Objectives of the course

• Wave mechanics / Atomic orbitals (AOs)

– The basis for rejecting
j g classical mechanics (the
( Bohr Model)) in treatingg
An introduction to electrons
– Wave mechanics and the Schrödinger equation
Molecular Orbital Theory – Representation
i off atomici orbitals
bi l as wave functions
f i
– Electron densities and radial distribution functions
– Understanding the effects of shielding and penetration on AO energies

6 Lecture Course • Bonding

– Review VSEPR and Hybridisation
Prof G. W. Watson – Linear combination of molecular orbitals (LCAO), bonding / antibonding
Lloyd
Ll d IInstitute
tit t 2.36
2 36 – Labelling
L b lli off molecular
l l orbitals
bi l (MOs) ( π and
(MO ) (σ, d g, u))
watsong@tcd.ie – Homonuclear diatomic MO diagrams – mixing of different AO’s
– More complex molecules (CO,
(CO H2O ….))
– MO diagrams for Inorganic complexes
2

Lecture schedule Literature

Lecture 1 Revision of Bohr model of atoms • Book Sources: all titles listed here are available in the Hamilton Library

Lecture 2 Schrödinger equation, atomic wavefunctions and radial – 1. Chemical Bonding, M. J. Winter (Oxford Chemistry primer 15)
distribution functions of s orbitals Oxford Science Publications ISBN 0 198556942 – condensed text,
excellent diagrams
Lecture 3 More complex wavefunctions and radial distribution
functions and electron shielding
g – 2. Basic Inorganic
g Chemistryy ((Wiley)
y) F.A.Cotton,, G. Wilkinson,, P. L.
Gaus – comprehensive text, very detailed on aufbau principle
Lecture 4 Lewis bonding, Hybridisation, and molecular orbitals
– 3
3. Inorganic
I i Chemistry
Ch i (Prentice
(P i Hall)
H ll) C.
C Housecroft,
H f A.A G.
G Sharpe
Sh –
Lecture 5 Labelling MO’s. 1st row homonuclear diatomics comprehensive text with very accessible language. CD contains
interactive energy diagrams

Lecture 6 MO approach to more complex molecules and CO bonding

in transition metals complexes – Additional sources:
h
http://winter.group.shef.ac.uk/orbitron/
// i h f k/ bi / - gallery
ll off AO
AOs and
d MO
MOs

3 4
 Tutorials
• Expectation
– Tutorials are to g
go through
g pproblems that students are having
g with the
course An introduction to
– Tutorials
i l are NOT forf the
h lecturer
l to give
i you the
h answers to the
h
Molecular Orbital Theory
questions – or to give you another lecture.

– All student must BEFORE the tutorial

• Look at the notes for the course and try to understand them Lecture 1 The Bohr Model
• Attempt the questions set – and hence find out what you can not do!
• Bring a list of questions relating to aspects of the course which you could
not understand (either from looking at the notes or attempting the Prof G. W. Watson
questions) Lloyd Institute 2.05
watsong@tcd.ie
• It is a waste of both the lecturers and students time if the tutorial to ends up
being a lecture covering questions.
5

Adsorption / Emission spectra for Hydrogen Bohr model of the atom (1913)
http://www.youtube.com/watch?v=R7OKPaKr5QM

Johann Balmer (1885) measured line spectra for hydrogen Assumptions

364.6 nm (uv), 410.2 nm (uv), 434.1 nm (violet), 486.1 nm (blue), and 1) Rutherford (1912) model of the atom (Planetary model with central
656.3 nm (red). nucleus + electrons in orbit)

2) Planck (1901),
(1901) Einstein (1905) – the energy electromagnetic waves is
quantised into packets called photons (particle like property).

E = hν
Balmer discovered these lines occur in a series - both absorption and emission -
where ℜ is the Rydberg constant (3.29 ×1015 Hz) Velocity, c Wavelength, λ
Fluctuatting electrric
netic field

⎛ 1 1⎞
v = ℜ⎜⎜ 2 − 2 ⎟⎟
⎝ n1 n2 ⎠
/magn

Balmer series n1=2 and n2=n1+1, n1+2, n1+3 …..

Other series for n1=1
1 (Lyman – UV), n1=3
3 (Paschen – IR) etc.
An stationary observer counts
} i.e. frequency = v Hz , cycles/sec,
ν waves passing per second
Electrons must have specific energies – no model of the atom could explain this sec-1
7 8
 Bohr model of the atom Bohr model of the atom
Speed of electromagnetic waves (c) is constant (ν and λ vary) 3) Electron assumed to travel in circular orbits.

c = ν λ, ν = c / λ, E = h ν, E = h c / λ 4) Apply quantisation to orbits - only orbits allowed have quantised

angular momentum (comes from observation of spectra)
As frequency increases, wavelength decreases. Given λ Æ ν ⎛ h ⎞
mvr = n⎜ ⎟
⎝ 2π ⎠
e g radiowaves:
e.g. λ = 0.1
01m X rays: λ = 1 x 10-12 m
X-rays:
ν = 3 x 109 Hz ν = 3 x 1020 Hz 5) Classical electrodynamical theory rejected (charged particles
E = 2 x 10-24 J E = 2 x 10-13 J undergoing acceleration must emit radiation)

6) Radiation adsorbed or emitted only when electrons jump from one

orbit to another
E – energy (J), h – Plancks constant (J s), ν – frequency (Hz),
ΔE = Ea − Eb
c – speed of light (m-1), λ – wavelength (m)

where a and b represent the energy of the start and finish orbits

9 10

Bohr model – calculating the energy and radius

Bohr model
NOT EXAMANABLE
Electron travelling around nucleus in circular − Ze 2 1
• Energy = − mv 2
orbits – must be a balance between attraction 8πε 0 r 2
to nucleus and flying off (like a planets orbit)
⎛ h ⎞
mvr = n⎜ ⎟
Electron feels two forces – must be balanced • Quantised angular momentum ⎝ 2π ⎠

− Ze 2 − Ze 2
1) Centrapedal (electrostatic) F= PE = − Ze 2 1 − (mvr )2 − n 2 h 2
4πε 0 r 2 4πε 0 r = − mv 2 = = 2 2
• Combining the two 8πε 0 r 2 2mr 2 8π mr
2) Centrafugal mv 2
1
F= KE = mv 2
r 2 r 2 − n 2 h 2 8πε 0 n 2 h 2ε 0
= r=
Equalize magnitude of forces Resulting energy
• Rearranging to give r
r (
8π 2 m − Ze 2 ) πmZe 2

mv 2 Ze 2 Ze 2 1 − Ze 2 − Ze 2 1 − Ze 2 − mZ 2e 4
= ⇒ mv 2
= E = mv 2 + = = − mv 2 • Substitute r into energy gives =
r 4πε 0 r 2 4πε 0 r 2 4πε 0 r 8πε 0 r 2 8πε 0 r 8n 2 h 2ε 02

