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Wave mechanics / Atomic orbitals (AOs) The basis for rejecting classical mechanics (the Bohr Model) in treating j g ( ) g electrons Wave mechanics and the Schrdinger equation Representation of atomic orbitals as wave functions i f i bi l f i 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 L b lli of molecular orbitals (MOs) (, and g, u) Labelling f l l bi l (MO ) ( d ) Homonuclear diatomic MO diagrams mixing of different AOs More complex molecules (CO, H2O .) (CO ) MO diagrams for Inorganic complexes
2
6 Lecture Course
Prof G. W. Watson Lloyd Institute 2 36 Ll d I tit t 2.36 watsong@tcd.ie
Lecture schedule
Lecture 1 Lecture 2 Revision of Bohr model of atoms Schrdinger equation, atomic wavefunctions and radial distribution functions of s orbitals More complex wavefunctions and radial distribution functions and electron shielding g Lewis bonding, Hybridisation, and molecular orbitals Labelling MOs. 1st row homonuclear diatomics MO approach to more complex molecules and CO bonding in transition metals complexes
Literature
Book Sources: all titles listed here are available in the Hamilton Library 1. Chemical Bonding, M. J. Winter (Oxford Chemistry primer 15) Oxford Science Publications ISBN 0 198556942 condensed text, excellent diagrams 2. Basic Inorganic Chemistry ( g y (Wiley) F.A.Cotton, G. Wilkinson, P. L. y) , , Gaus comprehensive text, very detailed on aufbau principle 3 Inorganic Chemistry (Prentice Hall) C. Housecroft, A. G. Sharpe 3. I i Ch i (P i H ll) C H f A G Sh comprehensive text with very accessible language. CD contains interactive energy diagrams Additional sources: http://winter.group.shef.ac.uk/orbitron/ - gallery of AO and MO h // i h f k/ bi / ll f AOs d MOs
3 4
Lecture 3
Tutorials
Expectation Tutorials are to go through p g g problems that students are having with the g course Tutorials are NOT for the lecturer to give you the answers to the i l f h l i h h 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 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 questions)
It is a waste of both the lecturers and students time if the tutorial to ends up being a lecture covering questions.
5
Assumptions 1) Rutherford (1912) model of the atom (Planetary model with central nucleus + electrons in orbit) 2) Planck (1901), Einstein (1905) the energy electromagnetic waves is (1901) quantised into packets called photons (particle like property). E = h
Fluctuat ting electr ric /magn netic field Velocity, c Wavelength,
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 n n 1 2
Balmer series n1=2 and n2=n1+1, n1+2, n1+3 .. Other series for n1=1 (Lyman UV), n1=3 (Paschen IR) etc. 1 3 Electrons must have specific energies no model of the atom could explain this
7
An stationary observer counts } i.e. frequency = v Hz , cycles/sec, waves passing per second sec-1
8
h mvr = n 2 5) Classical electrodynamical theory rejected (charged particles undergoing acceleration must emit radiation) Radiation adsorbed or emitted only when electrons jump from one orbit to another
E = Ea Eb
6)
E energy (J), h Plancks constant (J s), frequency (Hz), c speed of light (m-1), wavelength (m)
where a and b represent the energy of the start and finish orbits
9 10
Bohr model
Electron travelling around nucleus in circular orbits must be a balance between attraction to nucleus and flying off (like a planets orbit) Electron feels two forces must be balanced 1) Centrapedal (electrostatic) 2) Centrafugal
F= Ze 2 4 0 r 2 PE = Ze 2 4 0 r
h mvr = n 2
F=
mv r
Ze 2 (mvr )2 n 2 h 2 1 = mv 2 = = 2 2 8 0 r 2 2mr 2 8 mr
r 2 n 2 h 2 8 0 = r 8 2 m Ze 2
1 KE = mv 2 2
Resulting energy
1 Ze 2 Ze 2 1 E = mv 2 + = = mv 2 2 4 0 r 8 0 r 2
Rearranging to give r
r=
n 2 h 2 0 mZe 2
mv 2 Ze 2 Ze 2 = mv 2 = r 4 0 r 4 0 r 2
Ze 2 mZ 2e 4 = 2 8 0 r 8n 2 h 2 0
-Ze nuclear charge, e electron charge, 0- permittivity of free space, r - radius of the orbit, m mass of electron, v velocity of the electron
11
Energy is dependent on n2 and Z2 (2s and 2p the same only true for 1 electron systems
12
r=
n 2 h 2 0 mZe 2
n 2 a0 Z
a0 (Bohr) radius of the 1s electron on Hydrogen 52.9 pm (n =1, Z =1) 1 Radius (r) depends on n2 and () p Z Substitute r back into energy expression gives
En = mZ e 13.6056 Z 2 (in eV) 2 2 2 = 8n h 0 n2
2 4
n 1 2 3 4 5
nucleus
Energy of 1s electron in H is 13.6056 eV = 0.5 Hartree (1eV = 1.602 10-19 J) Energy (E) depends on
1 and Z2 n2
13
Note. The spacing reflects the energy not the radius of the orbit.
