Chemistry Lecture

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Chemistry Lecture

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6 Lecture Course

Prof S.M.Draper

SNIAMS Institute 2.5

smdraper@tcd.ie

Objectives of the course

• Wave mechanics / Atomic orbitals (AOs)

– The basis for rejecting classical mechanics (the Bohr Model) in the

treatment of electrons

– Wave mechanics and the Schrödinger equation

– Representation of atomic orbitals as wave functions

– Electron densities and radial distribution functions

– Understanding the effects of shielding and penetration on AO energies

• Bonding

– Review VSEPR and Hybridisation

– Linear combination of molecular orbitals (LCAO), bonding / antibonding

– Labelling of molecular orbitals (MOs) (s, p and g, u)

– Homonuclear diatomic MO diagrams – mixing of different AO’s

– More complex molecules (CO, H2O ….)

– MO diagrams for Transition metal complexes

2

Lecture schedule

Lecture 1 Revision of Bohr model of atoms and Schrödinger equation

and p orbitals

functions and electron shielding. Revision of Lewis bonding

in transition metals complexes

3

Literature

• Book Sources: all titles listed here are available in the Hamilton Library

Oxford Science Publications ISBN 0 198556942 – condensed text,

excellent diagrams

Gaus – comprehensive text, very detailed on aufbau principle

comprehensive text with very accessible language. CD contains

interactive energy diagrams

– Additional sources:

http://winter.group.shef.ac.uk/orbitron/ - gallery of AOs and MOs

4

Tutorials

they are YOUR chance to understand the material and to ask questions

You MUST attempt the sheets before and during the tutorial and read the

through the lectures preceding it

5

Where it All Began

Prof. S.M.Draper

SNIAMS Rm 2.5

smdraper@tcd.ie

Adsorption / Emission spectra for Hydrogen

Johann Balmer (1885) measured line spectra for hydrogen

364.6 nm (uv), 410.2 nm (uv), 434.1 nm (violet), 486.1 nm (blue), and

656.3 nm (red).

Balmer discovered these lines occur in a series - both absorption and emission -

where is the Rydberg constant (3.29 ×1015 Hz)

1 1

v 2 2

n1 n2

Other series for n1=1 (Lyman – UV), n1=3 (Paschen – IR) etc.

Electrons must have specific energies – no model of the atom to explain this.

7

Bohr model of the atom (1913)

http://www.youtube.com/watch?v=R7OKPaKr5QM

Assumptions

1) Rutherford (1912) model of the atom (Planetary model with central

nucleus + electrons in orbit)

quantised into packets called photons (particle like property).

E = hn

Velocity, c Wavelength, l

Fluctuating electric

/magnetic field

} i.e. frequency = v Hz , cycles/sec,

n waves passing per second

s-1

8

Bohr model of the atom

Speed of electromagnetic waves (c) is constant (n and l vary)

c = n l, n = c / l, E = h n, E = h c / l

n 3 x 109 Hz n 3 x 1020 Hz

E = 2 x 10-24 J E = 2 x 10-13 J

E – energy (J)

h – Plancks constant (J s)

n – frequency (Hz)

c – speed of light (m-1)

l – wavelength (m)

9

Bohr model of the atom

observed in spectra)

h

mvr n

2

• Classical electromagnetic theory rejected (charged particles

undergoing acceleration must emit radiation) at these small

dimensions

orbit to another

E Ea Eb

where a and b represent the energy of the initial and final orbits

Bohr model

Electron travelling around nucleus in circular

orbits – must be a balance between attraction

to nucleus and flying off (like a planets orbit)

Ze2 Ze2

1) Centripetal (electrostatic) F PE

4e 0 r 2 4e 0 r

2) Centrifugal mv 2 1 2

F KE mv

r 2

Equalize magnitude of forces Resulting energy E = KE + PE

mv 2 Ze2 Ze2 1 2 Ze 2 Ze 2 1

mv

2

E mv mv 2

r 4e 0 r 2

4e 0 r 2 4e 0 r 8e 0 r 2

r - radius of the orbit, m – mass of electron, v – velocity of the electron

11

Bohr model – calculating the energy and radius

will not be examined

• Energy Ze2 1

mv2 E

8e 0 r 2

h

mvr n

• Quantised angular momentum 2

1 2 mvr n2h2 Ze2

2

• Combining the two mv 2 2 E

2 2mr 2

8 mr 8e 0 r

• Rearranging to give r

r 2 n 2 h 2 8e 0 n 2 h 2e 0

r

r

8 2 m Ze 2 mZe 2

• Substitute r into energy gives

Ze2 mZ 2e 4

E 2 2 2

8e 0 r 8n h e 0

• Energy is dependent on 1 and Z2 (2s and 2p the same – only true for 1

electron systems) n2

12

Taking Important findings: Energy levels of Hydrogen

Substitute quantised momentum into energy expression and rearrange

in terms of r (radius) (see previous slide)

n 2 h 2e 0 n 2 a0

r

mZe2 Z

a0 (Bohr) radius of the 1s electron on Hydrogen 52.9 pm (n =1, Z =1)

1

2

Radius (r) depends on n and

Z

mZ 2e 4 13.6056 Z 2

En 2 2 2 = (in eV)

8n h e 0 n 2

1 2

Energy (E) depends on and Z

n2

13

n=4

Radius of orbits

distance

13.6056

r n 2 a0 En n=2

n2

n=1

n energy (eV) r (pm) nucleus

1 -13.6056 52.9

2 -3.4014 211

3 -1.5117 476

4 -0.8504 847

5 -0.3779 1322

0.0000

Note. The spacing reflects the radius of the

Orbit – not the energy.

