Atomic Structure

Particle in a Box

The vibrations of a guitar string produce standing waves because the string is bound at both ends so that the waveform cannot propagate along the string.

Standing Wave

Travelling Wave

The electron in an atom is also bound (i.e. its movement is restricted to a small region of space due to its attraction to the nucleus) and therefore its motion also leads to standing waves and quantization of energy.

Particle in a Box
The so-called Particle-in-a-Box model serves to illustrate how the wave nature of a bound electron in an atom naturally leads to quantized energy levels. Consider an electron confined to move along a wire fixed between two rigid walls at a distance L apart.

Particle in a Box
A classical description of the electrons motion allows the electron to move back and forwards along the wire. The kinetic energy, E, of the electron is given by

E = mu
2

Since the electron can have any velocity, u, its energy, E, can take any value, even zero. No position along the wire is more favorable than any other and the exact position and velocity of the electron can be known simultaneously.

Particle in a Box
A wave description of the electrons motion inside the one-dimensional box is analogous to the vibrations of a fixed guitar string.

The wavelength of the vibrations are restricted to whole numbers of halfwavelengths.

Particle in a Box
Like the vibrations of a guitar string, the wavefunction of the electron must fit exactly inside the box and thus the wavelength, !, of the electron is restricted. The length, L, of the box must be a whole number of half-wavelengths, i.e.

&' # L=n$ ! %2"

where the integer n can be considered as a quantum number. Rearranging to solve for the wavelength of the electron gives

2L != n

Particle in a Box
To calculate the kinetic energy of the electron we need to know its velocity, u. This can be obtained from rearranging the de Broglie equation to give

h u= m!
Substituting for u in the equation for the kinetic energy of the electron gives
2 E = 1 mu = 2 2m!2

h2

Particle in a Box
Substituting for ! using the earlier expression relating ! to the box length, L, gives

h nh E= = 2 2 2m! 8mL
Since n is an integer, the kinetic energy of the electron is restricted to multiples of h2/8mL2 and is therefore quantized.

2 2

Particle in a Box
Energy Levels & Wave Functions for a Particle in a Box

Energy/(h2/8mL2 )

2L != n

Particle in a Box
The smallest value of n is 1, therefore the lowest energy level (ground state) is at h2/8mL2. Unlike the classical model, the kinetic energy of the electron cannot be zero, i.e. the electron is never at rest. This lowest, irremovable energy is known as the zero-point energy and corresponds to a continuous fluctuating motion of the electron between the two walls of the box.

Particle in a Box
Since the energy levels are proportional to 1/mL2, they become more closely spaced as the box gets bigger or as the mass of the particle gets larger.
Energy ! E5 E4 E3 E2 E1

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Small m or L

Large m or L

For macroscopic particles with large relative mass, the levels are so closely spaced that the energy is effectively no longer quantized.

Particle in a Box
The wavefunctions " for the particle-in-a-box model do not correspond to an oscillation of the wire but instead describe the shape of the electron wave inside the box. The amplitude of the electron wave at any point along the wire is related to the probability of finding the electron and is proportional to "2. Unlike the classical model, the probability is not identical everywhere and in fact can be zero at certain points (nodes) along the wire. The number of nodes is given by n 1.

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Particle in a Box
Wavefunctions for the Particle-in-a-Box Model

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Wavefunction

Square of Wavefunction

Particle in a Box
The particle in a box model has a number of parallels with the quantum model of the atom: 1.! The motion of the electron is described by standing waves. 2.! The energy of the electron is quantized. 3.! The wavefunctions and energy levels are dependent on the integer n, analogous to the principal quantum number in an atom. 4.! The probability of finding the electron is related to the square of the wavefunction and is not the same at all points.

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Absorption Spectra
The particle in a box model can be used to rationalise the absorption spectra of cyanine dyes which have the general formula

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(CH3)2N! (!CH=CH!)k!C=N(CH3)2
These dyes are positively charged linear molecules containing conjugated double bonds. Their very intense colours make them useful in many applications including tunable lasers. The absorption maxima of the dyes show a strong correlation with the number of conjugated bonds, k.

Absorption Spectra
Absorption Spectra of Cyanine Dyes
k=4 k=5

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Absorbance

k=3 k=2

Wavelength, # / nm

Absorption Spectra
If the chain of conjugated double bonds are approximated as a wire of length, L, along which the $ electrons are free to travel,

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(CH3)2N! CH=CH!CH=CH!CH=CH!C=N(CH3)2 L
then the energy levels for the system can be calculated using

n2h2 E= 8mL2

n = 1, 2, 3, .

