Atomic Models
Discussion
Rutherford
Rutherford's assistants did all the work. Rutherford's idea was, "well let's see if these guys (Geiger, Marsden etc.) are good at detecting alpha particles scattered from gold foil. Make them look for them at large angles. That sounds like a really difficult task." But then, Geiger and Marsden actually found particles scattered at extreme angles.
Experiment — alpha particles bombarding gold foil (polonium a source)
A small fraction of the αparticles falling upon a metal plate have their directions changed to such an extent that they emerge again at the side of incidence.
Compared, however, with the thickness of gold which an αparticle can penetrate, the effect is confined to a relatively thin layer. In our experiment, about half of the reflected particles were reflected from a layer equivalent to about 2 mm of air. If the high velocity and mass of the aparticle be taken into account, it seems surprising that some of the αparticles, as the experiment shows, can be tamed within a layer of 6 × 10^{−5} cm. of gold through an angle of 90°, and even more. To produce a similar effect by a magnetic field, the enormous field of 10^{9} absolute units would be required.
Three different determinations showed that of the incident αparticles about 1 in 8000 was reflected, under the described conditions.
It was left to Rutherford to make conclusions from their observations
observation  ⇒  conclusion 

most particles did not deviate 
atoms are mostly empty space  
some deviated slightly 
there's something positive inside the atom  
a tiny fraction deviated 90°–180° 
a small positively charged region (nucleus) contains most of the atom's mass 

electrons orbit the nucleus like a planet orbiting the Sun 
Rutherford's own words.
§1 The observations, however, of Geiger and Marsden on the scattering of α rays indicate that some of the α particles, about 1 in 20,000 were turned through an average angle of 90 degrees in passing though a layer of goldfoil about 0.00004 cm. thick, which was equivalent in stoppingpower of the a particle to 1.6 millimetres of air…. It seems reasonable to suppose that the deflexion through a large angle is due to a single atomic encounter, for the chance of a second encounter of a kind to produce a large deflexion must in most cases be exceedingly small. A simple calculation shows that the atom must be a seat of an intense electric field in order to produce such a large deflexion at a single encounter….
§2 Consider an atom which contains a charge ±Ne at its centre surrounded by a sphere of electrification containing a charge ∓Ne supposed uniformly distributed throughout a sphere of radius R.e is the fundamental unit of charge, which in this paper is taken as 4.65 x 10^{−10} E.S. unit. We shall suppose that for distances less than 10^{−12} cm. the central charge and also the charge on the alpha particle may be supposed to be concentrated at a point. It will be shown that the main deductions from the theory are independent of whether the central charge is supposed to be positive or negative. For convenience, the sign will be assumed to be positive. The question of the stability of the atom proposed need not be considered at this stage, for this will obviously depend upon the minute structure of the atom, and on the motion of the constituent charged parts….
§7 In comparing the theory outlined in this paper with the experimental results, it has been supposed that the atom consists of a central charge supposed concentrated at a point, and that the large single deflexions of the α and β particles are mainly due to their passage through the strong central field.
Bohr
 dilemma
 electrons in orbit experience centripetal acceleration
 accelerating charge produces electromagnetic waves, electromagnetic waves transfer energy
 loss of energy would make atoms unstable (electron should spiral into nucleus)
 discrete spectra from energetic electrons
 Bohr's major new idea
 quantization of angular momentum in terms of ℏ = h/2π
 electrons occupy stationary states around the nucleus
 restricted angular momentums lead to restricted radii and energy levels
 transition between energy levels accompanied by emission, absorption of photon. The atom only gains or loses energy when its electrons are transferred from one stationary state to another.
 Sommerfeld's major new idea
 electrons form standing waves around the nucleus
 discrete nature of harmonics leads to quantization of angular momentum
 new dilemma
 one dimensional
 does not work for other elements — anything with more than one electron
 there are additional spectroscopic phenomena where discrete lines will split that it cannot explain (to be discussed elsewhere)
 Zeeman effect
 hyperfine splitting
 applications
 spectroscopy
 discrete emission/absorption lines correspond to allowed energy level transitions
 Kirchhoff rules (KirchhoffBunsen rules?)
 hot objects produces light with a continuous spectrum
 an energized gas produces light with a discrete spectrum
 a hot object behind a cooler gas produces light with a nearly continuous spectrum with gaps at discrete wavelengths
 atomic spectra are atomic fingerprints or barcodes or another identification analog
 quantum optical effects
 fluorescence
 phosphorescence
 photochemistry
 dissociation (ozone, for example)
 photosynthesis
 photography
 photochromism (orthonitrotoluenes, for example)
 cistrans isomerism (visual purple, for example; tioindigos, anils, and azo compounds)
 shifting of position of double bonds (ergostgerol converts to vitamin D, for example)
 laser
 Light Amplification through the Stimulated Emission of Radiation
 Looking At Source Erases Retina
 spectroscopy
NielsBohr (1885–1962) Denmark
Let us at first assume that there is no energy radiation. In this case the electron will describe stationary elliptical orbits….
The circumstance that the frequency can be written as a difference between two functions of entire numbers [whole numbers] suggests an origin of the lines in the spectra in question similar to the one we have assumed for hydrogen; i.e. that the lines correspond to a radiation emitted during the passing of the system between two different stationary states.
For this it will be necessary to assume that the orbit of the electron can not take on all values, and in any event, the line spectrum clearly indicates that the oscillations of the electron cannot vary continuously between wide limits….
Let us now try to overcome these difficulties by applying Planck's theory to the problem….
The subject of direct observation is the distribution of radiant energy over oscillations of the various wave lengths. Even though we may assume that this energy comes from systems of oscillating particles, we know little or nothing about these systems. No one has ever seen a Planck's resonator, nor indeed even measured its frequency of oscillation; we can observe only the period of oscillation of the radiation which is emitted. It is therefore very convenient that it is possible to show that to obtain the laws of temperature radiation it is not necessary to make any assumptions about the systems which emit the radiation except that the amount of energy emitted each time shall be equal to hν, where h is the Planck constant and νf is the frequency of the radiation….
During the emission of the radiation the system may be regarded as passing from one state to another; in order to introduce a name for these states we shall call them "stationary" states, simply indicating thereby that they form some kind of waiting places between which occurs the emission of the energy corresponding to the various spectral lines….
Under ordinary circumstances a hydrogen atom will probably exist only in the state corresponding to n = 1. For this state W will have its greatest value and, consequently, the atom will have emitted the largest amount of energy possible; this will therefore represent the most stable state of the atom from which the system cannot be transferred except by adding energy to it from without.
In a letter to…
There appears to me one grave difficulty in your hypothesis, which I have no doubt you fully realize, namely, how does an electron decide at what frequency it is going to vibrate at when it passes from one stationary state to the other? It seems to me that you would have to assume that the electron knows beforehand where it is going to stop.
Only an integral number of wavelengths fit in an allowed electron orbit.
classical start
F_{c}  = F_{e}  
m_{e}v^{2}  =  1  e^{2}  
r  4πε_{0}  r^{2}  
v^{2}  =  1  e^{2}  
4πε_{0}  m_{e}r 
Bohr hypothesis
L = mvr  =  nh  
2π  
L^{2} = m^{2}v^{2}r^{2}  =  n^{2}h^{2}  
4π^{2}  
m_{e}^{2}  ⎛ ⎜ ⎝ 
1  e^{2}  ⎞ ⎟ ⎠ 
r^{2}  =  n^{2}h^{2}  
4πε_{0}  m_{e}r  4π^{2}  
r = n^{2}  ε_{0}h^{2}  = n^{2}a_{0}  
πe^{2}m_{e} 
de Broglie hypothesis
C  =  2πr  =  nλ = n  h  
mv  
C^{2}  =  4π^{2}r^{2}  =  n^{2}h^{2}  
m^{2}v^{2}  
4π^{2}r^{2}  =  n^{2}h^{2}  ⎛ ⎜ ⎝ 
4πε_{0}  m_{e}r  ⎞ ⎟ ⎠ 