14

Energy levels of Hydrogen

n=

n=5

n=4

For hydrogen (Z=1) n=3

energy n=2

13.6056

r n 2 a0 En n=1

n2

1 -13.6056

2 -3.4014

3 -1.5117

4 -0.8504

5 -0.3779

0.0000

Note. The spacing reflects the energy

Ionization energy = -13.6056 eV not the radius of the orbit.

15

Emission spectra

(http://www.youtube.com/watch?v=5z2ZfYVzefs)

1 1

E 13.6056 2 2

n

inital n final

Same form as fitted to emission specta

n=4 n=2 l = 486 nm

n=5 n=2 l = 434 nm

= 13.6056 eV = 3.29 ×1015 Hz

not the radius of the orbit.

16

Problems with the Bohr Model

• Only works for 1 electron systems

– E.g. H, He+, Li2+

– Modified Bohr-Sommerfield (elliptical orbits - not satisfactory)

• Cannot apply the model to interpret the emission spectra of complex atoms

– e.g. can be diffracted as they pass through a crystal (like x-rays)

– considered as classical particles in Bohr model

17

Wave / particle duality

http://www.youtube.com/watch?v=IsA_oIXdF_8

de Broglie (1923)

By this time it was accepted that EM radiation can have wave and particle

properties (photons)

particle duality). Particles could have an associated wavelength (l)

hc h

E mc 2 , E l

l mc

No experimental at time.

to Braggs Law (used for X-ray diffraction)

18

Wave Mechanics

• For waves: it is not possible to determine the position and momentum of the

electron simultaneously – Heisenberg ‘Uncertainty principle’

we will deal with are real)

(1927). The time-independent form of the Schrödinger equation for the

hydrogen atom is:

h 2

e 2

2

2 2

2

E

2

8 m

2

4e r

0

x y z2 2 2

energy energy energy

19

Wave mechanics and atoms

• What does this mean for atoms ?

wavelengths

– These create continuous or standing waves (like on a

guitar string)

– The wavefunction is not continuous

nature of the orbital energies.

20

Atomic solutions of the Schrödinger equation for H

• Schrödinger equation can be solved exactly for one electron systems

– Solved by trial and error manipulations for more electrons

dimensional space called an atomic orbital: n, l, m (and spin quantum

number describing the electron s)

For a given value of n, l has values 0 to (n-1).

For a given value of l, ml has values from +l through 0 to –l.

21

Solutions of the Schrödinger equation for H: each electron’s

unique ‘passport’ number

l has values 0 to (n-1) m has values from +l through 0 to –l

n 1 2 2 2 2

l 0 0 1 1 1

ml 0 0 -1 0 1

Orbital 1s 2s 2p 2p 2p

n 3 3 3 3 3 3 3 3 3

l 0 1 1 1 2 2 2 2 2

ml 0 -1 0 1 -2 -1 0 1 2

Orbital 3s 3p 3p 3p 3d 3d 3d 3d 3d

22

An introduction to

Molecular Orbital Theory

Schrödinger equation and wavefunctions.

Prof.S.M.Draper

SIAMS Rm 2.5

smdraper@tcd.ie

Last Lecture

• Recap of the Bohr model

– Electrons

– Assumptions

– Energies / emission spectra

– Radii

– Only works for 1 electron atoms

– Cannot explain splitting by a magnetic field

• Wave-particle duality

• Wave mechanics

– Schrödinger

– Solutions give quantum number n, l, ml atomic orbitals

24

Representations of Orbitals:

For an atomic system containing one electron (e.g. H, He+ etc.). The

wavefunction, Ψ, is a solution of the Schrödinger equation.

orbital (φ - phi).

Each wavefunction (φ ) has two parts:

radial part – which changes as a function of distance from the nucleus

angular part – which changes as a function of shape

φ xyz= φradial(r) φangular(,)

= Rnl(r) Ylm(,)

Orbitals have

• SHAPE determined by Ylm(,) - angular part (spherical harmonics)

• ENERGY determined by the Schrödinger equation. Calculated exactly for

one electron systems and by trial and error for more complex systems).

25

Polar Coordinates

• To describe the wavefunction of atomic orbitals we must describe it in

three dimensional space

Location of point P

Cartesian = x, y, z

r, ,

26

Wavefunctions for the 1s AO of H

Also the mathematical wavefunction for all hydrogen-like orbitals

Rnl(r) Ylm(,)

1s 3 1

Z 2 1 2 2Z

2 e ( r r 2)

r

a0 4 n a0

For hydrogen this simplifies as Z=1 and ao=1 (in atomic units) and thus r = 2.

Hence

Constants are such that

1

1s 2e( r ) 2 1

2

orbital must be 1 when all space

Angular component is a constant Spherical is considered

27

Graphical representation of Radial Wavefunction

• R(r) of the 1s orbital of H

it decays exponentially with r

R(r) = 2e( r ) it has a maximum at r = 0

probability but…. 3 (1s)2

R(r) in a.u.