-Ze – nuclear charge, e – electron charge, ε0- permittivity of free space, • Energy is dependent on n2 and Z2 (2s and 2p the same – only true for 1
r - radius of the orbit, m – mass of electron, v – velocity of the electron electron systems
11 12
 Energy levels of Hydrogen Energy levels of Hydrogen
n=∞
Substitute quantised momentum into energy expression and rearrange n=5
in terms of r (radius) (see previous slide) n=4
F hhydrogen
For d (Z
(Z=1)
1) n=3
n 3
n 2 h 2ε 0 n 2 a0
r= = energy n=2
π mZe 2 Z
− 13.6056 n=1
1
a0 (Bohr) radius of the 1s electron on Hydrogen 52.9 pm (n =1, Z =1) r = n 2 a0 En =
n2
1
Radius ((r)) depends
p on n2 and
Z
n energy (eV) nucleus
Substitute r back into energy expression gives 1 -13.6056
2 4
− mZ e 2 -3.4014
En = 13.6056 × Z 2
2 2 2 = (in eV) 3 -1.5117
8n h ε 0 n2
4 -0.8504
0 8504
Energy of 1s electron in H is 13.6056 eV = 0.5 Hartree (1eV = 1.602 × 10-19 J) 5 -0.3779
1 ∞ 0.0000
Energy (E) depends on and Z2 Note. The spacing reflects the energy
n2 not the radius of the orbit.
Ionization energy = -13.6056 eV
13 14

n=4
Radius of orbits Emission spectra
( p
(http://www.youtube.com/watch?v=5z2ZfYVzefs)
y )

Energy of emission is Einitial - Efinal= hv

For hydrogen (Z=1)

(Z 1) n=3 ⎛ 1 1 ⎞
distance ΔE = 13.6056 ⎜ 2 − 2 ⎟
⎜n ⎟
⎝ inital n final ⎠
− 13.6056
r = n 2 a0 En = n=2
n2 Same form as fitted to emission specta
n=1 Balmer series (Æ nfinal=2) 5 4 3 2 1
n energy (eV) r (pm) nucleus
1 -13.6056 52.9
2 -3.4014
3 4014 211
3 -1.5117 476
n=3 Æ n=2 Æ λ = 656 nm
4 -0.8504
0.8504 847
2 Æ λ = 486 nm
4 Æ n=2
n=4
5 -0.3779 1322
n=5 Æ n=2 Æ λ = 434 nm
∞ 0.0000 ∞
Note The spacing reflects the radius of the
Note.
Note. The spacing reflects the energy
Orbit – not the energy. ℜ = 13.6056 eV / c = 3.29 ×1015 Hz
not the radius of the orbit.
15 16
 Problems with the Bohr Model Wave / particle duality
http://www.youtube.com/watch?v=IsA
p y _oIXdF_8

• Only works for 1 electron systems de Broglie (1923)

– E.g.
g H,, He+, Li2+ Byy this time it was accepted
p that EM radiation can have wave and particle
p
properties (photons)
• Can not explain splitting of lines in a magnetic field
– Modified Bohr-Sommerfield (elliptical orbits - not satisfactory) d Broglie
de li proposedd that
h particles
i l couldld have
h wave properties
i (wave
( /
particle duality). Particles could have an associated wavelength (l)
• Can not apply the model to interpret the emission spectra of complex atoms hc h
E = mc 2 , E = ⇒ λ=
λ mc
• Electrons were found to exhibit wave-like properties
p p
– e.g. can be diffracted as they pass through a crystal (like x-rays) No experimental at time.
– considered as classical particles in Bohr model
1925 Davisson and Germer showed electrons could be diffracted according
to Braggs Law (used for X-ray diffraction)

Numerically confirm de Broglie’s equation

17 18

Wave Mechanics Wave mechanics and atoms

• For waves: it is impossible to determine the position and momentum of the • What does this mean for atoms
electron simultaneously – Heisenberg ‘Uncertainty principle’
• Electrons in “orbits” must have an integer number of
• Use probability of finding an electron from ψ2 (actually ψ*ψ – but functions wavelengths
we will deal with are real)
• E.g. n=4 and n=5 are allowed
Where ψ is is a wave function and a solution of the Schrödinger
g equation
q – These create continuous or standing waves (like on a
(1927). The time-independent form of the Schrödinger equation for the guitar string)
hydrogen atom is:
• E.g. n=4.33 is not allowed
−h 2
−e 2
∂ 2
∂ ∂ 2 2
– The wavefunction is not continuous
∇ Ψ 2
Ψ = EΨ ∇ =
2
+ +
8π m
2
4πε r
0
∂x ∂y ∂z
2 2 2

• The wave nature of electrons brings in the quantized

Kinetic Potential Total nature of the orbital energies.
energy energy energy

19 20
 Atomic solutions of the Schrödinger equation for H Solution of the Schrödinger equation for H
• Schrödinger equation can be solved exactly for 1 electron systems l has values 0 to (n-1) m has values from +l through 0 to –l
– Solved by trial and error manipulations for more electrons

• 3 quantum numbers describing a three dimensional space called an atomic n 1 2 2 2 2

orbital: n, l, m (and spin quantum number describing the electron s)
l 0 0 1 1 1
n = principal quantum number, defines the orbital size with values 1 to ∞ ml 0 0 -1 0 1
Orbital 1s 2s 2p 2p 2p
l= azimuthal or angular momentum quantum number, defines shape.
For a g
given value of n,, l has values 0 to ((n-1).
)
n 3 3 3 3 3 3 3 3 3
ml = magnetic quantum number, defines the orbital orientation. l 0 1 1 1 2 2 2 2 2
F a given
For i value
l off l,
l ml has
h values
l from
f +l through
th h 0 to
t –l.
l
ml 0 -1 0 1 -2 -1 0 1 2

Oribtal 3s 3p 3p 3p 3d 3d 3d 3d 3d

21 22

Last Lecture
• Recap of the Bohr model
– Electrons
An introduction to – Assumptions
– Energies / emission spectra
Molecular Orbital Theory – Radii

• Problems with Bohr model

– Only works for 1 electron atoms
– Can not explain splitting by a magnetic field
Lecture 2 – Representing atomic orbitals - The
Schrödinger equation and wavefunctions. • Wave-particle duality

Proff G
P G. W
W. W
Watson
t • Wave mechanics
Lloyd Institute 2.05 – Schrödinger
watsong@tcd.ie – Solutions give quantum number n, l ml Æ atomic orbitals
n l,

24
 Representations of Orbitals: Polar Coordinates
For an atomic system containing one electron (e.g. H, He+ etc.) • To describe the wavefunction of atomic orbitals we must describe it in
The wavefunction, Ψ, is a solution of the Schrödinger equation three dimensional space
It describes the behaviour of an electron in region of space called an atomic
orbital (φ - phi) • For an atom it is more appropriate to use spherical polar coordinates:

Each orbital wavefunction (φ ) is most easily described in two parts

radial term – which changes as a function of distance from the nucleus
angular
l terms – which
hi h changes
h as a function
f i off angles
l L ti off point
Location i tP

φ xyz= φradial((r)) φangular(φ,

(φ,θ)) = Rnl((r)) Ylm(φ,
(φ,θ)) Cartesian = x, y, z

Æ r, φ, θ
Orbitals have

• SIZE determined by Rnl(r) - radial part

• SHAPE determined byy Ylm(φ(φ,θ)) - angular
g part
p (spherical
(p harmonics))
• ENERGY determined by the Schrödinger equation
java applet on polar coordinates at http://qsad.bu.edu/applets/SPCExp/SPCExp.html
25 26

Wavefunctions for the AO’s of H Radial Wavefunction

General hydrogen like orbitals • R(r) of the 1s orbital of H
it decays exponentially with r
Rnl(r) Ylm(φ,θ) R(r) = 2e (−r ) it has a maximum at r = 0
3 1
⎛Z⎞ 2 ⎛ 1 ⎞ 2 ⎛ 2Z ⎞
1s 2⎜⎜ ⎟⎟ e ( − ρ r 2)
⎜ ⎟ ρ = ⎜⎜ ⎟⎟ • R(r) has no physical meaning
⎝ 4π ⎠
4
⎝ a0 ⎠ ⎝ n a0 ⎠
• Probability depends on R(r)2
3 (1s)2
For hydrogen this simplifies as Z=1 and ao=1 (in atomic units) and thus ρ = 2.

