prize in Physics for the discovery of the Zeeman effect. Pieter Zeeman 1865-1943

The Zeeman Effect The Zeeman effect is the splitting of a spectral line into several components in the presence of a static magnetic field. Zeeman's original data on Na atoms Pieter Zeeman 1865-1943

The Zeeman Effect The Zeeman effect can only be explained by the existence of two magnetic dipoles:* one from the orbital angular momentum of the electron in the atom one from the intrinsic angular momentum of the electron spin!! *Zeeman and Lorentz actually blew the explanation. They got the Nobel Prize anyway.

The Zeeman Effect The Zeeman effect can only be explained by the existence of two magnetic dipoles: one from the orbital angular momentum of the electron in the atom one from the intrinsic angular momentum of the electron Bohr magneton 9.274 x 10-24 Joules/Tesla S is spin!!

The Zeeman Effect The Zeeman effect can only be explained by the existence of two magnetic dipoles: one from the orbital angular momentum of the electron in the atom one from the intrinsic angular momentum of the electron electron orbital g-factor electron spin g-factor gl =1 gs = 2.002 S is spin!!

An isolated electron will align itself with an external magnetic field just like a classical bar magnet. But the directions an electron can point are QUANTIZED; there are only two possible directions, "up" (with the field) or "down" (against the field). These two states are represented by the quantum number ms:

L and S are both angular momentum vectors The orbital angular momentum quantum number L can vary from 0 to n-1. The magnetic quantum number ml represents the different directions that the orbital magnetic dipole moment can take, and varies from -L to +L. Example: L = 2 (d orbital) ml = -2, -1, 0, 1, 2

L and S are both angular momentum vectors The spin angular momentum quantum number S is ALWAYS 1/2. So we don't mention it in the H atom state. The spin magnetic quantum number ms represents the different directions that the spin magnetic dipole can take, and varies from -1/2 to +1/2. S = 1/2 (always) ms = -1/2, +1/2

Even though the Zeeman effect shows the effects of electron spin, it was not understood correctly until 1925: 1922 - the Stern-Gerlach experiment on Ag atoms in magnetic fields. 1925 - Sam Goudsmit and George Uhlenbeck propose that the electron has its own, intrinsic, angular momentum...called spin.

Otto Stern, After venting to release the vacuum, Gerlach removed the detector flange. But he could see no trace of the silver atom beam and handed the flange to me. With Gerlach looking over my shoulder as I peered closely at the plate, we were surprised to see gradually emerge the trace of the beam.... Finally we realized what [had happened]. I was then the equivalent of an assistant professor. My salary was too low to afford good cigars, so I smoked bad cigars. These had a lot of sulfur in them, so my breath on the plate turned the silver into silver sulfide, which is jet black, so easily visible. It was like developing a photographic film. ARTICLES Stern and Gerlach: How a Bad Cigar Helped Reorient Atomic Physics Bretislav Friedrich and Dudley Herschbach Physics Today, December 2003, page 53

Reenactment of the Stern-Gerlach cigar episode by Bretislav Friedrich and Dudley Herschbach. Friedrich holds the slide as Herschbach blows sulfurous cigar breath onto a silver-coated glass slide to test his hearing (or Otto Stern's telling) of the story more than 40 years ago. The silver film turns out to require exposure to cigar smoke (not simply sulfurous breath) to form any visible contrast between the masked (light) part of the slide--shaped in the form of the magnet pole pieces--and the outer (dark) part of the slide exposed to the smoke.

...but wait a second, why silver atoms? 145 http://cwx.prenhall.com/bookbind/pubbooks/hillchem3/medialib

...but wait a second, why silver atoms? 145 We'll deal with this in a bit....answer: Ag is 4d 10 5s 1

Samuel Goudsmit, in 1971... What the historians forget - and also the physicists - is that in the discoveries in physics chance, luck plays a very, very great role. Of course, we do not always recognize this. If someone is rich then he says "Yes, I have been clever, that is why I am rich"! And the same is being said of some one who does something in physics "yes, a really clever guy...". Admittedly, there are cases like Heisenberg, Dirac and Einstein, there are some exceptions. But for most of us luck plays a very important role and that should not be forgotten.

Part of a letter by L.H. Thomas to Goudsmit (25 March 1926). Reproduced from a transparency shown by Goudsmit during his 1971 lecture. The original is presumably in the Goudsmit archive kept by the AIP Center for History of Physics.

A memorial plaque honoring Otto Stern and Walther Gerlach, mounted in February 2002 near the entrance to the building in Frankfurt, Germany, where their experiment took place. The inscription, in translation, reads: "In February 1922... was made the fundamental discovery of space quantization of the magnetic moments of atoms. The Stern-Gerlach experiment is the basis of important scientific and technological developments in the 20th century, such as nuclear magnetic resonance, atomic clocks, or lasers...." So who was more lucky: Sam Goudsmit and George Uhlenbeck, or Otto Stern and Walther Gerlach?

By the way... Otto Stern was awarded the 1943 Nobel Prize in Physics, the first to be awarded since 1939. He was the sole recipient in Physics that year, and the award citation omitted mention of the Stern-Gerlach experiment, as Gerlach had remained active in Nazi-led Germany. Otto Stern 1888-1969

Hydrogen atom quantum numbers n is called the principal quantum number. n = 1, 2, 3... l is called the orbital angular momentum quantum number. l = 0, 1, 2...(n-1) = s, p, d, f... ml is called the magnetic quantum number. ml = l, l-1,...-l : a total of 2l + 1; l = 0 to n-1 ms is called the spin magnetic quantum number. ms= 1/2, -1/2 : a total of 2s + 1; s = 1/2

Looks aren't everything... Okay, now we're ready to explain the Periodic Table. multi-electron atoms Atomic Spectroscopy (Let's take a spin).