14
Radius of orbits
For hydrogen (Z=1) (Z 1) distance
r = n 2 a0
Emission spectra
( p (http://www.youtube.com/watch?v=5z2ZfYVzefs) y )
hv
En =
1 1 E = 13.6056 2 2 n inital n final Same form as fitted to emission specta Balmer series ( nfinal=2)
5 4 3 2 1
n=2 n=1
n 1 2 3 4 5
energy (eV) -13.6056 -3.4014 3 4014 -1.5117 -0.8504 0.8504 -0.3779 0.0000
nucleus
de Broglie (1923) By this time it was accepted that EM radiation can have wave and particle y p p properties (photons)
de d Broglie proposed that particles could have wave properties (wave / li d h i l ld h i ( particle duality). Particles could have an associated wavelength (l)
E = mc 2 , E =
No experimental at time.
hc
h mc
1925 Davisson and Germer showed electrons could be diffracted according to Braggs Law (used for X-ray diffraction) Numerically confirm de Broglies equation
17 18
Wave Mechanics
For waves: it is impossible to determine the position and momentum of the electron simultaneously Heisenberg Uncertainty principle Use probability of finding an electron from 2 (actually * but functions we will deal with are real) Where is is a wave function and a solution of the Schrdinger equation g q (1927). The time-independent form of the Schrdinger equation for the hydrogen atom is:
h 8 m
2 2 2
e = E 4 r
2
0
=
2
+ + x y z
2 2 2 2
Kinetic energy
Potential energy
Total energy
19
The wave nature of electrons brings in the quantized nature of the orbital energies.
20
n l ml Orbital n l ml Oribtal 3 0 0 3s
1 0 0 1s 3 1 -1 3p 3 1 0 3p 3 1 1 3p
2 0 0 2s 3 2 -2 3d
2 1 -1 2p 3 2 -1 3d
2 1 0 2p 3 2 0 3d 3 2 1 3d
2 1 1 2p 3 2 2 3d
ml = magnetic quantum number, defines the orbital orientation. For i F a given value of l ml h values from +l th l f l, has l f through 0 to l. h t l
21
22
Last Lecture
Recap of the Bohr model Electrons Assumptions Energies / emission spectra Radii Problems with Bohr model Only works for 1 electron atoms Can not explain splitting by a magnetic field Wave-particle duality Wave mechanics Schrdinger Solutions give quantum number n l ml n, l, atomic orbitals
24
Representations of Orbitals:
For an atomic system containing one electron (e.g. H, He+ etc.) The wavefunction, , is a solution of the Schrdinger equation It describes the behaviour of an electron in region of space called an atomic orbital ( - phi) Each orbital wavefunction ( ) is most easily described in two parts radial term which changes as a function of distance from the nucleus angular terms which changes as a function of angles l hi h h f i f l xyz= radial(r) angular(,) () (, ) Orbitals have SIZE determined by Rnl(r) - radial part y ( ) g p (p ) SHAPE determined by Ylm(,) - angular part (spherical harmonics) ENERGY determined by the Schrdinger equation
25
Polar Coordinates
To describe the wavefunction of atomic orbitals we must describe it in three dimensional space For an atom it is more appropriate to use spherical polar coordinates:
= Rnl(r) Ylm(,) () (, )
Radial Wavefunction
R(r) of the 1s orbital of H it decays exponentially with r it has a maximum at r = 0
4
Ylm(,)
R(r) =
2e
(r )
1 4
2Z n a0
For hydrogen this simplifies as Z=1 and ao=1 (in atomic units) and thus = 2. Hence Normalisation Constants are such that C h h Rnl(r) Ylm(,) 1s
2e
(r )
(1s)2
Misleading does not take into account the volume R(r)2 increases toward r = 0 Volume very small so probability of being at small r is small
27
R(r) in a.u.
