1

CHEM 1004 | Inorganic Chemistry

ATOMIC STRUCTURE

• An atom consists of a positively charged nucleus surrounded by negatively

charged electrons

• Nuclei contains protons and neutrons

• Isotopes arise due to varying number of neutrons for any given atom

Protons Neutrons Electron

Mass 1 1 1/1836
Charge +1 0 –1

• Electrons were found to behave as particles

p = mv

where p = momentum
m = mass (1/1836 of a proton)
v = velocity

• An electron can also have kinetic energy (KE = ½ mv2) and spin

• Spin refers to the presence of a magnetic component which for an electron can
take 2 values (+ ½ or up ↑ and down ↓)

• De Broglie wavelength relationship

h h
λ= =
p mv
where λ = wavelength
h = Planck’s constant (6.626 x 10-34 J s-1)
p = momentum

Leading to wave-particle duality

• Hence, some experiments were consistent with particles and some with waves
but no experiment were consistent with both. This phenomenon had already
been encountered with light
 2

Light

c
v= where λ = wavelength (m) v = frequency (Hz) c = speed of light (3 x 108 ms-
l
1
)

• Wave theory does not account for all properties of light. Some properties (e.g.
photoelectric effect and black body radiation) can be best described by a particle
model such that light can only be absorbed in discrete units or small packets of
fixed energy (i.e. quanta)

E = hv

• Where E = energy (J) h = Planck’s constant v = frequency (Hz)

• Manipulating E = mc2,

mc 2 = hv
hv h
mc = = =p
c l

• In other words, a particle-like property (p) is now related to a wave-like property

(v, λ )

Atomic Structure

Schrödinger Equation

QuickTimeª and a
decompressor
are needed to see this picture.

The Hydrogen Atom

• SE describes the behaviour of electrons in atoms (treating electrons as waves)

• Only certain solutions or energies are possible

• Quantisation results directly from boundary conditions

• A series of many possible solutions each with a certain energy and each
 3

described by a certain set of quantum numbers is obtained. Each one of these is

a wave function (given by ψ) and each describes a possible state for an electron

• Solutions to SE are called wave functions, ψ

• Ψ2 refers to the intensity or more precisely, a probability (ψ2 at any particular

point is the probability of finding the electron at that point)

• High values of ψ2 = high probability

Low values of ψ2 = low probability
Zero ψ2 = zero probability

• The lowest energy state / ground state is the one with the lowest value of the
quantum no.

Higher energy states – excited states

Wave Function

Ψ = R(r) . Y(θ ,φ )

• Can be separated into 2 parts: radial and angular

• Radial part R(r) depends only on the radial distance between the nucleus and
the electron and contains no information on direction or orientation (depends
on n and l)

• Angular part Y(θ ,φ ) depends on direction or orientation but not on distance

(depends on l and ml)

• The angles θ and φ define orientation with respect to a coordinate system

Quantum Numbers

Principal quantum no. (orbital size quantum no.) n

• Can take any integral value from 1, 2, 3 ... ∞

• Energy of the orbital depends on n but not l or ml

• Determines binding energy

Angular momentum quantum no. (orbital shape quantum no.) , l

 4

• Can take any integer value from 0 to n–1

l=0 s orbital
l=2 d orbital
l=3 f orbital

• For a given n, energy order is s < p < d < f

Magnetic quantum no. (orbital orientation quantum no.) ml

• Can take any integer value from – l ... 0 ... + l

• Indicates the no (2l + 1) of differently spatially oriented orbital’s for the given l
value

Note: A shell is a set of orbitals corresponding to any one value of n while a subshell is a
set of orbitals within a shell for which l is the same

• Degenerate orbitals refer to those of a particular n value having the same energy

• The degeneracy of any level (i.e. no of orbitals with identical energy) = n2

• Nodes are regions of zero electron density

• Total no of nodes = n – 1

• No of angular nodes = /

• No of radial nodes = n – / – 1

Radial Part of the wave function – R(r)

• Measure of orbital size and represents the variation of ψ as a function of distance

• For s orbitals, non-zero value of ψ at the nucleus

• For p orbitals, ψ=0 at the nucleus since angular momentum > 0

• For d orbitals, ψ=0 at the nucleus since angular momentum > 0 and sign does
not change for negative values of r
 5

• Ψ2 is the probability of finding an electron at that point or the electron density at

that point

• Note: we are interested in the distance; the greater the distance, the more points
on a sphere (i.e. proportional to the surface area of a sphere = 4π r2

• Multiplying R(r)2 by the surface area of the sphere at a distance r, we get

4π r2.R(r)2

• The radial distribution function (rdf) is a graph showing the probability that an
electron is at a certain distance r against 4π r2.R(r)2
 6

QuickTimeª and a
decompressor
are needed to see this picture.

