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Quantum Mechanics and Atomic Structure

Light and Matter (Continued)

Duality of Nature
Particle-like Behaviour
Photo-electron effect KE = 1/2mv2 E = hR

Note, v and R are different symbols

Energy of photon = Energy absorbed Ephoton = J + KEelectron . or Work Function (J) also called hR = KE+ J. Binding Energy (BE) also called Ionization energy (IE)

To the right is a schematic of the apparatus used for photoelectric effect measurements where R0 is called the threshold frequency. True or false, if light of a higher frequency is shone on the metal a larger current will be measured? 1. True 2. False

Example
The photoelectron spectrum of neon excited by light with P=9.89010-11 m shows these three peaks. What are the energy levels of the electrons ejected for each case The three peaks occur at: 383.4, 1205.2 and 1232.0 eV In the Bohr atom, the zero in energy is defined to be when electrons are fully separated from the atom (no interaction = no energy) Thus, the energy levels in the atom will all be negative. To remove an electron, we needed to give it sufficient energy to remove it from the atom (ionization energy or binding energy) J.

J = hR KE
hc hR = P = 6.626110-34Js 2.9979108m/s 9.89010-11m 1.602210-19J/eV = 1253.6 eV Unit Conversion factor

Example (Cont.)
J = hR KE J = 1253.6 eV KE
Do the subtraction three times, once for each measured KE of ejected electrons
KE(eV) 383.4 1205.2 1232.0 J (eV) 870.2 48.4 21.6

Now, we can sketch out the energy levels from which each of these electrons was ejected.

Atomic spectroscopy
Observation shows discrete frequencies of light absorbed or emitted.

Different atoms give different spectra

What we see

Neon

Argon

Mercury

Emission spectra

Hydrogen atom
Balmer/Rydberg equation

1 1 R ! RH 2  2 n1 n2
RH = 3.28811015 frequency (s-1)

or

1 1 hR ! RH 2  2 n1 n2
RH = 2.17910-18 Joules (J)

Predicts the transition energies for the atomic spectral lines in Hydrogen.

g 3 2 1

Example
What is Energy and wavelength of a photon emitted when e drops from the n=4 to n=2 energy level in a H atom?
E = 2.17910-18J 1 42 1 22 = 4.091019 J
(for one atom, assuming one atom absorbs one photon)

E = hR = hc/P P= hc/E = (6.626181034Js 2.9979108 ms1) / 4.091019 J P= 4.86 107m = 486 nm What about molar energy? E = 4.091019 J/atom * 6.0221023 atoms/mol = 246 kJ/mole of atoms

Bohr Atom
Bohr was able to explain the Rydberg results using a model whereby electrons existed in fixed orbits of distinct energies, labelled by integer n (= 1, g). He succeed in calculating the value for RH from fundamental constants:

me e 4 RH ! me 2 3 8I 0 h c1  mp

Heisenberg Uncertainty Principle


The accuracy to which we can measured momentum ((p) and position ((x) is limited according to the equation

((p) ((x) u h/4T


This is a consequence of the fact that to measure something, we must perturb it somewhat (bounce light off it, for example). At the macroscopic level, this is insignificant most times. At the atomic level, it is always significant. This means Bohrs atom cannot be correct since, in it, electron energy (momentum) is always well defined.

We need a better model

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