1 2
2 = 1
1s
0 1 2 3 4 5
that is the probability of the electron p in an orbital must be 1 when all space is considered
Radius (a.u)
28
3s(r)
2)
Consider a sphere volume as we move at a small slice is 4r2 r By differentiation, the volume of a sphere = so
V = 4r 2 r
4 3 r 3
8
1 Z 2 (6 6 r + ( r ) 2 )e ( r 9 3 a0
2)
2Z n a0
=
3s
2Z n a0
6 4r2 R(r)2 )
1s
For H
2s
1
Z=1, n=2, =1
2 2 (2 r ) e ( r 2)
2 0 0 1 2 3 4 5
2 1 2 ( r / 3) 6 4 r + r e 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)
29 30
Radius (a.u)
For H 3s(r) =
2 1 2 ( r / 3) 6 4 r + r e 9 3 3
R(r) = 0
RADIAL NODE
R R(r) in a. .u.
0.4 0.3 03
2s
R(r) in a.u. i
2s
6 8 10
R(r) in a.u. )
2s at (2-r) = 0 (i.e. r=2 a.u.) 3s changes sign twice with two nodes (r =1.9, 7.1 a.u.) Caused by the order of the polynomial !
0.4
(2s)2
0.2 02
-2s
Radius (a.u)
31
Radius (a.u)
10
Radius (a.u)
32
Radial Nodes
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 1s 1 peak. 2s 2 peaks 3s 3 3 peaks k 3d = 3 2 1 = 0
RDFs of ns orbitals
Maximum at r = a0 Maximum at r 5 a0 Maximum at r 13 a0 M i 0 - Bohr Model - Bohr Model -B h M d l Bohr Model radius of a0 radius of 4 a0 radius of 9 a0 di f
Why are there radial nodes ? Pauli exclusion principle no two electrons can have the same set of QNs Actually no two electron can overlap ( occupy same space) y p (i.e. py p ) Overlap integral = A B = 0 AOs are said to be Orthogonal
*
1s
6 4r2 R(r)2 R 4 2
2s 2 3s
(analogous to normalisation)
Satisfied for AOs with same l by having change(s) in the wave function sign AO s Satisfied for AOs with different l angular component ensures no overlap
33
10
15
20
Radius (a.u)
34
Boundary surface
Represent the wave function in 3D Draw a 3D contour at a given value of 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
R(r) in a.u. a
1s
1
Boundary surface
0 0 1 2 3 4 5
Radius (a.u)
35 36
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 p The angular terms are different different shapes (orientations) Angular terms are the same for different n 2px, 3px, 4px Wave function for 2p and 3p orbitals R(r)
R(2 p) = 1 Z 2 6 a0
3 2
= 2/3
3)
R (3 p ) =
Y( )
1
2Z n a0
1 2 r 2 r ( 2r 4 e 9 6 33
re ( r
2)
R(r) in a.u. )
1 Z 2 (4 r ) re ( r R (3 p ) = 9 6 a0
Polynomial nodes Equation for no. of radial nodes n l 1 2p =0 , 3p =1 Ensures 2p and 3p orthogonal All p orbitals are multiplied by r R(r) = 0 at r = 0 Required to match the angular function q g angular node
37
2p
3 Y ( px ) = 4
sin( ) sin( )
3p
Radius (a.u)
p orbitals RDFs
Radial distribution function show probability at a given radius 2p function no nodes, maximum at r = 4 a0 (same as n=2 for Bohr model) 3p function two peaks, maximum at r 12 a0 (not the same as Bohr)
2.5 2 1.5 1 0.5 0 0 5 10 15 20
cos( )
3 Y ( px ) = 4
sin( ) cos( )
3 Y ( px ) = 4
sin( ) sin( )
4r R( (r)
1 angular nodal plane px (yz plane), py (xz plane) pz (xy plane) Ensures that p orbitals are orthogonal to s orbitals g
2p 3p
Radius (a.u) ( )
39
40
Last week
Solutions of the Schrdinger equation for atoms Atomic orbitals () Defined three quantum number (n, l, ml) Defined polar coordinates radial and angular terms