• 4π r2 = 0 when r = 0 so rdf = 0 for all orbital’s at the centre of the nucleus. The
graph has a maximum, i.e. a most probable distance (r0)

• For a 1s orbital of H, this is called the Bohr radius (0.529 angstrom)

• Note: all functions tend to zero at large r

Some functions have R(r) = 0 – due to presence of radial nodes

• All rdfs have a maximum at some value of r (r0 increases with n; i.e. n determines
orbital size and for a given n, orbital’s are similar in size)

• For orbitals with radial nodes, secondary maxima occurs close to the nucleus
(important in polyelectron atoms)

Angular part of the wavefunction

• Determined by quantum no. l

• In fact, l = no of angular nodes, i.e. planes in which ψ = 0

 7

• For s orbitals, l = 0 (no angular nodes)

Spherical with no dependence on θ and φ )

• For p orbitals, l = 1 (1 angular node which is planar and divides the orbital into 2
lobes of opposite spin)

All p orbital’s have this shape, always 3 for any n value (ml = -1,0,+1; 3 possible
orientations: Px, Py, Pz)

• For d orbitals, l = 2 (2 perpendicular nodes and 4 lobes)

ml = -2, -1, 0, +1, +2

dxz, dxy, dyz, dz2, dx2-y2

• For f orbitals, l = 3

ml = -3, -2, -1, 0, +1, +2, +3

• Note: ψ2 is a probability and must be either positive or zero. Ψ can be zero,

positive or negative. These signs are relative and are on opposite sides of a node
(important in molecular orbitals)

• For a p orbital, the electron can be on either side with equal probability but never
on the node (treat electron density as waves using a particle model)

Polyelectronic Atoms

• The SE can only be solved exactly for H atom but that for polyelectronic atoms
can only be solved approximately. Calculations indicate that orbitals for other
atoms are similar to those found for H

• Comparing polyelectronic atoms to the H atom, the same quantum no are found,
same angular functions (hence same shpe and types of orbitals)

• Radial functions are similar but they are contracted to smaller radii as orbitals
shrink due to increasing nuclear charge, lower energies, and energies now
depend on l and n

Pauli Exclusion Principle

• 4th quantum no: ms = associated with electron itself and ‘spin’

 8

• ms = + ½

• States that no 2 electrons in the same atom may have the same set of 4
quantum no

• Since each orbital is defined by 3 quantum no (n, l, ml), it follows that 2 electrons
can be associated with any orbital, one with ms = +½ and one with ms = -½

• 2 such electrons are said to be ‘spin paired’ or have opposite spin

Aufbau Principle

• Electrons go into the lowest energy orbitals available

• Building up electronic configuration for an atom by adding electrons, 2 to each, to

the lowest energy orbital

• Note: in general, s < p < d for a given value of n

Hund’s Rule

• For a set of degenerate orbitals, electrons start by going one into each
with spins aligned / parallel

• Reason: electrons go into different orbitals if possible since they are

further apart from each other to minimise interelectronic repulsion. When singly
occupied, e.g. C and N, spin paralle is more stable than spin paired

• Electrons in singly occupied orbital are less effectively shielded from the
nucleus and the orbitals contract due to stronger electrostatic attractions

• From the graph, s orbitals penetrate the inner shells well and drop
steadily as Z increases

• P orbitals are slightly higher in energy than corresponding s orbitals as

they do not penetrate as effectively

• 3d orbitals are well-shieleded by 1s, 2s, 2p, 3s, 3p and remain fairly
constant until Ar (Z=18). At Z=19, 4s is below 3d so K: [Ar]4s1 and Ca: [Ar]4s2
(i.e. 3d penetrate 4s and then drops in energy. At Z=21, 3d < 4s so 3d orbitals fill
to give TM
 9

QuickTimeª and a
decompressor
are needed to see this picture.

Energy depends on n and l for non-H atoms

• The energies of the least tightly held electrons (those with highest energy)
and the energy of the next available orbitals (empty ones with lowest energy) are
the most important orbitals in determining the chemistry of the different elements

• These electrons and orbitals are involved in chemical bonding and

reactions

• Complete removal of the highest energy electron: ionisation of the atom

and energy required = IE

• In general, IEs are not equal to orbital energies but are related by

IE(M) = total E(M) – total E(M+)

• Removal of 1 electron generally affects the energies of other electrons so

only in certain special cases is E(M) = orbital energy of the removed e- (e.g. H)

Example

• IE(H) = 1313 kJ mol-1 while IE(He) = 2372 kJ mol-1 and IE(He+) = 5250 kJ mol-1
 10

• The 2 electrons in the 1s orbital of He are at higher energy than the single
electron in He+

• Reason: interelectronic repulsion partly offsets electron-nucleus attraction. It is as

if the electron partially shields each other from the full attraction of the nucleus

Penetration and Shielding

• Comparing rdf for 1s and 2s, most of the 2s orbital lies outside the main bulk of
1s electron density

• E.g. The two 1s electrons of Li provide a lot of shielding for the 2s electron
whereas they provide much less shielding for each other and the 2s electron
does not shield the 1s electron at all

• Valence electrons are those with highest energies (usually highest n value) and
involved directly in chemistry and bonding

• Core electrons are inner shell electrons with lower n values and are present in
completely filled orbital groups. They act as a less-than-complete shield of the
nuclear charge and are too tightly bound to the nucleus to be involved in
chemistry (i.e. too low in energy)

• Zeff (effective nuclear charge) can be estimated and used to calculate

approximate orbital and ionisation energies and compare them with observed IE

Calculated Zeff = Z – S

For s and p outer electrons, the contributions to the shielding constant S from the outer
electrons in the atom are:

• Zero for any electrons with a higher n (no shielding).