R(r) in a.u.
Hence – Misleading – does not take
Normalisation into account the volume 2
C
Constants are such
h that
h
Rnl(r) Ylm(φ,θ)
– R(r)2 increases toward r = 0
2
∫ ϕ ∂τ = 1
1
1 1s
1s (−r )
2e 2 π – Volume very small so
that is the probability of the electron probability of being at 0
Angular component is a constant p
in an orbital must be 1 when all space small r is small 0 1 2 3 4 5
Æ Spherical is considered Radius (a.u)

27 28
 Radial distribution functions (RDF) Wave functions of 2s and 3s orbitals
• Probability of an electron at a radius r (RDF) is given by probability of an 2s(r) 3s(r)
electron at a point which has radius r multiplied by the volume at a radius of r
3 3
General 1 ⎛Z⎞ 2 1 ⎛Z⎞ 2
⎜ ⎟ ( 2 − ρ r )e ( − ρ r 2)
⎜ ⎟ (6 − 6 ρ r + ( ρ r ) 2 )e ( − ρ r 2)
• Consider a sphere – volume as we move at a small slice is 4πr2 δr 2 2 ⎜⎝ a0 ⎟⎠ 9 3 ⎜⎝ a0 ⎟⎠

⎛ 2Z ⎞ ⎛ 2Z ⎞
– By differentiation, 8 ρ = ⎜⎜ ⎟⎟ ρ = ⎜⎜ ⎟⎟
⎝ n a0 ⎠ ⎝ n a0 ⎠
4 3
the volume of a sphere = πr 6
3 For H 2s Æ Z=1, n=2, ρ =1 3s Æ Z=1, n=3, ρ =2/3
1s

4πr2 R(r))2
∂V
1 ⎡ ⎛ 2 ⎞ ⎤ ( − r / 3)
2
so = 4πr 2 4
1
∂r (2 − r ) e ( −r 2) ⎢6 − 4 r + ⎜ r ⎟ ⎥ e
2 2 9 3 ⎢⎣ ⎝ 3 ⎠ ⎥⎦
2
RDF( ) = 44πr2 R(r)
• RDF(r) R( )2
The form of the wave functions is the important concept – not the precise equation
0
• Maximum for 1s at a0 (like Bohr!) 0 1 2 3 4 5 Note R(r) has functional form
Radius (a.u)
Normalisation constant * polynomial (increasing order with n) * exponential (-r/n)
29 30

Wave functions of Hydrogen 2s and 3s orbitals What does a negative sign mean
1 ⎡ • The absolute sign of a wave function is not important.
⎛ 2 ⎞ ⎤ ( − r / 3)
2
1
For H 2s(r) = (2 − r ) e ( −r 2) For H 3s(r) = ⎢6 − 4 r + ⎜ r ⎟ ⎥ e – The wave function has NO PHYSICAL SIGNIFICANCE
2 2 9 3 ⎢⎣ ⎝ 3 ⎠ ⎥⎦
– the electron density is related to the square of the wave function
exponential decreases more slowly than 1s, e ( − r / n ) Æ more diffuse orbital – This is the same irrespective of the sign
• Wavefunction signs matter when two orbitals interact with each other (see
later)
Wavefunctions changes sign • Some books have the 2s as opposite sign – you can see that the electron
05
0.5
density R(r)2 is the same
R(r) = 0 Æ RADIAL NODE 0.4 2s 0.8
R(r) in a..u.

0.6
03
0.3 04
0.4
2s at (2-r) = 0 (i.e. r=2 a.u.) 0.4

R(r)) in a.u.
R(r) iin a.u.

0.2 0.2 2s
(2s)2
3s changes sign twice with two
R

01
0.1 0
3s 02
0.2
nodes (r =1.9, 7.1 a.u.) -0.2 0 2 4 6 8 10
0 -2s
-0.4
0 2 4 6 8 10 12 14 16
ÆCaused by the order of -0.1
01 -0 6
-0.6 0
the polynomial ! Radius (a.u) -0.8 0 2 4 6 8 10
Radius (a.u) Radius (a.u)
31 32
 Radial Nodes RDF’s of ns orbitals
• Number of radial node = n – l – 1 1s – 1 peak. Maximum at r = a0 - Bohr Model Æ radius of a0
2s – 2 peaks Maximum at r ≈ 5 a0 - Bohr Model Æ radius of 4 a0
1s = 1 – 0 – 1 = 0
3 – 3 peaks
3s k M i
Maximum at r ≈ 13 a00 - Bohr
B h M d l Æ radius
Model di off 9 a0
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 Shape important for orbital energies
8
• Why are there radial nodes ? 1s
– Pauli exclusion principle – no two electrons can have the same set of QN’s 6

R(r)2
– Actually
y – no two electron can overlap
p ((i.e. occupy
py same space)
p ) 4

4πr2 R
2
2s
* 3s
– Overlap integral = ∫ ϕ A ϕ B ∂τ = 0 (analogous to normalisation) 2

AO’s are said to be Orthogonal

0
0 5 10 15 20
– Satisfied for AO’s
AO s with same l by having change(s) in the wave function sign Radius (a.u)
– Satisfied for AO’s with different l angular component ensures no overlap
33 34

Representing atomic orbitals Boundary surface

• Represent orbitals, so far radial and angular terms
• In 2D we can use dot diagrams to look at the whole wave function
– s orbitals have no angular component – spherical symmetry
– Dot diagrams show electron density within a plane – no sign
– Can see where density goes to zero – nodes
– Can see how greater volume as r increases makes most probable
• Represent the wave function in 3D
– Draw a 3D contour at a given value of φ
– Alternatively can define contour such that in enclosed a space which the
electron spends most of its time
– Shows the shape and size of the orbital
– Can not see the inner structure of the wave function
2

distance.
1s Boundary surface
a.u.