Examined wavefuntions of the s orbitals Angular term constant for s orbitals Wavefunction as constant * polynomial * exponential Decays as e ( r / n ) the larger n the more diffuse the orbital Defined radial nodes and examined there number (polynomial n l -1) Discussed the requirement for radial nodes Pauli exclusion principle p orbitals Radial functions similar to s orbital (except additional r) R(0) =0 0 Angular terms define shapes px, py and pz same for different n
Radial distribution function for p orbitals
42
Wave functions slightly more complicated (constant * polynomial * r2 * exp) Radial wave functions same for all 3d orbital
R (3d ) = 1 Z 2 ( r ) 2 e ( r 9 30 a0
0.1 0.08
Five different angular function e.g. Two angular nodes planes orthogonal to s (0) and p (1) e.g. dxy Nodal planes in g p xy and xz (yz) dxy (xz)
15 Y (d xz ) = 16
2)
Max probability at r = 9 a0
R( in a.u. (r)
1.5
AOs with 0 nodes have max probability at same radius as Bohr model 4d orbital has 1 node
4r2 R(r)2
3d - R(r)
3d - RDF
1
0.5
dz
Radius (a.u)
43
44
f orbitals
Almost no covalent bonding shape not really important
Penetration
The RDFs of AOs within a given principle QN (n) have different shapes Number of nodes n l - 1 3s 2 nodes n=3
l=3 Seven different angular function for each n (n 4) 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
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 These close peaks have a very strong p y g interaction with the nucleus 3s is said to be the most penetrating Penetration 3s > 3p > 3d
3d
3p 3s
1 4r R(r)
2 2
0.5
0 0 5 10 15 20
Radius (a.u)
45
46
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 are filled in increasing energy (Aufbau principle) and electrons fill degenerate (same energy) levels singularly first to give maximum spin (Hund s (Hunds rule) E(4s) < E(3d) K, Ca 1s 3d 5d 4f
48
1s
4r R(r)
2p 2s
2s 3s 4s 6s
1s 2p 3p
47
More complex results of penetration and shielding Energy levels vs atomic number gy
For H (Z=1) all orbitals within a principle QN have same energy For multi electron atoms p penetration follows
s>p>d>f
3d shielded very effectively by orbitals of n 3 and 3d almost does not change in energy with Z until Z = 19 4s filled before 3d
3d 4s 4
4p
4s
However n = 4 does not shield 3d effectively energy drops Similar pattern for 4d and 4f
49
3d
Increasing Z K Ca Sc Ti
50
51
52
Lewis bonding
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 Stability since all valence levels filled Diatomics F2
2H
+ F
F F
Lewis bonding in H2O Oxygen has 8 electron, hydrogen has 2 electron yg , y g Oxygen hydrogen interactions share 2 electron Oxygen also has two lone pairs
H O
O O
4 electron shared bond order = 2 OO
53
Shape VSEPR Electrons repel each other (lone pairs repulsion > than bonding pairs) Oxygen has 2 bond pairs and 2 lone pairs 4 directions to consider Accommodate 4 directions Tetrahedral shape p o H2O is bent with H-O-H angle of 104.5 Compares with a perfect tetrahedral of 109.45o lone pair repulsion
54
4H
2 C H
H C C
CC CH
F P F F F
120o
Carbon atoms share 4 electron bond order = 2 Carbon hydrogen interactions share 2 electrons
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)
(only the electrons round the P are shown for clarity) F atoms have 3 lone pairs (6 electrons) + 2 in each bond 8 P atom has 5 bond pairs with 2 electrons each 10 electrons !