• 0.35 from every other electron with the same n (not very good shielding)

• 0.85 from every electron with n one less than our chosen electron (rather better
shielding), i.e. n-1.

• 1.00 from every electron with lower values of n (complete shielding).

 11

Periodic Table and Trends

• From Li to Ne, adding 2s and 2p electrons, for each step across the Period, Z
increases by 1 and S by 0.35. Zeff increases rapidly

• Due to the gradual increase in net attrction by the nucleus, the atomic orbitals get
smaller across the series and the atoms (and ions) have a smaller effective size

• Hence, IE increases as atomic radii decreases across the Period, and a change
in chemistry from cation (electropositive metals) to covalent to anion
(electronegative elements) to inert gas is observed

• Energy depends on l and n (i.e. 2s and 2p are not degenerate) due to the radial
wavefunctions and the particular importance of small inner lobes

• Reason: 1s electron partially shields the 3rd electron by getting between it and the
nucleus since 1s electron lies much closer to the nucleus

• However, a small part of the 2s orbital lies even closer to the nucleus than the
maximum of the 1s lobe and this contribution lowers the 2s energy compared
with the 2p energy. The electrons in the 2s orbital is said to ‘penetrate’ the core
better (similarly for 3s which penetrates more than 3p)

QuickTimeª and a
decompressor
are needed to see this picture.

• In other words, the smaller maxima (from the s orbital being nearer to the
nucleus) outweighs the larger maxima (of the p orbital), hence electrons in the s
orbital penetrate the core better
 12

• Exceptions in IE for B and O: Penetration makes s electrons lower than p

electrons in energy. For B, removal of 2p electron (highest energy) requires less
energy

• For B, C, N, removal of a 2p electron which are spin-parallel in their orbitals. For

O, F and Ne, removal of one of a pair of electrons from 2p.

Spin-paired in the same orbital are less stable (due to interelectronic repulsion)
than spin parallel and hence, less energy is needed

• Successive IE becomes increasingly endothermic as the removal of a 2nd

electron will be harder than that of the 1st as Zeff increases when the first electron
is removed (i.e. overcome the stronger attractions between ions of increasing
positive charge)

• Example: Al [Ne] 3s2 3p1 | 1st IE involves removing a 3p electron and 2nd and 3rd
involve removing the 3s electrons. After that, an electron with n=2 (a core
electron) which is nowhere near as well-shielded as valence electrons (n=3) is
removed. Thus, 4th IE of Al is very high and Al4+ is not observed

• Cation chemistry is only important for electropositive elements as forming cations

becomes harder as IE increase rapidly across the Period. In the middle and on
the righ, the chemistry becomes covalent or even anionic

• Electron affinity of a molecule or atom is the enthalpy change when an electron is

added to the neutral species to form a negative ion in the gaseous state

• An atom with a negative EA is more likely to gain an electron

• EA becomes more negative (i.e. becomes more favourable) across the Period –
the incoming electron will be attracted to the nucleus more tightly in a small atom
with high effective nuclear charge. (i.e. rhs) than in a large atom with low
effective nuclear charge. As with IE, the period trend is irregular

• Where adding an electron would generate a stable electronic configuration, EA

values will be more negative (i.e. more favourable) than would be predicted on
charge/size grounds alone, e.g. with Li, C and F

• Where adding an electron would destroy a stable electronic configuration we find

EA values less negative (i.e. less favourable) than would be predicted on
charge/size grounds alone, e.g. with B, N and Ne

• Inert gases have high IE and low EA and have little tendency to form anions and
cations
 13

Periodic Table

• For H, 2s and 2p are degenerate, so are 3s, 3p and 3d. Energy depends only on
n for one-electron system

• For all other atoms, the s, p, d etc. orbitals for any given n are no longer
degenerate and they split apart in energy due to different shielding and
penetration effects for different orbitals (s < p < d for a given n)

• All s orbitals penetrate inner shells well and have high Zeff than corresponding p
and d orbitals (drop in energy as Z increases)

• All p orbitals penetrate inner shells well except that they are well shielded from
the nucleus by the s electrons. They drop steadily after staying level for the first
few elements

• For d orbitals (e.g. 3d), they do not penetrate the lower orbitals (1s → 3p) at all as
they lack radial nodes (hence no smaller inner lobes) and are well-shielded while
the 1s to 3p orbitals are being filled and stay about the same energy as the H
atom