3s
R(r) in a

1
1s 2
2s
1

0
0 1 2 3 4 5
Radius (a.u)

35 36
 p orbitals - wavefunctions p orbitals – radial functions
• There are three p orbitals for each value of n (px, py, pz) • Radial wave function for hydrogen p orbitals (Z=1)
– The radial function is the same for all npp orbitals p n=2Æρ=1
for 2p p n = 3 Æ ρ = 2/3
for 3p
– The angular terms are different Æ different shapes (orientations)
– Angular terms are the same for different n Æ 2px, 3px, 4px 1 1 ⎛ 2 r ⎞ 2 r ( − 2r
R(2 p) = re ( −r 2)
R (3 p ) = ⎜4 − ⎟ e
3)
2 6 9 6⎝ 3⎠3
⎛ 2Z ⎞
• Wave function for 2p and 3p orbitals ρ = ⎜⎜ ⎟⎟
R(r) Y(θ φ) ⎝ n a0 ⎠ • Polynomial Æ nodes
1 – Equation for no. of radial nodes 0.2
3 ⎛ 3 ⎞ 2
1 ⎛Z⎞ 2 Y ( p z ) = ⎜ ⎟ cos(θ ) – n – l – 1 Æ 2p =0 , 3p =1 2p
R(2 p) = ⎜ ⎟ ρre ( − ρ r 2)
⎝ 4π ⎠ 0.15
2 6 ⎜⎝ a0 ⎟⎠ 1 – Ensures 2p and 3p orthogonal

R(r)) in a.u.
⎛ 3 ⎞ 2
Y ( p x ) = ⎜ ⎟ sin(θ ) cos(φ ) 0.1
3 ⎝ 4π ⎠ • All p orbitals are multiplied by r
1 ⎛Z⎞ 2 Æ R(r) = 0 at r = 0
⎜⎜ ⎟⎟ (4 − ρr ) ρre ( − ρ r 2) 1 0.05
R (3 p ) = ⎛ 3 ⎞ 2 3p
9 6 ⎝ a0 ⎠ Y ( px ) = ⎜ ⎟ sin(θ ) sin(φ )
⎝ 4π ⎠ • Required
q to match the angular
g function 0
Æ angular node 0 5 10 15 20
Note the functional form of R(r) Æ Constant * polynomial * r * exponential -0.05
Radius (a.u)
37 38

p orbitals – angular functions boundary surfaces p orbitals – RDF’s

1
• All p orbitals have the same shape ⎛ 3 ⎞ 2 • Radial distribution function show probability at a given radius
Y ( pz ) = ⎜ ⎟ cos(θ )
⎝ 4π ⎠
1
• Angular function give rise to direction ⎛ 3 ⎞ 2 • 2p function – no nodes, maximum at r = 4 a0 (same as n=2 for Bohr model)
Y ( px ) = ⎜ ⎟ sin(θ ) cos(φ )
⎝ 4π ⎠ • 3p function – two peaks, maximum at r ≈ 12 a0 (not the same as Bohr)
• Can represent p orbital as dot diagrams or 1
⎛ 3 ⎞ 2
boundary surfaces Y ( px ) = ⎜ ⎟ sin(θ ) sin(φ )
⎝ 4π ⎠ 2.5

2 2p
• 1 angular nodal plane px (yz plane), py (xz plane) pz (xy plane)
1.5
– Ensures that p orbitals are orthogonal
g to s orbitals
2
4πr R((r)

1 3p
2

0.5

0
0 5 10 15 20
Radius ((a.u))

39 40
 Last week
• Solutions of the Schrödinger equation for atoms
– Atomic orbitals (φ)
An introduction to – Defined three quantum number (n, l, ml)

Molecular Orbital Theory • Defined polar coordinates Æ radial and angular terms

• Examined wavefuntions of the s orbitals

Lecture 3 – More complex wave functions, radial distribution – Angular term constant for s orbitals
functions and electron shielding – Wavefunction as constant * polynomial * exponential
– Decays as e ( − r / n ) Æ the larger n the more diffuse the orbital
Revision of Lewis bonding and hybridization – Defined radial nodes and examined there number (polynomial Æn – l -1)
– Discussed the requirement for radial nodes Æ Pauli exclusion principle
Prof G. W. Watson
Lloyd Institute 2.05 • p orbitals
watsong@tcd.ie
t @t d i – Radial functions similar to s orbital (except additional r) Æ R(0) =0
0
– Angular terms define shapes px, py and pz – same for different n
– Radial distribution function for p orbitals
42

d orbitals – wave functions d orbitals – angular functions

• Five d orbitals for each value of n (n ≥ 3) Æ l = 2 , ml = -2, -1, 0, 1, 2 • Angular functions same for d xy , d yz , d xy , d z , d x − y irrespective of n
2 2 2

Æ same shape
p for 3d, 4d, 5d orbitals using g boundaryy surfaces
• Wave functions slightly more complicated (constant * polynomial * r2 * exp) 1
– Radial wave functions same for all 3d orbital Five different angular function e.g. ⎛ 15 ⎞ 2
Y (d xz ) = ⎜ ⎟ sin(θ ) cos(θ ) cos(φ )
3 ⎝ 16π ⎠
1 ⎛Z⎞ 2
R (3d ) = ⎜ ⎟ ( ρr ) 2 e ( − ρ r 2)
9 30 ⎜⎝ a0 ⎟⎠
Two angular nodes planes Æ
orthogonal to s (0) and p (1)
0.1 1.5
• Max probability at r = 9 a0
0.08 3d - RDF
3d - R(r) e.g.
g dxy Nodal p
planes in
R((r) in a.u.

1
• AO’s with 0 nodes have
4πr2 R(r)2

0.06
xy and xz
max probability at same dxy (yz)
0.04
0.5 dz 2

radius as Bohr model

0.02

0 0 (xz)
• 4d orbital has 1 node 0 5 10 15 20
Radius (a.u)

Note the functional form of R(r) Æ Constant * polynomial * r2 * exponential 43 44

 f orbitals Penetration
• Almost no covalent bonding Æ shape not really important • The RDF’s of AO’s within a given principle QN (n) have different shapes

• l = 3 Æ Seven different angular function for each n (n ≥ 4) • Number of nodes n – l - 1

– f block is 14 element wide, same shape for 4f, 5f etc – n=3 3s Æ 2 nodes 3p Æ 1 node 3d Æ 0 nodes
– Radial functions same for all nf orbitals
– Three angular nodes (nodal planes) Æorthogonal to s, p and d orbitals – 3s has a peak very close to the nucleus
– 3p has a peak close to the nucleus 1.5
3p

3d
• These close ppeaks have a veryy strong
g 1
3s

interaction with the nucleus

2
4πr R(r)
2
0.5
• 3s is said to be the most penetrating

0
• Penetration 3s > 3p > 3d 0 5 10 15 20
Radius (a.u)
Note the functional form of R(r) Æ Constant * polynomial * r 3* exponential 45 46