– Misleading – does not take 2

into account the volume

1

– R(r)2 increases toward r = 0 1s

very small so probability of 0 1 2 3 4 5

being at small r is small Radius (a.u)

28

Radial distribution functions (RDF)

• Probability of an electron at a radius r (RDF) is given by probability of an

electron at a point which has radius r multiplied by the volume at a radius of r

– By differentiation, 8

4 3

the volume of a sphere = r 6

3

1s

2

V

4r R(r)

so 4r 2 4

r

2

2

• RDF(r) = 4r2 R(r)2

0

• Maximum for 1s at a0 (like Bohr!) 0 1 2 3 4 5

Radius (a.u)

29

Wave functions of 2s and 3s orbitals

2s(r) 3s(r)

3 3

General 1 Z 2 1 Z 2

(2 r r )e( r r 2)

(6 6 r r ( r r ) 2 )e( r r 2)

2 2 a0 9 3 a0

2Z 2Z

r r

n a0 0

n a

1

2

1 ( r / 3)

2

( 2 r ) e ( r 2) 6 4 r r e

2 2 9 3 3

The form of the wave functions is the important concept – not the precise equation

Note R(r) has functional form

Normalisation constant * polynomial (increasing order with n) * exponential (-r/n)

30

Wave functions of Hydrogen 2s and 3s orbitals

1 2 ( r / 3)

2

1 ( r 2)

For H 2s(r) = (2 r ) e For H 3s(r) = 6 4 r r e

2 2 9 3 3

e( r / n) the larger n the more diffuse the orbital

0.5

These wavefunctions change sign

0.4 2s

R(r) = 0 RADIAL NODE

R(r) in a.u.

0.3

0.1 3s

3s changes sign twice with two

0

nodes (r =1.9, 7.1 a.u.)

0 2 4 6 8 10 12 14 16

-0.1

Caused by the order of Radius (a.u)

the polynomial !

31

What does a negative sign mean ?

• The absolute sign of a wave function is not important.

– The wave function has NO PHYSICAL SIGNIFICANCE

– the electron density is related to the square of the wave function

– This is the same irrespective of the sign

• Wavefunction signs matter when two orbitals interact with each other (see

later)

• Some books have the 2s as opposite sign – you can see that the electron

density R(r)2 is the same

0.8

0.6

0.4

0.4

R(r) in a.u.

R(r) in a.u.

0.2 2s

0

(2s)2

0.2

-0.2 0 2 4 6 8 10

-2s

-0.4

-0.6 0

-0.8 0 2 4 6 8 10

Radius (a.u) Radius (a.u)

32

Radial Nodes

• The point at which R(r) = 0 (not including the origin) is called a radial node

• Number of radial node = n – l – 1

1s = 1 – 0 – 1 = 0

2s = 2 – 0 – 1 = 1 2p = 2 – 1 – 1 = 0

3s = 3 – 0 – 1 = 2 3p = 3 – 1 – 1 = 1 3d = 3 – 2 – 1 = 0

• In general the more nodes contained within e.g. a set of s orbitals the higher the energy

of the orbital – like a wave that crosses the x axis many times

• Why are there radial nodes ?

– Pauli exclusion principle dictates that no two electrons can have the same set of

quantum numbers

– Actually – no two electron can overlap (i.e occupy same space)

– Overlap integral = A B 0 (analogous to normalisation)

*

– Satisfied for AO’s with same l by having change(s) in the wave function sign

– Satisfied for AO’s with different l because the angular component ensures no

overlap

Orthogonal orbitals

• Radial nodes ensure that orbital of the same angular momentum (s-s, p-p,

d-d) are orthogonal

• E.g. 1s – 2s

– Individual traces are 4 r 2 R(r )

– The two orbitals are orthogonal

34

RDF’s of ns orbitals

1s – 1 peak. Maximum at r = a0 - Bohr Model radius of a0

2s – 2 peaks Maximum at r ≈ 5 a0 - Bohr Model radius of 4 a0

3s – 3 peaks Maximum at r ≈ 13 a0 - Bohr Model radius of 9 a0

These maximum correspond to the distance from the nucleus at which the electron

has the highest probability of being found i.e. the optimum size of a sphere of very

small thickness in which to find an electron in a 1s, 2s or 3s oribtial.

8

6

2

4r R(r)

4

2

0

0 5 10 15 20

Radius (a.u)

Representing atomic orbitals

• How do the radial wavefunctions and the RDF reflect experimental

observations of electron density ?

– s orbitals have spherical symmetry

– The electron density is zero – radial nodes

– The most probable point for locating an electron is the nucleus

– The most probable shell at radius r for locating an electron increases

from 1s to 2s to 3s oribitals.

1s 2s 3s

Boundary Surfaces

• Represent the wave function/atomic orbital in 3D

– Draw a 3D surface at a given value of φ

– Define the surfac such that it encloses a space in which the electron spends

most of its time

– The surface now depicts outer shape and size of the orbital

– The inner structure of the wave function is hidden beneath the surface

1s Boundary surface

R(r) in a.u.

0

0 1 2 3 4 5

Radius (a.u)

Putting All the Representations Together

p orbitals - wavefunctions

• There are three p orbitals for each value of n (px, py, pz)

– The radial function is the same for all np orbitals

– The angular terms are different different shapes (orientations)

– Angular terms are the same for different n 2px, 3px, 4px i.e. have same

shape

2Z

• Wave function for 2p and 3p orbitals r

n a0

R(r) Y(

1

3 3 2

1 Z 2 Y ( p z ) cos( )

R(2 p) rre( r r 2)

4

2 6 a0 1

2

3

Y ( p x ) sin( ) cos( )

3 4

1 Z 2

R(3 p) (4 rr ) rre( r r 2)

3

1

2

9 6 a0 Y ( px ) sin( ) sin( )

4

Note the form of R(r) Constant * polynomial * r * exponential

39

p orbitals – radial functions

• Radial wave function for hydrogen p orbitals (Z=1)

for 2p n = 2 r = 1 for 3p n = 3 r = 2/3

1 1 2 r 2 r ( 2r

R(2 p) re( r 2)

R(3 p) 4 e

3)

2 6 9 6 33

• Polynomial nodes

– Equation for no. of radial nodes 0.2

– n – l – 1 2p =0 , 3p =1 2p

0.15

– Ensures 2p and 3p orthogonal

R(r) in a.u.