Absorption Spectra
The energy of the dye absorption is due to an electron being excited from the highest level occupied by the $ electrons to the lowest unoccupied level. The energy difference between two adjacent levels can be calculated using

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h2 "E = En+1 ! En = (2n + 1) 8mL2

For the dye absorption, n and n+1 are the quantum numbers for the highest occupied and lowest unoccupied levels, respectively.

Absorption Spectra
The quantum number n is connected with the number of $ electrons, N. Since each level accommodates two electrons, the highest occupied level has n = N/2. For the cyanine dyes the lone pair of electrons on the outer N atom are also included as $ electrons due to two possible resonance structures. Thus, N = 2k + 4

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(CH3)2N! (!CH=CH!)k!C=N(CH3)2 (CH3)2N= C!(!CH=CH!)k!N(CH3)2

Absorption Spectra
Energy Levels for (CH3)2N-(-CH=CH-)3-CH=N(CH3)2

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Absorption Spectra
The length, L, of the conjugated $ system can be expressed in terms of the number of $ electrons, N, and the bond length, do , as L = N do Substituting for n and L in the expression for %E gives

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h2 !E = ( N + 1) 2 8mN 2 do
Using the above expression with h = 6.63 x 10-34 J s, m = 9.11 x 10-31 kg and do = 140 x 10-12 m allows the excitation energy associated with the absorption spectra of cyanine dyes to be calculated.

Absorption Spectra
Using the simple relations

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hv = !E

and

v=

co

where v is the frequency and co = 3.0 x 108 m/s is the speed of light, the wavelength of the absorption maxima, #max, can be calculated from

"max

co hco = = v !E

Absorption Spectra
Calculated and Experimental Absorption Maxima #max of Cyanine Dyes (CH3)2N-(-CH=CH-)k-CH=N(CH3)2
k 0 1 2 3 4 5 6 N 4 6 8 10 12 14 16

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#max/nm
Calc 206 332 459 587 716 844 973 Expn 224 313 416 519 625 735 848

Colour of Soln Colourless Colourless Yellow Red Blue Green Colourless

Absorption Spectra
Substituting for %E in the expression for !max gives

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(max

2 hco & N 2 # 8md o co ! = =$ ! 'E $ N + 1 h % "

& N2 # ! =$ $ N + 1 ! 64.7 nm % "

As the number of $ electrons increases, N2 / N+1 & N. This implies that #max should increase linearly with N in agreement with the experimental data.

Absorption Spectra
Experimental Absorption Maxima (#max) vs Number of $ Electrons (N) for Cyanine Dyes
900 800 700 600

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(CH3)2N! (!CH=CH!)k!C=N(CH3)2
k=5 k=4 k=3 k=2 k=1 k=0
2 4 6 8 10

k=6

!max

500 400 300 200 100

(N = 2k + 4)
12 14 16 18

Molecular Orbital Model

25

The molecular-orbital (MO) model is the only bonding model which has its foundations based on the solution of the Schrdinger Wave Equation (SWE). Whereas atomic orbitals are solutions to the SWE in the atomic case, molecular-orbitals (MOs) are the solutions in the molecular case. MOs result from the overlap of atomic orbitals on adjacent atoms. The valence electrons involved in bonding are no longer localised on individual atoms but delocalised over the entire molecule.

General Rules

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The general rules which apply in using the molecular-orbital (MO) model are: ! Only valence orbitals need be considered when forming MOs. ! The number of MOs which form is equal to the number of atomic orbitals that interact. ! If two orbitals interact, an in-phase (bonding) MO and an out-of-phase (antibonding) MO result. ! The energy of the bonding MO is lower than the energy of the interacting orbitals while the energy of the antibonding MO is higher.

General Rules

27

Wavefunctions for orbitals have the same phase in the region of overlap and therefore reinforce one another

Wavefunctions for orbitals have opposite phase in the region of overlap and therefore cancel one another

General Rules

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Overlap of H 1s atomic orbitals to form bonding (inphase) and antibonding (out-of-phase) MOs in H2:

Out-of-Phase

In-Phase

General Rules
!1s" H !1s H2 AO MOs AO
Each MO accommodates at most only two electrons with opposite spin. H Since both electrons are lowered in energy relative to the isolated atoms, the H2 molecule is stable.

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From the Aufbau Principle, the lowest energy configuration (ground state) for H2 corresponds to both electrons in the ' bonding MO, i.e. '1s2.

General Rules
!1s" H !1s H2# H 2+ H H !1s !1s"

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The MO configuration for H2- is '1s2 '*1s1. Since two electrons are lowered in energy while one is raised, it only has half the stability of H2. Similarly for H2+, with a MO configuration of '1s1, it also has only half the stability of H2.