Multi electron atoms Periodic table

• Can nott analytically
C l ti ll solve
l the
th Schrödinger
S h ödi equation
ti for
f multi-electron
lti l t atoms
t
– We assume hydrogen like wave functions for multi-electron atoms • Shielding and penetration Æ E(ns) < E(np) < E(nd) < E(nf)
• Nuclear charge increases with atomic No.
• electrons repel each other and shield the nucleus from other electrons
• This gives rise to electronic configuration of atoms and the order of elements
• Effective nuclear charge Zeff = Z – S in the periodic table
S = a screening or shielding constant
• Electrons are filled in increasing energy (Aufbau principle) and electrons fill
• E.g. Li atom – why is the electronic configuration 1s22s1 and not 1s2 2p1 ? degenerate (same energy) levels singularly first to give maximum spin
8 (Hund’ss rule)
(Hund
– 1s electrons shields the valence
electrons from the nuclear charge
– 2s p
penetrates more effectivelyy
6 1s
• E(4s) < E(3d) 1s 1s
Æ feels a greater nuclear charge K, Ca 2s 2p
2

3s 3p
4πr R(r)

2p
– 2p penetrates less effectively 4
– 2s is filled first 2s 4s 3d
2

2
• E(6s) < E(5d) ≈ E(4f) 6s 5d
• E(1s) < E(2s) < E(2p)
La [Xe] 6s2 5d1
0
• E(ns) < E(np) < E(nd) 0 5 10 C [X
Ce [Xe]] 66s2 4f2 4f
Radius (a.u)

47 48
 More complex results of penetration and shielding
Energy
gy levels vs atomic number
The energy of the 4s and 3d orbitals
• For H (Z=1) all orbitals within a • For K and Ca the E(3d) > E(4s), Sc on the E(3d) < E(4s) (but close)
principle QN have same energy – 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
• For multi electron atoms diagram
ppenetration follows – Result is that TM
TM’ss loose 4s electrons first when ionized
s>p>d>f
Energy 4p {
• 3d shielded very effectively by
orbitals of n ≤ 3 and 3d almost 4p
does not change in energy with Z 3d {
until Z = 19 4
4s

• 4s filled before 3d
4s
• However n = 4 does not shield 3d
effectively Æ energy drops 3d
Increasing Z
• Similar pattern for 4d and 4f K Ca Sc Ti
49 50

Making Bonds
Drawing representations of AO’s Localised Bond Pictures
R i i off JF off Lewis
Revision L i Bonding
B di / VSEPR
• Need to be able to draw AO’s when considering their interactions in MO’s
– So far diagrams
g have been to helpp visualise the 3D nature of AO’s • L
Localised
li d view
i off bonding
b di
– Simple drawings are all you need !!!!! – Views covalent bonds as occurring between two atoms
– Each bond is independent
p 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

Each H has a share of 2

electrons Æ H ─ H

51 52
 Lewis bonding Lewis bonding – polyatomics (H2O)
• Oxygen atom has 6 valence electrons and each hydrogen has 1 electron
• Octet rule for main group elements / 18 electron rule for transition metals
– All atoms have ((or a share of)) 8 electrons ((main)) or 18 electrons (TM)
( )
– Gives rise to noble has configuration ×× ××
2H + × O × H ×O H

×
– Stability since all valence levels filled
×× ××
• Lewis bonding in H2O
• Diatomics ×× ××
– Oxygen y g has 2 electron Æ noble g
yg has 8 electron,, hydrogen gas config.
g
+ × F F × F

××
F

××
×
– F2
– Oxygen – hydrogen interactions share 2 electron Æ H ─ O
×× ××
– Oxygen also has two lone pairs
2 electron shared Æ bond order = 1
F─F
• Shape – VSEPR
– Electrons repel each other (lone pairs repulsion > than bonding pairs)
– O2 ×× ××
×O × × – Oxygen has 2 bond pairs and 2 lone pairs Æ 4 directions to consider
O + O × O
×× ×× – Accommodate 4 directions Æ Tetrahedral shape p
– H2O is bent with H-O-H angle of 104.5 o
4 electron shared Æ bond order = 2
O═O – Compares with a perfect tetrahedral of 109.45o Æ lone pair repulsion
53 54

Lewis bonding – polyatomics (ethene) Lewis structures – breaking the octet rule
• Used different symbols for electrons on adjacent atoms • Some structures to not obey the 8 electron rule.
– e.g
g PF5
×× H H 90o
F F
4H + 2× C × C ×× C
×
H H F
F × P F F P 120o

×
Carbon atoms share 4 electron Æ bond order = 2 Æ C ═ C × ×
F F F
Carbon –hydrogen interactions share 2 electrons Æ C ─ H
F
• Shape – VSEPR (only the electrons round the P are shown for clarity)
– Electrons repel each other
– Carbon atoms have 3 directions – bond to C and two bonds to H – F atoms have 3 lone pairs (6 electrons) + 2 in each bond Æ 8
– Accommodate 3 bond direction Æ 120o in a plane (molecule is flat) – P atom has 5 bond pairs with 2 electrons each Æ 10 electrons !

55 56
 TUTORIAL 1
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 An introduction to
n?
3 Draw sketches to represent the following for 3s
3. 3s, 3p and 3d orbitals
orbitals. Molecular Orbital Theory
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 Lecture 4 Revision of hybridisation
a) Explain what the terms penetration and shielding mean. Molecular orbital theory and diatomic molecules
b) How do these concepts help to explain the structure of the periodic
table
Proff G. W. Watson
5. Sketch the d orbitals as enclosed surfaces, showing the signs of the Lloyd Institute 2.05
wavefunction.
watsong@tcd.ie
g@
6. What does the sign of a wavefuntion mean ?

57

Last lecture Valence bond theory and hybridisation

• d orbitals • Valence bond theory (Linus Pauling)
– Radial wavefunctions, nodes and angular wavefunctions (shapes) – Based on localised bonding
– Hybridisation to give a geometry which is consistent with experiment.
• f orbitals – Hybridisation constructs new hybrid atomic orbitals from the AO’s
– Radial wavefunctions,
wavefunctions nodes and angular wavefunctions (shapes)

• Multielectron atoms • Use Lewis model (number of electron pairs) Æhybridisation Æ shape.
– Penetration and shielding – E.g. BeH2, Be – 1s2 2s2
– Atomic orbital energies, filling and the periodic table
H × Be H

×
• Valence bond theory (localised electron pairs forming bonds)
– Lewis structures Æ number of electron pairs
Æ bond order (electrons shares divided by 2) • Correctly predicted by VSEPR to be linear – can we explain it using AO’s
– VSEPR Æ repulsion of electron pairs (BP and LP) – Mix S with pz orbital Æ 2 sp hybridized orbitals
Æ molecular shape

59 60
 sp hybridisation Hybridisation – sp2 hybridisation
• sp hybridisation • Lewis structure Æ 3 directions
– Mix and a s and a p orbital – two combinations s + pz and s – pz
– Two AO’s Æ two hybrid AO’s
H H
– Relative sign is important when mixing orbitals
– sp therefore means that the hybrid orbital is 50% s and 50% p C ×× C
H H
ψ sp =
1
2
(ϕ 2s + ϕ 2 p z
) + • Molecular is planar