55
F P
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 n? 3. 3 Draw sketches to represent the following for 3s 3p and 3d orbitals 3s, 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 wavefuntion mean ?
57
Last lecture
d orbitals Radial wavefunctions, nodes and angular wavefunctions (shapes) f orbitals Radial wavefunctions, nodes and angular wavefunctions (shapes) wavefunctions Multielectron atoms Penetration and shielding Atomic orbital energies, filling and the periodic table Valence bond theory (localised electron pairs forming bonds) Lewis structures number of electron pairs bond order (electrons shares divided by 2) VSEPR repulsion of electron pairs (BP and LP) molecular shape
59
Use Lewis model (number of electron pairs) E.g. BeH2, Be 1s2 2s2
hybridisation
shape.
H Be
Correctly predicted by VSEPR to be linear can we explain it using AOs Mix S with pz orbital 2 sp hybridized orbitals
60
sp hybridisation
sp hybridisation Mix and a s and a p orbital two combinations s + pz and s pz Two AOs two hybrid AOs Relative sign is important when mixing orbitals sp therefore means that the hybrid orbital is 50% s and 50% p
H H C C
H H
sp = sp =
1 ( 2s + 2 p 2 1 ( 2s 2 p 2
) )
+ +
= 61
sp2 hybridisation
62
Hybridisation bonds
For ethene sp2 hybridisation bonding in three directions
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
x Each local bond can hold 2 electrons z Have not accounted for the second pair of electron shared by the C atoms Creates a bond above and below the plane of the molecule Could think of the C as going from s2 p2 (sp2)3 px1
H C H
sp3 hybridisation tetrahedral
4 electron pairs
H2O can also be thought of like this with two of the l b th ht f lik thi ith t f th 3 orbitals occupied by lone pairs. sp
O H
63
H
sp3 hybridisation tetrahedral
64
4 electron pairs
Hybridisation d orbitals
Trigonal Bipyramidal sp3d 5 electron pairs
(s ( + px + py + pz + dz2) d
Hybridisation summary
Lone pairs equatorial
Hybrid Atomic orbitals isation that are mixed Geometry General formula AB2 AB3 AB4 Examples
sp3d
sp3d2
s + px + py + pz +
dz2
dx2-y2
octahedral
AB6
SF6 [Ni(CN)4]2[PtCl4]2-
65
66
1 = ( a + b )
Constructive interference
Animation shows the in phase interaction of the s orbitals as they are brought together
67
68
12 = ( a + b )2
12 = [ a ]2 + [ b ]2 + 2[ a b ]
2 = ( a b )
Destructive interference Node between the atoms Animation shows the out of phase interaction (different colours) of the s y g g orbitals as they are brought together
This gives an enhanced density where the AOs overlap between the atoms referred to as positive overlap and pull the atoms together ( bonding) 1 = Out of phase interaction
2 2 = ( a b )2
2 2 = [ a ]2 + [ b ]2 2[ a b ]
This leads to reduced density between the atoms 2 = * referred to as negative overlap and pushes the atoms apart (* anti-bonding)
Interaction of 2 AO
n MOs
69
Energy level diagram represents this interaction Two s orbitals interaction to create a low energy bonding and high energy anti-bonding molecular orbital Electrons fill the lowest energy orbital (same rules as for filling AOs) Bonding energy = 2 E
Energy
(anti-bonding)
Where the coefficients C, indicate the contribution contrib tion of the AO to the MO E Energy gy H H2 H
71
a
So for
Ca > Cb
(bonding)
AB
B
72
LCAO
Generally we can write
* = Ca a Cb b
Ca < Cb
*
n =
No AO 's x = a...