General Rules

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An indication of the bond strength in a molecule is given by the bond order (BO) where
(No of bonding e ! ) ! (No of antibonding e ! ) BO = 2 For a molecule !" 1s to be stable, the bond order must be greater than !1s zero (BO > 0)
H 2+ Stability Bond Energy (kJ/mol) Bond Length () Bond Order stable 255 1.06 ! H2 stable 456 0.74 1 He2+ stable 251 1.08 ! He2 unstable N/A N/A 0

General Rules

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Overlap of s orbitals results in only ' and '* MOs. Overlap of p orbitals results in ', '*, $ and $* MOs. Overlap of d orbitals results in ', '*, $, $*, ( and (* MOs.

Diatomic Molecules
"2p* 2p "2p !2p
E

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!2p* 2p

!2s* 2s !2s
AO MOs AO

Qualitative MO diagram for 2nd row homonuclear diatomics which assumes ' overlap is greater than $.
2s

Diatomic Molecules
MO diagrams for O2 and F2
"2p* 2p "2p !2p !2p* 2p 2p "2p* "2p !2p !2p*

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2p

E
!2s* 2s !2s O atom O2 MOs O atom F atom F2 MOs 2s 2s !2s F atom !2s* 2s

Diatomic Molecules

35

Except for O2 and F2, all other 2nd row diatomics have the '2p and $2p MOs inverted due to mixing of 2s and 2pz orbitals.
!2p* !2p* "2p* 2p "2p E !2p !2s* 2s !2s MOs 2s 2s 2p 2p !2p "2p !2s* 2s !2s MOs "2p* 2p

Diatomic Molecules

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Inversion of '2p and $2p MOs explains paramagnetic behavior of B2 due to presence of unpaired electrons.
!2p* "2p* 2p "2p E !2p !2s* 2s !2s B2 MOs 2s 2s 2p 2p !2p* "2p* !2p "2p !2s* 2s !2s B2 MOs 2p

Unpaired electrons

Diatomic Molecules

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MO model rationalizes bond energy, bond lengths and magnetic properties of 2nd row diatomics.
!2p* "2p* !2p "2p !2s* !2s !2p* "2p* "2p !2p !2s* !2s

B2

C2

N2
3 942 110 diamag

O2
2 495 121 paramag

F2
1 154 kJ/mol 143 diamag

Bond Order 1 2 Bond Energy 290 620 Bond Length 159 131 Magnetism paramag diamag

Heteronuclear Diatomics
!"
Less Electronegative Atom More Electronegative Atom

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!
AO MOs AO

In heteronuclear diatomics the overlapping orbitals are at different energies. The valence orbitals on the more electronegative atom lie at lower energy.

Heteronuclear Diatomics

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A modified MO scheme is used to describe heteronuclear diatomics involving atoms with similar electronegativities such as CO and NO.
!" #" 2p ! # 2s !"
2s 2p !" #"

2p

! # !"

2p

2s C atom ! CO MOs O atom

N atom ! NO MOs

2s O atom

Heteronuclear Diatomics

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If the atoms have very different electronegativities, the MOs are largely localized on one or the other atoms and the bonding becomes more ionic in !" character, e.g. HF.
1s #nb !

The 2s orbital on F is so low in energy that only the 2pz orbital overlaps with the H 1s orbital to form ' and '* MOs.
H atom HF MOs

2p

2s F atom

Polyatomic Molecules

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In polyatomic molecules, the MOs are built up by forming combinations of equivalent atomic orbitals on symmetry-related atoms known as linear combinations of atomic orbitals (LCAOs). In BeH2 the two hydrogen atoms are related by symmetry and therefore their 1s orbitals can be combined to form two linear combinations given by: " = HA(1s) HB(1s)

HA

Be

HB
"+ = HA(1s) + HB(1s)

Polyatomic Molecules
#g Be (2s) + !+

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#g*

Be (2s) " !+

LCAOs formed from H 1s orbitals overlap with atomic orbitals on Be which have the same symmetry.
"

#u

Be (2pz) + !

#u* H Be H

Be (2pz) " !"

Since H 1s and Be 2s and 2pz orbitals are orientated along the internuclear axis, only ' bonding and antibonding MOs result.

Polyatomic Molecules
Be (2s) + !
"

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Be (2pz) + !+ Be (2px) + !+ Be (2py) + !+ Be (2px) + !" Be (2py) + !" H Be H

The Be (2s) + " and Be (2pz) + "+ combinations are nonbonding as in-phase overlap is cancelled by out-of-phase overlap. The Be 2px and 2py orbitals are non bonding as they do not have the correct symmetry to overlap with either "+ or ".

Polyatomic Molecules
#u* #g* 2p 2px,2py 2pz $unb

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2s !" #u #g Be AOs BeH2 MOs H 1s LCAOs !+