• Three directions each

ψ sp =
1
2
(ϕ 2s − ϕ 2 p z
) + at 120o

Æ mix s with 2 p orbitals

Æ sp2 hybridisation
= -
61 62

Hybridisation – π bonds Hybridisation – sp3

• For ethene sp2 hybridisation Æ bonding in three directions • 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
x
C
H H
– Each local bond can hold 2 electrons z 4 electron pairs sp3 hybridisation tetrahedral
– Have not accounted for the second pair of electron shared by the C atoms
– H2O can also
l beb thought
th ht off like
lik this
thi with
ith two
t off the
th
• Creates a π bond above and below the plane of the molecule 3
sp orbitals occupied by lone pairs.
– Could think of the C as going from s2 p2 Æ (sp2)3 px1
××
H × O H
×

××
4 electron pairs sp3 hybridisation tetrahedral
63 64
 Hybridisation – d orbitals Hybridisation – summary
Trigonal Bipyramidal Lone pairs equatorial
sp3d Æ 5 electron pairs Hybrid Atomic orbitals Geometry General Examples
(s d 2)
( + px + py + pz + dz isation that are mixed formula

spp s+p linear AB2 BeH2

AB3 BF3, CO32-
sp2 s + px + py trigonal planar
C2H4
SO42-, CH4,
sp3 s + px + py + pz tetrahedral AB4
NH3, H2O,
octahedra
sp3d2 Æ 6 electron pairs sp3d s + px + py + pz + dz2 Trigonal Bipyramidal AB5 PCl5, SF4
(s+ px+ py+ pz+ dz2+ dx2-y2)
s + px + py + pz + dx2-y2 square pyramidal

SF6
sp3d2 s + px + py + pz + dz2 + dx2-y2 octahedral AB6 [Ni(CN)4]2-
[PtCl4]2-

Lone pairs trans 65 66

Molecular orbital theory Molecular orbital theory of H2 - bonding

• Molecule orbital theory (Robert

Robert Mullikan) • H2 molecule – interaction of two hydrogen 1s orbitals ( ϕ a and ϕ b )

In Phase
• Electrons are delocalised In phase interaction (same sign)
1s + 1s
– Different to Lewis and hybridisation (these are not MO) ψ 1 = (ϕ a + ϕ b )
Æ Constructive interference
– Molecular orbitals are formed which involve all of the atoms of the
molecule

Animation shows the in phase interaction of the s orbitals as they are brought
– Molecular orbital are formed by addition and subtraction of AO
AO’ss together

Æ Linear Combination of Atomic Orbitals (LCAO)

( )

– like hybrid AO’s but the MO involves the whole molecule

67 68
 Molecular orbital theory of H2 - antibonding Charge density associate with MO’s in H2
• H2 molecule – interaction of two hydrogen 1s orbitas ( ϕ a and ϕ b ) • In phase interaction - charge density given by ψ2

ψ 12 = (ϕ a + ϕ b )2
Ö ψ 12 = [ϕ a ]2 + [ϕ b ]2 + 2[ϕ aϕ b ]
Out of Phase
Out of phase interaction (opposite sign) 1s - 1s

ψ 2 = (ϕ a − ϕ b ) – This gives an enhanced density where the AO’s overlap between the atoms
Æ Destructive interference – referred to as positive overlap and pull the atoms together (σ bonding) ψ 1 = ψ σ

Node between the atoms

• Out of phase interaction
Animation shows the out of phase interaction (different colours) of the s
y are brought
orbitals as they g together
g ψ 22 = (ϕ a − ϕ b )2
Ö ψ 22 = [ϕ a ]2 + [ϕ b ]2 − 2[ϕ aϕ b ]

– This leads to reduced density between the atoms ψ 2 =ψσ *

– referred to as negative overlap and pushes the atoms apart (σ* anti-bonding)

• C
Can nott create
t electrons
l t Æ New
N wave ffunctions
ti mustt be
b normalised
li d to
t ensure
probability in 1 !
Interaction of 2 AO Æ 2 MO’s – A general rule is that n AO Æ n MO’s
69 70

Energy level diagram for H2 What happens when the AO’s have different energies?
• Interference between AO wave functions Æ bonding
• Hypothetical molecule where the two s orbitals have different energies
– Constructively Æ bonding interaction
E (ϕ a ) < E (ϕ b )
– Destructively Æ anti-bonding interaction
• What would the MO’s be like
– Bonding
B di MO will ill be
b muchh more like
lik the
th low bit l ϕ a
l energy orbital
• Energy level diagram represents this interaction – Anti-bonding MO will be much more like high energy orbital ϕ b
– Two s orbitals interaction to create a low energy bonding and high energy
anti-bonding molecular orbital • We can say that the bonding MO is ψ(anti-bonding)
Energy
– Electrons fill the lowest energy orbital (same rules as for filling AO’s)
– Bonding energy = 2 ΔE
(
ψ σ = Caσ ϕ a + Cbσ ϕ b ) ϕb

• Where the coefficients C, indicate the

contrib tion of the AO to the MO
contribution
ΔE ϕa
σ σ ψ(bonding)
Energy
gy So for ψσ Ca > Cb

H H2 H A AB B
71 72
 Linear Combination of Atomic Orbitals - LCAO LCAO
• We wrote an equation using coefficients for the contribution of AO’s to the • Generally we can write
bonding MO, we can do the same for the anti-bonding MO No AO 's
ψn = C xnϕ x
( )
∑
(
ψ σ = Caσ ϕ a + Cbσ ϕ b ) σ*
ψ σ * = Ca ϕ a − Cb ϕ b σ* x = a...

where the coefficients are different are reflect the contribution to each MO x = a,b,c
a b c …. (all of the AO
AO’ss in the molecule) n = 11,2,3…..(the
2 3 (the resulting MO
MO’s)
s)
* *
Caσ > Cbσ Caσ < Cbσ
1 1 1 1
• So MO(1) = ψ 1 = Caϕ a + Cbϕ b + Ccϕ c + Cd ϕ d + ....
• The sign can be adsorbed into the coefficient and we can write all of the MO’s
in a general way 2 2 2 2
MO(2) = ψ 2 = Ca ϕ a + Cb ϕ b + Cc ϕ c + Cd ϕ d + ....
n=1 ψ1 = (
Ca1ϕ a + Cb1ϕ b ) Ca1 = 0.8, Cb1 = 0 .2
(
ψ n = Canϕ a + Cbnϕ b ) MO(3) = ψ 3 = Ca3ϕ a + Cb3ϕ b + Cc3ϕ c + Cd3ϕ d + ....

n=2 (
ψ 2 = Ca2ϕ a + Cb2ϕ b ) Ca2 = 0.2, Cb2 = −0.8
C1x - coefficients for MO(1), C x2 - coefficients for MO(2) etc.