n Cx x
where the coefficients are different are reflect the contribution to each MO
Ca > Cb
*
The sign can be adsorbed into the coefficient and we can write all of the MOs in a general way
n n n = Ca a + Cb b
So
n=1 n=2
1 =
1 Ca a
1 + Cb b
1 Ca
1 0.8, Cb
= 0 .2
2 2 2 = Ca a + Cb b
2 2 Ca = 0.2, Cb = 0.8
The coefficients contains both phase (sign) of the AOs and how big their contribution (size) is to a particular MO
73
And an examination of the coefficients tells us the bonding characteristics of the MOs
74
+ve -ve ve
Must define orientation and stick to it for all orbitals. Thus pz + pz -ve pz pz +ve i.e. i e for sigma bond between P orbital need opposite sign coefficients !
Negative Overlap g p
Zero overlap
75
76
Last lecture
Hybridisation combining AOs on one atom to hybridisation made consistent with structure y
hybrid orbitals
Molecular orbital theory (delocalised view of bonding) LCAO all AOs can contribute to a MO n AOs n MOs Filled in same way as AOs Energy Example of H2 H Molecular orbitals for AOs of different energy H2 H
Linear Combination of Atomic Orbitals (LCAO) Use of coefficient to describe (i) phase of interaction and (ii) size of No AO 's contribution of a given AO ib i f i n n = Cx x
x = a...
78
= one nodal plane which passes through the bond axis
dzx + px
Additional * if a nodal plane exits between the atoms, that is if the p , wavefunction changes sign as you go from one atom to the other.
*
= two nodal plane which pass through the bond axis (end on dxy or d x 2 y 2 )
79 80
Possible interactions between 1s, 2s and 2p As you go from one side of wave function through the centre of the bond the sign of g the wavefunction reverses not centrosymmetric u = ungerade or odd
px + px
px - px
bonding
s s, pz pz
bonding
px px, py - py
2p
2g 1u 3g 2u
Label MOs starting from the bottom although often only valence orbitals
How does the energy of the 2s and 2p vary with Z (shielding / penetration) 2p 2s No sp mixing
2s
3 g
2s 1g Energy difference too big to interact with valence orbitals 1s AOs very small very small overlap in lower levels ll l i l l l (small E)
83
sp mixing i i Energy Li Be B C N O F Ne
84
Energy 1s 1 O
2 u
1s 1
1 g
MO diagram for N2
2s and 2p energies sufficiently close for interaction 1 and 2 shift to lower energy gy 3 shifted 4 shifted to high energy 3 now above 1 levels unaffected more complex
Making sense of N2
Take basic model for oxygen no s p interaction Examine how the MOs can interact and can not interact zero overlap level remain the same Examine interactions
4 u
4u 2 2p 2
u
2g 2p 2p 3g 1 u
2s
2s
2 u 1 g
85
2s 1u
Making sense of N2
Now examine the anti-bonding interaction (2 and 4) 4u 2u 2p 2 1g 3u 2 2s 1u
87
u
4*
2* Thus 2u goes down in energy and 4u goes up in energy For bonding with anti-bonding (1 4 or 2 3) the sign changes on one wave function zero overlap.
s p mixing
MO treatment of BeH2
VSEPR linear molecule, H Be H 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 MOs Interaction between H 1s and Be 2s Z
bonding
anti-bonding i b di
bonding b di
anti-bonding
2u 1g
Be Each of these is delocalised over three atoms and can hold up to two electrons
px and py have zero overlap
BeH2
2H
non bonding
89
Compare these two MOs with no sp mixing with the localised model of two Equivalent bonds formed via sp hybridization
90
Alternative approach
Step wise approach (ligands first) Mix hydrogen 1s orbitals first two Molecular orbitals H Be H Z
Be 3 3 *g
2p
2s 2u 1g
Be
BeH2
2H
92
91
Last lecture
LCAO I Interaction of AOs with different energy i f AO i h diff contribution Representing contribution as coefficient p g AO interactions that were possible MOs positive, negative and zero overlap labelling of MOs ( / , *, g / u)
Lecture 6 More complex molecules and CO bonding in transition metal complexes Prof G. W. Watson G W Lloyd Institute 2.05 watsong@tcd.ie g@
2nd row homo nuclear diatomics 2s 2p mixing occurs up to N energy different too big after this (O2, F2) p g p gy g ( Difference in MO diagram for N2 and O2 Molecular orbital treatment of BeH2
94
MO treatment of H2O
z H
O H x Three orbitals
MOs of H2O
three MOs anti - bonding
z H
O H x
H2O is not linear but why ? We will examine the MOs for an non linear tri-atomic and find out. What orbitals are involved 2 H 1s + O 2s O 2px O 2py and O 2pz Lets start by creating MO s from the hydrogen 1s orbitals. MOs orbitals
2pz
Taking the in p g phase p first- it will interact with the O 2s and O 2pz (zero overlap pair p ( p with O 2px and O 2py)
approx. 2pz - 2s + H
+
MOs of H2O
Out of phase H 1s orbitals Only interact with px 2 MOs y Zero overlap with py
z H
O H x
O H x
Slightly bonding Pz Non bonding Py non b di py bonding Very different to the VB concept of two identical sp3 filled orbital
H H
H2O
2H
H
98
MO theory correct.