0.1

• All p orbitals are multiplied by r

R(r) = 0 at r = 0 0.05 3p

angular node 0 5 10 15 20

-0.05

Radius (a.u)

40

p orbitals – angular functions boundary surfaces

1

• All p orbitals have the same shape 3 2

Y ( pz ) cos( )

4

1

• Angular function give rise to direction 3 2

Y ( px ) sin( ) cos( )

4

• Can represent p orbital as dot diagrams or 1

3 2

boundary surfaces Y ( py ) sin( ) sin( )

4

• 1 angular nodal plane px (yz plane), py (xz plane) pz (xy plane)

– Ensures that p orbitals are orthogonal to s orbitals

41

p orbitals – RDF’s

• Radial distribution function show probability at a given radius

• 3p function – two peaks, maximum at r ≈ 12 a0 (not the same as Bohr)

2.5

2 2p

1.5

2

4r R(r)

1 3p

2

0.5

0

0 5 10 15 20

Radius (a.u)

42

An introduction to

Molecular Orbital Theory

Lecture 3

Prof S.M.Draper

smdraper@tcd.ie

SNIAMS 2.5

Where Have we Been ? Last lectures

• Solutions of the Schrödinger equation for atoms

– Atomic orbitals (φ)

– Defined three quantum number (n, l, ml)

– Angular term constant for s orbitals

– Wavefunction as constant * polynomial * exponential

– Decays as the larger n the more diffuse the orbital

– Defined radial nodes and examined the number of radial nodes (polynomial n – l

-1)

( r / n)

– Discussed theerequirement for radial nodes Pauli exclusion principle

• p orbitals

– Radial functions similar to s orbital (except additional r) R(0) =0

– Angular terms define shapes px, py and pz – same for different n

– Radial distribution function for p orbitals

44

Where are we going ?

Lecture 3

• Brief wavefunction considerations: d and f orbitals

• Using wavefunctions and radial distribution functions (RDFs) to

– compare atomic orbitals (AOs)

– define penetration and shielding

– explain the ‘aufbau’ building-up principle

• Revision

- Localised bond pictures

- Hybridisation

d orbitals – wave functions

• Five d orbitals for each value of n (n ≥ 3) l = 2 , ml = -2, -1, 0, 1, 2

– Radial wave functions same for all 3d orbital

3

1 Z 2

R(3d ) ( rr ) 2 e( r r 2)

9 30 a0

0.1 1.5

• Max probability at r = 9 a0

0.08 3d - RDF

3d - R(r)

R(r) in a.u.

1

• AO’s with no nodes have

4r2 R(r)2

0.06

0.5

radius as Bohr model

0.02

0 0

• 4d orbital has 1 node 0 5 10 15 20

Radius (a.u)

d orbitals – angular functions

• Angular functions same for d xy , d yz , d xy , d z 2 , d x2 y 2 irrespective of n

same shape for 3d, 4d, 5d orbitals using boundary surfaces

1

Five different angular function e.g. 15 2

Y (d xz ) sin( ) cos( ) cos( )

16

Two angular nodes planes

orthogonal to s (0) and p (1)

xy and xz (note: +ve lobe points

between +x and +y axes)

dxy (yz) dz 2

(xz)

47

f orbitals

• Almost no covalent bonding shape not really important

– f block is 14 element wide, same shape for 4f, 5f etc

– Radial functions same for all nf orbitals

– Three angular nodes (nodal planes) orthogonal to s, p and d orbitals

Penetration

• RDF allow us to directly compare AOs on the same graph

• The RDFs of AOs within a given shell (n) have different maxima

• Number of nodes n – l - 1

– n=3 3s 2 nodes 3p 1 node 3d 0 nodes

– 3s has a peak very close to the nucleus

– 3p has a peak close to the nucleus 1.5

3p

3d

• These close peaks have a very strong 1

3s

2

4r R(r)

2

0.5

• 3s is said to be the most penetrating

0 5 10 15 20

Radius (a.u)

Multi-electron Atoms

• Multi-electron atoms are assumed to have hydrogen-like wave functions.

• Differences are the increase in atomic number and the effective nuclear charge.

• In reality the electrons repel each other and shield the nucleus

S = a screening or shielding constant

• Li atom – why is the electronic configuration 1s22s1 and not 1s2 2p1 ?

8

– 1s electrons shield the valence

electron from the nuclear charge 6 1s

– 2s penetrates more effectively

feels a greater nuclear charge

4r2 R(r)2

4 2p

– 2p penetrates less effectively 2s

– 2s is filled first

2

0

• E(ns) < E(np) < E(nd) 0 5 10

Radius (a.u)

Periodic Table

• Shielding and penetration E(ns) < E(np) < E(nd) < E(nf)

• This gives rise to electronic configuration of atoms and the order of elements

in the periodic table

electrons fill degenerate (same energy) levels singularly first to give

maximum spin (Hund’s rule)

K, Ca 2s 2p

3s 3p

4s 3d

• E(6s) < E(5d) ≈ E(4f) 6s 5d

La [Xe] 6s2 5d1

Ce [Xe] 6s2 4f2 4f

51

More complex results of penetration and shielding

Energy levels vs atomic number

• For H (Z=1) all orbitals within a

principle QN have same energy

penetration follows

s>p>d>f

orbitals of n ≤ 3

energy with Z until Z = 19

• 4s filled before 3d

effectively energy drops

52

The Transition Metal Hiccup !