• The coefficients contains both phase (sign) of the AO’s and how big their • And an examination of the coefficients tells us the bonding characteristics of
contribution (size) is to a particular MO the MO’s
73 74

What interactions are possible What interactions are NOT possible

• We have seen how s orbitals interact – what about other orbitals • Some orbital can not interact – they give rise to zero overlap

• If you have positive overlap • Positive overlap (constructive interference) on one side in cancelled by
reversing the sign Ænegative overlap negative overlap (destructive interference) on the other
Positive
os ve Overlap
Ove p

E.g. s + s and px + px Æ +ve • s + px positive overlap above the axis is cancelled by negative overlap below
s – s and px – px Æ -ve
ve – Same is true for the other interactions below

• Must define orientation and

stick to it for all orbitals.
Thus Zero overlap
Negative
g Overlap
p
pz + pz Æ -ve
pz – pz Æ +ve
i e for sigma bond between
i.e.
P orbital need opposite sign coefficients !
75 76
 Last lecture
• Hybridisation Æ combining AO’s on one atom to Æ hybrid orbitals
Æ hybridisation
y made consistent with structure
An introduction to
Molecular Orbital Theory • Molecular orbital theory (delocalised view of bonding)
– LCAO – all AO’s can contribute to a MO
– n AO’s Æ n MO’s
– Filled in same way as AO’s ΔE
– Example of H2 Energy
Lecture 5 Labelling MO’s. 1st row homonuclear diatomics
H H2 H
• Molecular orbitals for AO’s of different energy
Prof G. W. Watson
Lloyd Institute 2.05 • Linear Combination of Atomic Orbitals (LCAO)
watsong@tcd.ie – Use of coefficient to describe (i) phase of interaction and (ii) size of
contribution
ib i off a given
i AO No AO 's
ψ n = ∑ C xnϕ x
x = a...
78

Labelling molecular orbitals Labelling molecular orbitals

1) Symmetry of bonding
2) bonding and anti-bonding (already met this label)
σ = spherical symmetry along the bond axis - same symmetry as s orbital no
nodes pass through the bond axis (can be at right angles Æ σ*) – Nothingg if bondingg ((no nodes between bonded atoms))

σ
π

π = one nodal plane which passes

through the bond axis
– Additional * if a nodal p
plane exits between the atoms,, that is if the
dzx + px wavefunction changes sign as you go from one atom to the other.

σ*
σ
δ = two nodal plane which pass π*
through the bond axis
(end on dxy or d x 2 − y 2 )
79 80
 Labelling molecular orbitals 2nd row homonuclear diatomics
3) Is there a centre of inversion ? i.e. is it Centrosymmetric ? • Li-Li Æ Ne-Ne
– The final label indicated whether the MO has a centre of inversion symmetry
y y
– Possible interactions between 1s, 2s and 2p
px + px px - px
As you go from one side of Wave function does σ bonding s – s, pz – pz π bonding px – px, py - py
wave function through the not change sign
centre of the bond the sign
g of Æ centrosymmetric
y
the wavefunction reverses Æ g = gerade or
Æ not centrosymmetric even
Æ u = ungerade or odd

• MO e g σs or σp
MO’ss sometimes labelled with the type of AO forming them e.g.

81 82

Energy level diagram for O2 Other possible interactions

• Will σ interactions between s and pz be important
• 2s and 2p energies sufficiently spaced to give little interaction
– Depends on energy difference
– Simple
p picture
p of the MO
U i d electrons
Unpaired l t b t
between s and
d pz
6 σ∗ u 4σ∗u ÆParamagnetic – If large then no effect
2π∗g 2π∗g
2p 2p Label MO’s starting from the
1πu bottom although often only
1πu • How does the energy of the 2s and 2p vary with Z (shielding / penetration)
valence orbitals
5σg 3σg 2p No sp mixing
4 σ∗ u 2σ∗u 2s
2s 2s
3 σg 1σg Energy difference too big to
interact with valence orbitals sp mixing
i i
Energy 2 σ∗ u Energy
1s AO’s very small Æ very
1
1s 1
1s Li Be B C N O F Ne
small
ll overlap
l ini lower
l levels
l l
1 σg (small ΔE) • Gap increases – 2p more effectively shielded - critical point between O and N
O O
83 84
 MO diagram for N2 Making sense of N2
• Take basic model for oxygen – no s p interaction
• 2s and 2p energies sufficiently close for interaction Æ more complex – Examine how the MO’s can interact
– 1σ and 2σ shift to lower energygy – π and σ can not interact – zero overlap Æ π level remain the same
– 3σ shifted 4σ shifted to high energy – Examine σ – σ interactions
– 3σ now above 1π 4 σ∗ u 4σ∗u Bonding interactions can interact
– π levels unaffected 2π∗ with each other 1σu and 3σu
u
2π∗g
2
2p 3σ
2p 2p
3σg
1πg
1 πu
3σu

2σ∗u
1
1σ
2 σ∗ u
2s 2s 2s Thus 1σu goes down in energy and 3σu
1 σg goes up in energy
1σu
85 86

Making sense of N2 MO diagrams for 2nd row diatomics

• The effect of the overlap between 2s and 2p is greatest for the Li. The MO
• Now examine the anti-bonding
4σ* diagram changes systematically as you go across the periodic table
interaction (2σ and 4σ)

4σ∗u
2π∗u
2σ*
2
2p
Thus 2σ∗u goes down in energy and 4σ∗u
1πg goes up in energy
3σu
For bonding with anti-bonding (1σ – 4σ
or 2σ – 3σ) the sign changes on one
2σ∗u
wave function Æ zero overlap.

2s
• s – p mixing Æ B2 – paramagnetic and C2 diamagnetic
1σu
87 88
 MO treatment of BeH2 Energy level diagram for BeH2
• VSEPR Æ linear molecule, H – Be – H Z 4σ*u
– 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 Æ 6 MO’s 3σ*g

2
2p
Interaction between H 1s and Be 2s Interaction between H 1s and Be 2pz Non bonding px and py

2s
bonding 2σu
anti-bonding
i b di b di
bonding anti-bonding

1σg
Be BeH2 2H
Each of these is delocalised over three atoms and can hold up to two electrons
Compare these two MO’s with no sp mixing with the localised model of two
px and py have zero overlap Æ non bonding Equivalent bonds formed via sp hybridization
89 90

Alternative approach Alternative energy level diagram for BeH2

• Step wise approach (ligands first) H – Be – H Z
Mix hydrogen 1s orbitals first
4σ*u
Æ two Molecular orbitals
Be
33σ*g

Be Be 2p Non bonding px and py

Then mix with s (zero overlap with pz) Then mix with pz (zero overlap with s)
2s
2σu

1σg
Be BeH2 2H

91 92
 Last lecture

• LCAO

An introduction to – Interaction
I i off AO’s
contribution
AO’ withi h different
diff energy Æ lower
l AO hhas bi
bigger

Molecular Orbital Theory – Representing

p g contribution as coefficient

• AO interactions that were possible Æ MO’s

– positive, negative and zero overlap
– labelling of MO’s (σ / π , *, g / u)
Lecture 6 More complex molecules and CO bonding
in transition metal complexes
• 2nd row homo nuclear diatomics
– 2s – 2pp mixingg occurs upp to N Æ energy
gy different too bigg after this (O
( 2, F2)
Prof G.
G W.
W Watson
– Difference in MO diagram for N2 and O2
Lloyd Institute 2.05
watsong@tcd.ie
g@ • Molecular orbital treatment of BeH2

94

MO treatment of H2O z O MO’s of H2O z O

H H H H
• H2O is not linear – but why ? x • Three orbitals Æ three MO’s x
– We will examine the MO’s for an non linear tri-atomic and find out. anti - bonding approx -2
approx. 2p z + H
– What orbitals are involved – 2 H 1s + O 2s O 2px O 2py and O 2pz

