CH2102 - Bonding and Structure

CH2102

–

Bonding and Structure

The Breakdown of Classical Ideas1898

–

JJ Thompson introduced the ‘fruit cake’ model, a positive mass containing the negatively

charged electrons within it1909

–

Rutherford proposed a model involving a positive nucleus with orbiting electrons.The problem with this model is that opposite forces attract and, since the proposedcentrifugal force of the electrons would irradiate energy, it would simply collapse intoitself.Atomic SpectraWhen an atom is given energy it is absorbed, allowing it to reach an excited state. This energy is thenemitted again in order to reach the ground, stable, state and as it is released it is seen as discretelines of colours. This shows that light is quantised into energy gaps equivalent to those between theground and excited state of the atom, and as such can be used to determine the energy levels withinatoms according to the formula;

ΔE=hν (where h=Planck’s constant=6.626x10

-34

Js)Bohr Theory



Electrons possess fixed energy orbits



Each energy level is characterised by the quantum number, ‘n’



Lines in the atomic spectra show the transitions between orbitsHowever;



Each line in the atomic spectrum is, in fact, several lines close together. Therefore, each

orbit must contain ‘sub

-

shells’.

Considering Wave Mechanics in Remaking Our Description of the ElectronLight is both a wave and a particle, everything with a mass also has a wavelength and vice-verse,

light is therefore defined as being composed of photons, or ‘packets’ of light energy.

If E=hν defines the energy of light, and E=mc

2

defines the energy of a particle then the two must beequal for a wave-particle duality, this gives rise to the de Broglie relationship;

hν=mc

2

but

ν=c/λ

So;

h

νλ

=mc

2

,h

λ

=mc and mc=

ρ

(momentum)

Therefore;

h

λ

=

ρ

, relating wave and particle behaviour,

The de Broglie Relationship

.Electrons also act similarly to light, experimentally shown as they can be diffracted. Note however,most objects do not display wave-particle behaviour.

The Heisenberg Uncertainty PrincipleFor a particle it is possible to measure position and momentum at the same time.For a wave-particle this is not possible, the more accurately we measure the position, the lessaccurately we can find momentum. This is because to view the electron we must use light, which inturn gives the electron energy, distorting the results. This is an inherent property of nature andcannot be circumvented.When po

sition=x, y, z and error=Δx, Δy, Δz

and momentum =ρx, ρy, ρz and error=Δρx, Δρy, Δρz;

Δ

x+

Δρ

x

≥

h4

π

This makes it meaningless to talk of electron position in orbits since both values simply can’t be

evaluated effectively. We therefore exchange orbits for orbitals

–

a probability distribution of spacein which the electron moves and not a precise position.Wave Mechanics



An electron in a stable state must also be in a stationary state, meaning it returns to thesame point repeatedly in order to give the diameter of the orbital an integer number of wavelengths since wave mechanics will only allow for these values.The Schrodinger Equation

δ

2

ψδ

x

2

+

δ

2

ψδ

y

2

+

δ

2

ψδ

z

2

+8

π

2

h

2



E

−

v

ψ

=0

Where the blue describes the position of the electron, the red is a constant value and the green, v, isthe potential energy (the sum of all attractive/repulsive forces).

Ψ is the wave function, it is the equivalent of y in y=sinx

ψ itself is simply numerical and provides no information, ψ

2

however gives the probability of findingan electron at any given Cartesian point defined by (x, y, z).

ψ has two parts;



=





,

ℓ

.





,



ℓ

,



where R= the radial wave function, dependant on distance from nucleusand Y= the angular wave function, dependant on the Cartesian co-ordinates.The Quantum Numbers



n

–

the principle quantum number-

takes integral values, n≠0

-determines the energy level of the orbital



ℓ

–

the azimuthal quantum number-takes integral values from 0 ->n-1-determines orbital shape

i.e.

ℓ

=0=s-orbital

ℓ

=1=p=orbital etc.



m

ℓ

–

the magnetic quantum number-takes integral values from -

ℓ

->

ℓ

-

determines the orbital’s orientation in 3d space

Radial Wave Function, RWhen n=1, m

ℓ

and ℓ must equal

0; this gives rise to a 1s orbital.The radial wave function for a 1s orbital is, graphically, shown as;And for 2s (where n=2, m

ℓ

=0 and ℓ=0);

Note that in this graph R is negative in places;



this is nothing to do with electron presence orelectrostatic charges



the sign is purely mathematical and is part of R, thedescription of the electron. It describes the phase, an importantfactor in bonding.Since R is not measureable we look at the radial distributionfunction for which we consider the electron density (related to

ψ

2

)At the nucleus, r=0, there is a high probability of finding anelectron but only a tiny amount of space available to possiblyoccupy. For small values of r there are more points to occupy butless probability, until you reach large values of r where there areR (Å

-3/2

)r(Å)

N.B. Thispoint isasymptotic