MOs of Benzene
bonding is more important for reactivity independent of (zero overlap) six px orbitals combine to form six MOs
Different ways of arranging six px orbitals on a ring Lowest energy all in phase owes e e gy a p ase 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)
CH2 (s) 102o NH2 OH2 103o 105o 90 H2O CH2(T) 180
99
Energy increases with number of nodes as in AOs Also the number of nodes on a ring must be even continuous wavefunction Lowest energy all in phase All coeffcients the same
100
MOs of Benzene
Next occupied degenerate pair 1 nodal plane Two ways of doing this between atoms and through a pair of atoms
MO diagram for CO
Same orbitals as homo nuclear diatomics different energies g rise to significant 2s - 2p mixing g give g p g confusing set of orbitals
4
C-O anti - bonding (more C) (uneven more carbon) Primarily carbon (pz) bond (uneven more oxygen) Primarily oxygen (pz)
2p As the wavefunction goes through 0 (at the node) the smooth wavefunction has smaller coefficients next to the node zero at the node 2 electron per MO spread over 6 atoms Compare with Lewis structure with individual double bonds With local bonding have to resort to resonance structures to explain benzene 2p
2 3 1
2
2s 2s
1
101
LUMO 2* Comes f from standard i d d interaction i however lower oxygen orbital means has has more oxygen and * more carbon
t1u ligands in one axis contribute With opposite phase one nodal plane Interaction with p orbitals 3
3 C O
O
103 104
Electrons from filled orbitals on the ligands fill all the bonding orbitals
d electrons fill t2g (non bonding) and e*g (antibonding) Example is d6 e.g. Co3+ These are the orbitals considered in ligand filed theory. Note the e*g 6 ligand is anti-bonding ! orbitals What really decided oct is the interaction
106
oct
t2g
eg
t1u
a1g
105
oct
t2g
oct
t*2g t2g
e*g
oct t
t2g
?
107
without
with
ligand
Strong interaction with filled orbitals with interaction leads to reduction in oct (box shows the orbitals considered in ligand field theory)
108
Tutorial 2 part a
1. Explain the MO approach for the interaction of a) two s orbitals of identical energy ) gy b) two s orbitals of slightly different energy c) two s orbital of very different energy. Consider the bonding in the molecule O2 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 MOs 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
110
2.
oct
t2g
oct
t2g
without
with
ligand
St Strong interaction with empty orbitals with i t i t ti ith t bit l ith interaction leads to increase ti l d t i in oct (box shows the orbitals considered in ligand field theory)
109
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 MOs and interactions with the central atom (iii)what do h (iii) h d the resulting MOs look like? l i MO l k lik ? (iv)sketch an MO energy level diagram. ) g g d) What difference are there in the details of the bonding diagram between the Lewis and MO treatments 4. 4 Perform the same analysis for BeH2, HF BH3, and CH4 HF, 5. Use molecular orbital theory to explan a) The splitting of the d orbitals by sigma interactions with ligands b) The effect of interaction on the ligand field strength.
111 112
THE END