• Lets start by creating MO

MO’ss from the hydrogen 1s orbitals.
orbitals

2pz
approx. 2pz - 2s + H
Approximately
• Taking
g the in pphase ppair first- it will interact with the O 2s and O 2ppz ((zero overlapp g
non-bonding +
with O 2px and O 2py) 2s

Bonding approx. 2s + 2pz (a little) + H

O 2H
• Problem - This is mixing three orbitals Æ must produce three orbital
95 96
 MO’s of H2O z O Energy level diagram for H2O z O
H H H H
• Out of phase H 1s orbitals x x
– Only y interact with px Æ 2 MO’s
There are not two lone pairs !
– Zero overlap with py

H H
anti - bonding 2py, n.b.
2p Slightly bonding Pz
σ n.b. Non bonding Py
2σ
non bonding
b di py Very different to the VB
2s concept of two identical sp3
filled orbital
2ppx
1σ H H

H H
Bonding O H2O 2H
O 2H MO theory correct.
97 98

Comparison of H2O and BeH2 π MO’s of Benzene

• Both cases of XA2 Æ same MO – different No of electrons • π bonding is more important for reactivity –independent of σ (zero overlap)
– Bonding MO’s as a function of A-X-A bond angle – six px orbitals Æ combine to form six MO’s

• Different ways of arranging six px orbitals on a ring

– Lowest
owes energy
e e gy – aall in phase
p ase
BeH2 linear – Degenerate levels (1 nodal plane Æ 2 nodes)
– Degenerate levels (2 nodal planes Æ 4 nodes)
BH2 131o – Highest energy – all out of phase (3 nodal planes Æ 6 nodes)
CH2 (t) 134o
– Energy increases with number of nodes – as in AO’s
CH2 (s) 102o
– Also the number of nodes on a ring must be even Æ continuous wavefunction
NH2 103o
• Lowest energy all in phase
OH2 105o – All coeffcients the same

90º H2O CH2(T) 180º

99 100
 π MO’s of Benzene MO diagram for CO
• Next occupied degenerate pair Æ 1 nodal plane
– Two ways of doing this – between atoms and through a pair of atoms • Same orbitals as homo nuclear diatomics
– different energies
g ggive rise to significant
g 2s - 2pp mixing
g
– confusing set of orbitals
4σ C-O anti - bonding (more C)

2π∗ π∗ (uneven – more carbon)

2p
2p
– As the wavefunction goes through 0 (at the node) the smooth wavefunction 3σ Primarily carbon (pz)
has smaller coefficients next to the node zero at the node
1π π bond (uneven – more oxygen)

• 2 electron per MO spread over 6 atoms

– Compare with Lewis structure with individual double bonds 2s 2σ Primarily oxygen (pz)
– With local bonding have to resort to resonance structures to explain benzene 2s
1σ C-O bonding interaction (more O)
101 102

The HOMO and LUMO of CO Interaction of the CO 3σ with d orbitals

• For chemical reaction the HOMO (Highest Occupied Molecular Orbital) and • Three sets of interaction based on symmetry of ligand AO’s
the LUMO (Lowest unoccupied Molecular Orbital) are the most important. – Generallyy applicable
pp to σ bonding
g TM ligands
g

HOMO – 3σ LUMO – 2π* • a1g all ligand AO’s in phase

l energy Oxygen orbitals
low bi l Comes from
f d d π interaction
standard i i – Interaction with s orbital Æ 1
makes 2σ Æ mainly O pz however lower oxygen orbital
Æ in 3σ mainly C pz means π has has more oxygen and – t1u ligands in one axis contribute
π* more carbon – With opposite phase – one nodal plane
Some anti-bonding mixes in – Interaction with p orbitals Æ 3
due to sp mixing π π∗
3σ
C O

C O C O
103 104
 Interaction of the CO 3σ with d orbitals MO diagram for Tm (σ-L)6
• eg ligand phases have two nodal planes
• Electrons from filled σ orbitals on
– Interact with d z 2 d x 2 − y 2 Æ 2 t*1u the ligands fill all the bonding
orbitals
a*1g

4p • d electrons fill t2g (non bonding)

e*g and e*g (antibonding)
4s
Δoct
• Example is d6 – e.g. Co3+
3d t2g

• Three remaining d orbitals point between ligands • These are the orbitals considered
in ligand filed theory. Note the e*g
– zero overlap (t2g) eg 6 σ ligand
is anti-bonding !
orbitals
t1u
• What really decided Δoct is the π
a1g interaction

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π interactions with TMs Low ligand field situation

• Li
Ligandd orbitals
bi l are low
l energy andd filled
fill d (e.g.
( F)
• Orbitals with π character can interact with the t2g d orbitals – Filled orbitals interact in a π fashion
– Must be correct symmetry (t2g) Æ 3 arrangements – Bondingg combinations are reduced in energy gy and filled (like
( ligand
g orbitals))
possible using dxy, dyx, dxz – Antibonding combination are raised in energy and filled (like d orbitals)

• Two extreme situations e*g e*g

– Ligand orbitals are low energy and filled (e.g. F)
Δoct
– Ligand orbitals are high energy and empty (e.g.
(e g CO) Δoct
t*2g
Interaction with Interaction with t2g
high energy l energy
low
e*g
empty ligand filled ligand
orbitals t2g
Δoctt orbitals

? t2g
? 107
without π with π ligand

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

Δoct (box shows the orbitals considered in ligand field theory)
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 High ligand field situation Tutorial 2 – part a
• Ligand orbitals are high energy and empty (e.g. CO 2π*)
1. Explain the MO approach for the interaction of
– Filled orbitals interact in a π fashion
a)) two s orbitals of identical energy
gy
– Bonding
B di combinations
bi ti are reduced
d d ini energy (like
(lik d orbitals)
bit l )
– Antibonding combination are raised in energy and empty (like ligand b) two s orbitals of slightly different energy
orbitals) c) two s orbital of very different energy.

e*g e*g 2. Consider the bonding in the molecule O2

a) Draw a Lewis structure for O2
Δoct
Δoct b) Determine the hybridization
c)) Perform an MO treatment of O2
t2g
(i) What orbitals are involved?
t2g (ii) what interactions are possible?
without π with π ligand (iii) what do the resulting MO’s look like?
(iv) sketch an MO energy level diagram.
– St
Strong interaction
i t ti with
ith empty
t orbitals ith π interaction
bit l with i t ti leads
l d to
t increase
i d) What difference are there in the details of the bonding diagram
in Δoct (box shows the orbitals considered in ligand field theory) between the Lewis and MO treatments
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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.
involved
(ii) Generate appropriate ‘ligand’ MO’s and interactions with the
central atom
(iii) h ddo the
(iii)what h resulting
l i MO’s
MO’ look
l k like?
lik ? THE END
(iv)sketch an MO energy level diagram.
d)) What difference are there in the details of the bondingg diagram
g
between the Lewis and MO treatments

4 Perform the same analysis for BeH2, HF,

4. HF BH3, and CH4

5. Use molecular orbital theory to explan

a) The splitting of the d orbitals by sigma interactions with ligands
b) The effect of π interaction on the ligand field strength.
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