The energy of the 4s and 3d orbitals

• For K and Ca the E(3d) > E(4s),

• At Sc on the E(3d) < E(4s) (but close)

– If 4s electron go into 3d orbital the extra e-e repulsion and shielding cause

the 3d to rise above 4s again – hence the strange energy level diagram

– Result is that TM’s lose 4s electrons first when ionized

Energy 4p {

4p

3d {

4s

4s

3d

Increasing Z

K Ca Sc Ti

53

Drawing representations of AO’s

• Need to be able to draw AO’s when considering their interactions i.e when

they form MO’s

– Diagrams help to visualise the 3D nature of AO’s

– Simple drawings are all you need !!!!!

54

Making Bonds

Localised Bond Pictures

Revision of JF Lewis Bonding / VSEPR

– Views covalent bonds as occurring between two atoms

– Each bond is independent of the others

– Each single bond is made up of two shared electrons

– One electron is usually provided by each atom

– Each 1st and 2nd row atom attains a noble gas configuration (usually)

– Shape obtained by VSEPR (Valence Shell Electron Pair Repulsion)

e.g. H2

H + × H H × H

electrons H ─ H

55

Lewis bonding

• Octet rule for main group elements / 18 electron rule for transition metals

– All atoms have a share of 8 electrons (main group : s + three p orbitals )

or 18 electrons (TM : s + three p + five d orbitals) to fill all their valence

atomic orbitals. This makes them stable

• Diatomics

– F2 ××

××

××

+ × F F × F

××

F

×× ××

2 electrons shared bond order = 1

F─F

– O2

×× ××

O + × O ×

O ×× O

×× ××

4 electrons shared bond order = 2

O═O

Lewis bonding – polyatomics (H2O)

– Oxygen (Group 16) has 6 valence electrons, each hydrogen (Group 1) has 1

electron

– Oxygen has two lone pairs

×× ××

+ ×O × H ×O H

×

2H

×× ××

• Shape – VSEPR

– Electrons repel each other (repulsion between lone pair electrons >

repulsion between electrons in bonding pairs)

– Oxygen has 2 bond pairs and 2 lone pairs 4 directions to consider

– Accommodate 4 directions Tetrahedral shape

– H2O is bent with H-O-H angle of 104.5o

– Compares with a perfect tetrahedral of 109.45o lone pair repulsion

Lewis bonding – polyatomics (ethene)

• Used different symbols for electrons on adjacent atoms

×× H H

4H + 2× C × C ×× C

H H

Carbon atoms share 4 electron bond order = 2 C ═ C

Carbon –hydrogen interactions share 2 electrons C ─ H

• Shape – VSEPR

– Electrons repel each other

– Carbon atoms have 3 directions – bond to C and two bonds to H

– Accommodate 3 bond direction 120o in a plane (molecule is flat)

58

Lewis structures – breaking the octet rule

• Some structures to not obey the 8 electron rule.

– e.g PF5

90o

F F

×

F

F × P F F P 120o

×

× ×

F F F

F

(only the electrons round the P are shown for clarity)

– P atom has 5 bond pairs with 2 electrons each 10 electrons !

59

TUTORIAL 1 - Monday !

1. What is the relationship between the possible angular momentum quantum

numbers to the principal quantum number?

2. How many atomic orbitals are there in a shell of principal quantum number

n?

3. Draw sketches to represent the following for 3s, 3p and 3d orbitals.

a) the radial wave function

b) the radial distribution

c) the angular wave function

4. Penetration and shielding are terms used when discussing atomic orbitals

a) Explain what the terms penetration and shielding mean.

b) How do these concepts help to explain the structure of the periodic

table

5. Sketch the d orbitals as enclosed surfaces, showing the signs of the

wavefunction.

6. What does the sign of a wavefunction mean ?

60

An introduction to

Molecular Orbital Theory

Molecular orbital theory and diatomic molecules

Prof S.M.Draper

SNIAMS 2.5

smdraper@tcd.ie

Where did we go last lecture ?

• d orbitals

– Radial wavefunctions, nodes and angular wavefunctions (shapes)

• f orbitals

– Radial wavefunctions, nodes and angular wavefunctions (shapes)

• Multi-electron atoms

– Penetration and shielding

– Atomic orbital energies, filling and the periodic table

– Lewis structures number of electron pairs

bond order (electrons shares divided by 2)

– VSEPR repulsion of electron pairs (BP and LP)

molecular shape

62

Lecture 4 – where we are going

• Revision of hybridisation

- Mixing atomic orbitals on the same atom

- How atomic orbitals on different atoms interact

- The labelling of the new molecular orbitals

- The energies of the resulting molecular orbitals

Valence bond theory and hybridisation

• Valence bond theory (Linus Pauling)

– Based on localised bonding

– Hybridisation to give a geometry which is consistent with experiment.

– Hybridisation constructs new hybrid atomic orbitals from the AO’s

– E.g. BeH2, Be – 1s2 2s2

H × Be H

×

• Correctly predicted by VSEPR to be linear – can we explain it using AO’s

– Mix S with pz orbital 2 sp hybridized orbitals

64

sp hybridisation

• sp hybridisation

– Mix and a s and a p orbital – two combinations s + pz and s – pz

– Two AO’s two hybrid AO’s

– Relative sign is important when mixing orbitals

– sp therefore means that the hybrid orbital is 50% s and 50% p

sp

1

2

2 s 2 pz +

sp

1

2

2 s 2 pz +

= -

65

Hybridisation – sp2 hybridisation

• Lewis structure 3 directions

H H

C ×× C

H H

• Molecular is planar

at 120o

two p orbitals

sp2 hybridisation

66

Hybridisation – bonds

• For ethene sp2 hybridisation bonding in three directions

– Have not accounted for the second pair of electrons shared by the C

atoms

– Could think of the C as going from s2 p2 (sp2)3 px1

67

Hybridisation – sp3

• For tetrahedral molecules we have to mix the s with all the p orbitals (sp3)

– This give rise 4 equally spaced orbitals e.g. methane

H H

C

H H

4 electron pairs sp3 hybridisation tetrahedral

sp3 orbitals occupied by lone pairs.