m_{e}^{2}  1  e^{2}  
r = n^{2}  ε_{0}h^{2}  = n^{2}a_{0}  
πe^{2}m_{e} 
Bohr radius, a_{0}…
 
 

Thus the diameter of a hydrogen atom in its ground state is approximately 10^{−10} m, a unit also known as an ångstrom and represented with the symbol Å.
energy levels of hydrogen: total energy is the sum of the kinetic and electric potential energy of the electron
E = K + U =  1  m_{e}v^{2} −  1  e^{2}  
2  4πε_{0}  r 
Replace speed with the equation derived earlier for the speed of an electron in a classical circular orbit. Then simplify.
E =  1  m_{e}  ⎛ ⎜ ⎝ 
1  e^{2}  ⎞ ⎟ ⎠ 
−  1  e^{2}  
2  4πε_{0}  m_{e}r  4πε_{0}  r 
E =  −  1  e^{2}  
4πε_{0}  2r 
Replace radius with the equation derived earlier for the radius of an electron in an allowed orbit. Then simplify.
 
 

ground state energy, ionization energy of hydrogen





or in electronvolts
E_{1} =  − 2.179 × 10^{−18} J  = − 13.60 eV 
1.602 × 10^{−19} C/e 
energy level changes are followed by the emission of a photon
∆E = hf
Spectroscopists like wavelengths, which leads to the following funky formula — the Rydberg equation for hydrogen.
1  = −R_{∞}  ⎛ ⎜ ⎝  1  −  1  ⎞ ⎟ ⎠ 
λ  n^{2}  n_{0}^{2} 
It can be derived from the Bohr model.
c =  fλ  
E_{n} =  e^{4}m_{e}  1  
8ε_{0}^{2}h^{2}  n^{2}  
∆E =  hf  
1  = −  e^{4}m_{e}  ⎛ ⎜ ⎝ 
1  −  1  ⎞ ⎟ ⎠ 
λ  8ε_{0}^{2}h^{3}c  n^{2}  n_{0}^{2} 
Rydberg constant, R_{∞}
R_{∞} = 


