Chemistry 5

Chapter-9
Electrons in Atoms
Part-3
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30 October 2002

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p-orbitals (l = 1)
Key features:
1- angular node at r = 0.
probability density is not spherically
symmetric; 2-lobed orbitals

Three degenerate p-orbitals: ml = 0, 1

n-2 radial nodes in wave function
signs (+, -) correspond to phases of
wavefunction, , and do not signify charge.
n = 2; l = 1

n = 3; l = 1

d-orbitals (l = 2)

Key features:
Two angular nodes at r = 0.
probability density is not spherically

symmetric; four-lobed orbitals designated

with respect to x,y,z axes

Five degenerate d-orbitals; ml = 0, 1, 2

n-3 radial nodes in wave function

signs (+, -) correspond to

phases of wavefunction,

Orbitals Summary
Variation of n for fixed l
For a given value of l, and increase in n leads to an
increase in the average distance of electron from nucleus
and thus average size of orbital.

Nodal properties
An orbital with quantum numbers n and l has l angular
nodes and n l 1 radial nodes with total of n 1
nodes.
For 1-electron atom energy depends only on the total
number of nodes (i.e., n, but not l or m).

Probability at nucleus
As r approaches zero, vanishes for all orbitals except
s. Hence, electrons in s orbitals are said to penetrate to
the nucleus.

Electron Spin
Experimental observation?
A beam of atoms, which have an odd
number of electrons, is split into two
component when passed through an
inhomogeneous magnetic field: Stern
Gerlach experiment.

Electron Spin Quantum Number, ms

This observation can be explained by
introducing a fourth quantum number, the
spin quantum number, ms = , where
+ signifies spin up (), and - spin
down ().
Qualitatively, this can be thought of in
classical picture where spinning electron
creates magnetic field (but dont take too
literally!).

Multielectron Atoms
Moving beyond hydrogen atom?

Subshells within a shell lose their degeneracy due to the

interactions between electrons.

Electron Configurations
Given a set of orbitals, how are these filled with electrons?
Minimize energy:

Electrons occupy (are added to) orbitals in way that minimizes the energy of an atom;
this generally means starting with subshells of sequentially higher principle quantum
number.
The general order is: 1s; 2s, 2p; 3s, 3p, 4s, 3d, 4p, 5s, 4d, 5p, 6s,

Pauli exclusion principle:

No two electrons in an atom may have the same 4 quantum numbers if two electrons
occupy the same orbital then these electrons must have opposite spins, ms = .
Hence, the electron capacity of a given subshell is 2x orbital degeneracy: s subshell can
hold 2 electrons; p subshell can hold 6 electrons.

Hunds rule:
When orbitals of the same energy are available degnerate orbitals electrons
occupy orbitals singly with spin parallel; alternatively, maximize the number of
unpaired electrons in degenerate orbitals.

Lets apply these ideas look at real atoms!

Building Up Atoms: Start Simple

1s
Hydrogen: 1 electron

2p

1s
Helium: 2 electrons

2s

1s1

2s

2p
1s2

1s

2s

2p
1s12s1
excited state

orbital diagram breaks each subshell into individual orbital boxes, which are
filled with electrons of spin up/down configuration.
spdf notation shows number of electrons in each subshell starting with lowest
principle quantum number

Building Up Atoms: More Interesting Examples?

1s

2s

1s

2s

1s

2s

1s

2s

1s

2s

1s

2s

1s

2s

1s

Ne

Li
Be
B
C

2p

1s22s1 or [He]2s1
2p

1s22s2 or [He]2s2
2p

1s22s22p1 or [He]2s22p1

2p

1s22s22p2 or [He]2s22p2

2p

2p

1s22s22p3 or [He]2s22p3

1s22s22p4 or [He]2s22p4

2s

2p

1s22s22p5 or [He]2s22p5

1s22s22p6 or [He]2s22p6

2p

Periodic Trends: Beginning

H
1s1

He
1s2

Li
2s1

Be
2s2

B
2p1

C
2p2

N
2p3

O
2p4

F
2p5

Ne
2p6

Na
3s1

Mg
3s2

Al
3p1

Si
3p2

P
3p3

S
3p4

Cl
3p5

Ar
3p6

K Ca Sc

Examples:
1. Phosphorous, P:

[Ne]3s23p3

2. Calcium, Ca:

[Ar]4s2

3. Scandium, Sc:

[Ar]3d14s2

Periodic Trends: Overview & Predictions

Examples:
1. Thallium, Tl:
[Xe]4f145d106s26p1
2. Neodymium, Nd:
[Xe]4f35d16s2