××

H ×O H

×

××

4 electron pairs sp3 hybridisation tetrahedral

68

Hybridisation – d orbitals

Trigonal Bipyramidal Lone pairs equatorial

sp3d 5 electron pairs

(s + px + py + pz + dz2)

octahedral

sp3d2 6 electron pairs

(s+ px+ py+ pz+ dz2+ dx2-y2)

69

Hybridisation – summary

isation that are mixed formula

AB3 BF3, CO32-

sp2 s + px + p y trigonal planar

C2H4

SO42-, CH4,

sp3 s + px + py + pz tetrahedral AB4

NH3, H2O,

SF6

sp3d2 s + px + py + pz + dz2 + dx2-y2 octahedral AB6 [Ni(CN)4]2-

[PtCl4]2-

70

Molecular orbital theory

– Different to Lewis and hybridisation (these are not MO)

– Molecular orbitals are formed which involve all of the atoms of the

molecule

(hybridisation effects only the central atom)

71

Molecular orbital theory of H2 - bonding

In Phase

In phase interaction (same sign)

1s + 1s

1 a b

Constructive interference

Animation shows the in phase interaction of the s orbitals as they are brought

together

72

Molecular orbital theory of H2 - antibonding

• H2 molecule – interaction of two hydrogen 1s orbitas ( a and b )

Out of Phase

Out of phase interaction (opposite sign) 1s - 1s

2 a b

Destructive interference

Animation shows the out of phase interaction (different colours) of the s

orbitals as they are brought together

73

Charge density associate with MO’s in H2

Overlap

integral = ab d

– In phase interaction enhance density between the atoms

12 a b 2 12 a 2 b 2 2ab

referred to a positive overlap (s bonding) 1 s

22 a b 2 22 a 2 b 2 2 ab

referred to a negative overlap (s* anti-bonding) 2 s *

Energy level diagram for H2

• Interference between AO wave functions bonding

– Constructively bonding interaction

– Destructively anti-bonding interaction

– Two s orbitals interaction to create two molecular orbitals: one is a low

energy bonding and the other high energy anti-bonding

– Electrons fill the lowest energy orbital (same rules as for filling AO’s)

– Bonding energy = 2 E

E

Energy

H H2 H

75

What happens when the AO’s have different energies?

E ( a ) E (b )

– Bonding MO will be much more like the low energy orbital a

– Anti-bonding MO will be much more like high energy orbital b

Energy

s Cas a Cbs b b

contribution of the AO to the MO

a

s s ψ(bonding)

So for ψs Ca Cb

A AB B

76

Linear Combination of Atomic Orbitals - LCAO

• We wrote an equation using coefficients for the contribution of AO’s to the

bonding MO, we can do the same for the anti-bonding MO

s

s Ca a Cb b s

s*

s * Ca a Cb b s*

where the coefficients are different this reflects the contribution to each MO

s s s* s*

Ca Cb Ca Cb

• The sign can be adsorbed into the coefficient and we can write all of the MO’s

in a general way

n=1

1 Ca1 a Cb1b Ca1 0.8, Cb1 0.2

n Can a Cbnb

n=2 2

Ca2 a Cb2b Ca2 0.2, Cb2 0.8

• The coefficients contain information on both phase (sign) of the AO’s and how

big their contribution (size) is to a particular MO

77

LCAO

• Generally we can write

No AO's

n C xx

n

x a...

x = a,b,c …. (all of the AO’s in the molecule) n = 1,2,3…..(the resulting MO’s)

1 1 1 1

• So

MO(2) = 2 Ca a Cb b Cc c Cd d ....

2 2 2 2

the MO’s

78

What interactions are possible ?

• We have seen how s orbitals interact – what about other orbitals

reversing the sign negative overlap Positive Overlap

s – s and px – px -ve

stick to it for all orbitals.

Thus Negative Overlap

pz + pz -ve

pz – pz +ve

i.e. for sigma bond between

p orbital need opposite sign coefficients !

79

What interactions are NOT possible ?

• Some orbitals cannot interact – they give rise to zero overlap

negative overlap (destructive interference) on the other

– Same is true for the other interactions below

Zero overlap

80

An introduction to

Molecular Orbital Theory

Prof S.M.Draper

SNIAMS 2.05

smdraper@tcd.ie

Last lecture

• Hybridisation combining AO’s on one atom to hybrid orbitals

hybridisation made consistent with structure

– LCAO – all AO’s can contribute to a MO

– n AO’s n MO’s

– Filled in same way as AO’s E

– Example of H2 Energy

H H2 H

• Molecular orbitals for AO’s of different energy

– Use of coefficient to describe (i) phase of interaction and (ii) size of

contribution of a given AO No AO's

n C xn x

x a...

82

Labelling molecular orbitals

1) Symmetry Label

s spherical symmetry along the bond axis - same symmetry as s orbital - no

nodes pass through the bond axis (can be at right angles s*)

through the bond axis

dzx + px

through the bond axis

(end on dxy or d x2 y 2 )

83

Labelling molecular orbitals

2) bonding and anti-bonding label (already met this label)

– Nothing if bonding (no nodes between bonded atoms)

s

wavefunction changes sign as you go from one atom to the other.

s*

*

84

Labelling molecular orbitals

3) Is there a centre of inversion ? i.e. is it Centrosymmetric ?