R_{∞} =  (1.602 × 10^{−19} C)^{4} (9.109 × 10^{−31} kg)  
8(8.854 × 10^{−12} C^{2}/N m^{2})^{2} 

R_{∞} =  1.097 × 10^{7} m^{−1}  
spectral lines are classified according to the energy level the electron lands on
photochemistry
 GrotthussDraper law: Light must be absorbed by a chemical substance in order for a photochemical reaction to take place. Molecules that do not absorb light of a particular frequency will not undergo a photochemical reaction when irradiated at that frequency
 StarkEinstein law (photoequivalence law): Each photon of light can cause a photochemical reaction of only one light absorbing molecule.
 The amount of photoreaction that takes place is directly proportional to the product of the light intensity and the time of illumination. In other words, more light produces more photoproduct.
Schrödinger
dilemma
Electrons have threedimensional extent, but the Bohr model assumes the electron to be a onedimensional standing wave wrapped around the nucleus.
major new idea
Electrons form threedimensional standing waves around the nucleus, electron clouds, restricted wavelengths (spherical harmonics)
Erwin Schrödinger (1887–1961) Austria, Abhandlungen zur Wellenmechanik. Wave equation for matter reminiscent of Maxwell's equations for electromagnetic waves. The story I heard is that Schrödinger went to Switzerland with two goals: to keep his mistress happy and to derive a wave equation for matter. How successful he was with the former is open to speculation.
full, timedependent form
iℏ  ∂  Ψ(r,t) = −  ℏ^{2}  ∇^{2}Ψ(r,t) + U(r)Ψ(r,t) 
∂t  2m 
can be separated into two halves
Ψ(r,t) = ψ(r)φ(t)
spatial, timeindependent half
Eψ(r) = −  ℏ^{2}  ∇^{2}ψ(r) + U(r)ψ(r) 
2m 
temporal, timedependent half
φ(t) = e^{−iEt/ℏ} n — energy quantization, linear momentum quantization? (K, L, M, N, O, … originally A, B, …) principal quantum number
 ℓ — angular momentum quantization (s, p, d, f, g, … sharp, principal, diffuse, fine/fundamental/faint, … ) (reduced? orbital?) azimuthal quantum number
 m (m_{ℓ}) — space quantization magnetic quantum number
 s (m_{s}) — spin quantization (up, down) spin quantum number
Wolfgang Pauli (1900–1958) Austria — exclusion principle
The ground states of all elements follow the pattern of the excited states in the hydrogen atom. The structure of the periodic table, which was determined empirically, can be derived theoretically from first principles. Chemistry is secretly a branch of physics.
n shells 
ℓ subshell 
m orbital 
orbital name 
orbital shape 


1, 2, 3, 4, 5, 6,…  0  0  s  spherical  
2, 3, 4, 5, 6, …  1  +1  p  x  dumbbell 
0  p  y  dumbbell  
−1  p  z  dumbbell  
3, 4, 5, 6, …  2  +2  d  xy  double dumbbell 
+1  d  xz  double dumbbell  
0  d  z^{2}  dumbbelltorus  
−1  d  yz  double dumbbell  
−2  d  x^{2} − y^{2}  double dumbbell  
4, 5, 6, …  3  +3  f  y(3x^{2} − y^{2})  flat triple dumbbell 
+2  f  xyz  quadruple dumbbell  
+1  f  yz^{2}  triple dumbbell  
0  f  z^{3}  dumbbelldouble torus  
−1  f  xz^{2}  triple dumbbell  
−2  f  z(x^{2} − y^{2})  quadruple dumbbell  
−3  f  x(3y^{2} − x^{2})  flat triple dumbbell  
5, 6,…  4  −4 to +4  g  manylobed 
Dirac
1928: Dirac developed the relativistic quantum theory. Paul Dirac states his relativistic electron quantum wave equation. Charles G. Darwin and Walter Gordon solve the Dirac equation for a Coulomb potential. Paul Dirac combines quantum mechanics and special relativity to describe the electron.
Is this right?
⎡ ⎢ ⎣ 
γ^{μ}c  ⎛ ⎜ ⎝ 
i  ∂  − eA_{μ}  ⎞ ⎟ ⎠ 
− m_{e}c^{2}  ⎤ ⎥ ⎦ 
Ψ(x^{ν}) = 0 
∂x^{μ} 
This equation…
 agrees with special relativity (is Lorentz invariant)
 has four solutions
 contains within it the notion of spin up and spin down (the first two solutions)
 predicts the existence of antimatter (the second two solutions)
Dirac showed that there are no stable electron orbits for more than 137 electrons, therefore the last chemical element on the periodic table will be untriseptium (_{137}Uts) also known informally as feynmanium (_{137}Fy). It's full electron configuration would be something like…
1s^{2}
or is it…
1s^{2}
finish it