Quantum Numbers and Atomic Structure

Refining Bohrs Model

By: Vishal Singh XI-A

What are Quantum Numbers?

Bohr defined the principal energy levels (n = 1,2,3,4) experimental evidence indicated the need for changes to this simple system quantum numbers are quantized values used to describe electrons in an atom there are four quantum numbers represented by the letters n (Bohrs number), l, ml and ms

The Principal Quantum Number, n

(Bohr, 1913)

based on Bohrs observations of line spectra for different elements n relates to the main energy of an electron allowable values: n = 1, 2, 3, 4, electrons with higher n values have more energy

The Secondary Quantum Number, l

(Sommerfeld, 1915)

based on the observation (Michelson, 1891) that lines on line spectra are actually groups of multiple, thin lines l relates to the shape of the electrons orbits allowable values: l = 0 to l = n - 1 i.e. for n = 4: l = 0, 1, 2, or 3 the l values 0, 1, 2, and 3 correspond to the shapes we will call s, p, d and f, respectively

The Magnetic Quantum Number, ml

(Sommerfeld and Debye, 1915)

based on the observation (Zeeman, 1897) that single lines on line spectra split into new lines near a strong magnet ml relates to the direction/orientation of the electrons orbits allowable values: ml = - l to + l i.e. for l = 2: ml = -2, -1, 0, 1, or 2 electrons with the same l value but different ml values have the same energy but different orientations

The Spin Quantum Number, ms

(Pauli, 1925)

based on the observation that magnets could further split lines in line spectra, and that some elements exhibit paramagnetism ms relates to the spin of an electron allowable values: ms = - or + i.e. for any possible set of n, l, and ml values, there are two possible ms values when two electrons of opposite spin are paired, there is no magnetism observed; an unparied electron is weakly magnetic

Defining Electrons Using Quantum Numbers

Lets look at the energy level n = 2: Possible l values: 0, 1 For l = 0, ml = 0 For l = 1, ml = -1, 0 or 1 For every value of ml, there are two electrons (ms = and ms = - ) So, there would be 8 electrons found in principal energy level 2 and they would have the following designations

Electrons in energy level 2: Electron

1 2 3

n
2 2 2

l
0 (or s) 0 (or s) 1 (or p)

ml
0 0 -1

ms
-

4
5 6 7 8

2
2 2 2 2

1 (or p)
1 (or p) 1 (or p) 1 (or p) 1 (or p)

-1
0 0 1 1

-
- -

Orbits vs. Orbitals

initially, electrons were thought to travel in orbits (2D, travels around nucleus at fixed distance in a circular path, 2n2 electrons per orbit) quantum theory describes electrons as existing in orbitals (3D region, distance from nucleus varies, no path, 2 electrons per orbital)

For our purposes:

primary energy level (n) = shell energy sublevel (l) = subshell orbitals are named as a combination of the n and l values

e.g. an electron may exist in a 2p orbital (n = 2, l = 1 or p)

shapes of these orbitals will be discussed soon

Energy-Level Diagrams

now we can be more specific for every n, energy increases from spdf quantum number restrictions state that there can only be:
one s orbital (= 2 electrons) for any value of n three p orbitals (= 6 electrons) for n = 2,3,4, five d orbitals (= 10 electrons) for n = 3,4,5, seven f orbitals (=14 electrons) for n = 4,5,6,

Relative Energies of Electron Orbitals

When Placing Electrons in Orbitals

aufbau principle: fill lower-energy orbitals first Hunds rule: within the same energy level, give each orbital one electron before pairing up electrons Pauli exclusion principle: two electrons within the same orbital must have opposite spins

Aufbau (building up) Diagram

this diagram will help you remember the proper order for filling orbitals

7s 6s 5s 4s 3s 2s 1s

7p 6p 5p 4p 3p 2p

7d 6d 5d 4d 3d

7f 6f 5f 4f

Energy-Level Diagram for Vanadium

vanadium has 23 electrons

The Following is Just Beautiful

The quantum theory of the atom agrees completely with the periodic table, which had been around for 30 years and was developed without any knowledge of electron arrangements.

Wait for it

Relationship between the first two quantum numbers and the periodic table:

Referring to quantum theory and the periodic table of the elements:

The unity of these concepts is a triumph of scientific achievement that is unparalleled in the past of present.

Electron Configurations

More concise than energy-level diagrams but provide same information

e.g. for vanadium: V: 1s2 2s2 2p6 3s2 3p6 4s2 3d3
Try chlorine right now Cl: 1s2 2s2 2p6 3s2 3p5

Shorthand Electron Configurations

use noble gases as a starting point

e.g. for vanadium: V: [Ar] 4s2 3d3

for chlorine: Cl: [Ne] 3s2 3p5

The Power of What You Now Know

You have seen that the periodic table is explained for you as never before Charges of ions can be explained
e.g. lead Pb: 6s2 4f14 5d10 6p2 Pb2+ ion: remove two electrons from 6p Pb4+ ion: remove two electrons from 6p and two electrons from 6s