– The final label indicates whether the MO has a centre of inversion

px + px px - px

As you go from one side of Wave function does

wave function through the not change sign

centre of the bond the sign of centrosymmetric

the wavefunction reverses g = gerade or

not centrosymmetric even

u = ungerade or odd

85

2nd row Homonuclear Diatomics

• Li-Li Ne-Ne

s bonding - s and s, pz and pz

bonding - px and px, py and py

86

Objectives – a fundamental understanding

• Wave mechanics / Atomic orbitals

– The flaws in classical quantum mechanics (the Bohr Model) in the

treatment of electrons

– Wave mechanics and the Schrödinger equation

– Representations of atomic orbitals including wave functions

– Electron densities and radial distribution functions

– Understanding shielding and penetration in terms of the energies of

atomic orbitals

• Bonding

– Revision of VSEPR and Hybridisation

– Linear combination of molecular orbitals (LCAO), bonding /

antibonding

– Labelling of molecular orbitals (s, p and g, u)

– Homonuclear diatomic MO diagrams

– MO diagrams for Inorganic Complexes

Energy level diagram for O2

• 2s and 2p energies sufficiently different to give little interaction between each

other – NO MIXING

– Simple picture of the MO Unpaired electrons

*

6s u *

4s u Paramagnetic

2*g 2*g

2p 2p Label MO’s starting from the

1u 1u

bottom although often only

valence orbitals

5sg 3sg

4s*u 2s*u

2s 2s

3sg 1sg Energy difference too big to

interact with valence orbitals

Energy 2s*u 1s AO’s very small very

1s 1s small overlap in lower levels

1sg (small E)

O O

88

Other possible interactions

• Can s interactions between s and pz be important ?

– Depends on energy difference

between s and pz

– If large then no effect

• How does the energy of the 2s and 2p vary with Z (shielding / penetration)

2p No sp mixing

2s

sp mixing

Energy

Li Be B C N O F Ne

89

MO diagram for N2

• 2s and 2p energies sufficiently close for interaction more complex

– 1s and 2s shift to lower energy

– 3s shifted 4s shifted to high energy

– 3s now above 1 4s*u

– levels unaffected

2*g

2p 2p

3sg

1u

2s*u

2s 2s

1sg

90

Making sense of N2

• Take basic model for oxygen – no s p interaction

– Examine how the MO’s can interact

– and s cannot interact – zero overlap level remain the same

– Examine s – s interactions

4s*u Bonding interactions can interact

2*u with each other 1su and 3su

2p 3s

1g

3su

2s*u

1s

goes up in energy

1su

91

Making sense of N2

• Now examine the anti-bonding

interaction (2s* and 4s*) 4s*

4s*u

2*g

2s*

2p

Thus 2s*u goes down in energy and 4s*u

1u goes up in energy

3sg

For bonding with anti-bonding (1s – 4s

2s*u or 2s – 3s) the sign changes on one

wave function zero overlap.

2s

1sg

92

MO diagrams for 2nd row diatomics

• The effect of the overlap between 2s and 2p is greatest for the Li. The MO

diagram changes systematically as you go across the periodic table

93

Homonuclear Diatomic MO energy diagrams

No mixing Mixing

O2 to Ne2 Li2 to N2

4s*u

4s*u

2*g

2p 2*g

1u

3sg

3sg 2p

2p

1u

2s*u

2s

1sg 2s 2s*u

1sg 2s

MO diagram for CO

• Same orbitals as homonuclear diatomics isoelectronic with N2

– different energies give rise to significant 2s - 2p mixing

– As heteronuclear diatomic the orbitals have either C or O character

2p

2p

3s Primarily carbon (pz)

1 bond (uneven – more oxygen)

2s

C

O 1s C-O bonding interaction (more O)

What about triatomic molecules ? MO treatment of BeH2

• VSEPR linear molecule, H – Be – H Z

– Be – 1s2 2s2 2p0 H – 1s1

– Examine interaction of 6 AO with each other

– 2 H 1s, Be 2s and Be 2px, Be 2py Be 2pz 6 MO’s

Each of these is delocalised over three atoms and can hold up to two electrons

96

Energy level diagram for BeH2

4s*u

3s*g

2p

Non bonding px and py

2s

2su

1sg

Be BeH2 2H

Compare these two MO’s with no sp mixing with the localised model of two

Equivalent bonds formed via sp hybridization

97

Alternative approach

• Stepwise approach (ligands first) H – Be – H Z

Mix hydrogen 1s orbitals first

two Molecular orbitals

Be

Be Be

Then mix with s (zero overlap with pz) Then mix with pz (zero overlap with s)

98

Alternative energy level diagram for BeH2

4s*u

3s*g

2s

2su

1sg

Be BeH2 2H

99

An introduction to

Molecular Orbital Theory

in transition metal complexes

Prof. S.M.Draper

SNIAMS 2.5

smdraper@tcd.ie

Last lecture

• LCAO

– Interaction of AO’s with different energy lower AO has bigger

contribution

– Representing contribution as coefficient

– positive, negative and zero overlap

– labelling of MO’s (s / , *, g / u)

– 2s – 2p mixing occurs up to N energy different too big after this (O2, F2)

– Difference in MO diagram for N2 and O2

101

MO treatment of H2O z O

H H

• H2O is not linear – but why ? x

– We will examine the MO’s for a non linear tri-atomic and find out.

– What orbitals are involved – 2 H 1s + O 2s O 2px O 2py and O 2pz

• Taking the in-phase pair first- it will interact with the O 2s and O 2pz (zero overlap

with O 2px and O 2py)

102

MO’s of H2O z O

H H

• Three orbitals three MO’s x

anti - bonding approx. -2pz + H

2pz

approx. 2pz - 2s + H

Approximately

non-bonding +

2s

O 2H

103

MO’s of H2O z O

H H

• Out of phase H 1s orbitals x

– Only interact with px 2 MO’s

– Zero overlap with py

anti - bonding

2px

Bonding

O 2H

104

Energy level diagram for H2O z O

H H

x

H H

2py, n.b.

2p Slightly bonding Pz

s n.b. Non bonding Py

2s

non bonding py Very different to the VB

2s concept of two identical sp3

filled orbital

1s H H

H H

O H2 O 2H

MO theory correct.

105

Comparison of H2O and BeH2

• Both cases of XA2 same MO – different No of electrons

– Bonding MO’s as a function of A-X-A bond angle

BeH2 linear

BH2 131o

CH2 (t) 134o

NH2 103o

OH2 105o

106

MO’s of Benzene

• bonding is more important for reactivity –independent of s (zero overlap)

– six px orbitals combine to form six MO’s

– Lowest energy – all in phase

– Degenerate levels (1 nodal plane 2 nodes)

– Degenerate levels (2 nodal planes 4 nodes)

– Highest energy – all out of phase (3 nodal planes 6 nodes)

– Also the number of nodes on a ring must be even continuous wavefunction

– All coeffcients the same

107

MO’s of Benzene

• Next occupied degenerate pair 1 nodal plane

– Two ways of doing this – between atoms and through a pair of atoms

– As the wavefunction goes through 0 (at the node) the smooth wavefunction

has smaller coefficients next to the node zero at the node

– Compare with Lewis structure with individual double bonds

– With local bonding have to resort to resonance structures to explain benzene

108

MO diagram for CO

• Same orbitals as homonuclear diatomics

– different energies give rise to significant 2s - 2p mixing

– confusing set of orbitals

4s C-O anti - bonding (more C)

2p

2p

3s Primarily carbon (pz)

1 bond (uneven – more oxygen)

2s

1s C-O bonding interaction (more O)

109

The HOMO and LUMO of CO

• For chemical reaction the HOMO (Highest Occupied Molecular Orbital) and

the LUMO (Lowest unoccupied Molecular Orbital) are the most important.

low energy Oxygen orbitals Comes from standard interaction

makes 2s mainly O pz however lower oxygen orbital

in 3s mainly C pz means has has more oxygen and

* more carbon

Some anti-bonding mixes in

due to sp mixing *

3s

C O

C O C O

110

Interaction of the CO 3s with d orbitals

• Three sets of interaction based on symmetry of ligand AO’s

– Generally applicable to s bonding TM ligands

– Interaction with s orbital 1

– With opposite phase – one nodal plane

– Interaction with p orbitals 3

111

Interaction of the CO 3s with d orbitals

• eg ligand phases have two nodal planes

– Interact with d z 2 d x2 y 2 2

– zero overlap (t2g)

112

MO diagram for Tm (s-L)6

t* 1u the ligands fill all the bonding

orbitals

a*1g

e*g and e*g (antibonding)

4s

oct

• Example is d6 – e.g. Co3+

3d t2g

in ligand field theory. Note the e*g

eg 6 s ligand

is anti-bonding !

orbitals

t1u

• The size of oct is important and it

a1g is decided by the interaction

113

interactions with TMs

• Orbitals with character can interact with the t2g d orbitals

– Must be correct symmetry (t2g) 3 arrangements

possible using dxy, dyx, dxz

– Ligand orbitals are low energy and filled (e.g. F)

– Ligand orbitals are high energy and empty (e.g. CO)

high energy low energy

e*g

empty ligand filled ligand

orbitals orbitals

oct

? t2g

? 114

Ligand Orbitals are high energy and empty: High ligand field situation

– Filled orbitals interact in a fashion

– Bonding combinations are reduced in energy (like d orbitals)

– Antibonding combination are raised in energy and empty (like ligand

orbitals)

e*g e*g

oct

oct

t2g

t2g

in oct (box shows the orbitals considered in ligand field theory)

115

Ligand orbitals are low energy and filled: Low ligand field situation

– Filled orbitals interact in a fashion

– Bonding combinations are reduced in energy and filled (like ligand orbitals)

– Antibonding combination are raised in energy and filled (like d orbitals)

e*g e*g

oct

oct

t*2g

t2g

t2g

– Strong interaction with filled orbitals with interaction leads to reduction in Doct

(box shows the orbitals considered in ligand field theory)

116

Tutorial 2 – part a

1. Explain the MO approach for the interaction of

a) two s orbitals of identical energy

b) two s orbitals of slightly different energy

c) two s orbital of very different energy.

a) Draw a Lewis structure for O2

b) Determine the hybridization

c) Perform an MO treatment of O2

(i) What orbitals are involved?

(ii) what interactions are possible?

(iii) what do the resulting MO’s look like?

(iv) sketch an MO energy level diagram.

d) What difference are there in the details of the bonding diagram

between the Lewis and MO treatments

117

Tutorial 2 – part b

3. Consider the molecule BeH2

a) Draw a Lewis structure

b) Determine the hybridization

c) Perform an MO treatment of O2

(i) What orbitals are involved.

(ii) Generate appropriate ‘ligand’ MO’s and interactions with the

central atom

(iii)what do the resulting MO’s look like?

(iv)sketch an MO energy level diagram.

d) What difference are there in the details of the bonding diagram

between the Lewis and MO treatments

4. Perform the same analysis for BeH2, HF, BH3, and CH4

a) The splitting of the d orbitals by sigma interactions with ligands

b) The effect of interaction on the ligand field strength.

118

THE END

119

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