Lecture 16 C1403 October 31, Molecular orbital theory: molecular orbitals and diatomic molecules
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1 Lecture 16 C1403 October 31, Molecular orbital theory: molecular orbitals and diatomic molecules 18.2 Valence bond theory: hybridized orbitals and polyatomic molecules Bond order, bond lengths, connections of MO theory and VB theory with Lewis structures
2 + _ + + _ + + _ + _ + _ + _ +
3 Making of a! z and! z * orbital from overlap of two 2p z orbitals Making of a " x and " x * orbital from overlap of two 2p x orbitals Making of a " y and " y * orbital from overlap of two 2p y orbitals
4 Potential energy curves for the! and!* orbitals of a diatomic molecule Distance dependence of the energy of a! and!* orbital
5 The reason for the switch in the s and p MOs Larger gap between! 2s and! 2p with increasing Z Switch
6 O 2 Bond length = 1.21Å Bond order? O 2 + O 2 - O 2 2- Bond length = 1.12 Å Bond length = 1.26 Å Bond length = 1.49 Å
7 Compare the Lewis and MO structures of diatomic molecules C 2 N 2 O 2 F 2
8 What is the bond order of NO in Lewis terms and MO theory?
9 18.2 Polyatomic molecules Valence bond versus molecular orbital theory Hybridization of atomic orbitals to form molecular orbitals sp, sp 2 and sp 3 hybridized orbitals Hybridized orbitals and Lewis structures and molecular geometries Double bonds and triple bonds
10 18.2 Bonding in Methane and Orbital Hybridization
11 Structure of Methane tetrahedral bond angles = bond distances = 110 pm but structure seems inconsistent with electron configuration of carbon
12 Electron configuration of carbon 2p only two unpaired electrons should form! bonds to only two hydrogen atoms 2s bonds should be at right angles to one another
13 sp 3 Orbital Hybridization 2p Promote an electron from the 2 2s to the 2 2p orbital 2s
14 sp 3 Orbital Hybridization 2p 2p 2s 2s
15 sp 3 Orbital Hybridization 2p Mix together (hybridize) the 2 2s orbital and the three 2 2p orbitals 2s
16 sp 3 Orbital Hybridization 2p 2 sp 3 4 equivalent half-filled orbitals are consistent with four bonds and tetrahedral geometry 2s
17 Shapes of orbitals p s
18 Nodal properties of orbitals p + s +
19 Shape of sp 3 hybrid orbitals p + take the s orbital and place it on top of the p orbital s +
20 Shape of sp 3 hybrid orbitals s + p + + reinforcement of electron wave in regions where sign is the same destructive interference in regions of opposite sign
21 Shape of sp 3 hybrid orbitals sp hybrid + orbital shown is sp hybrid analogous procedure using three s orbitals and one p orbital gives sp 3 hybrid shape of sp 3 hybrid is similar
22 Shape of sp 3 hybrid orbitals sp hybrid + hybrid orbital is not symmetrical higher probability of finding an electron on one side of the nucleus than the other leads to stronger bonds
23 The C H C! Bond in Methane In-phase overlap of a half-filled 1s 1 orbital of hydrogen with a half-filled sp 3 hybrid orbital of carbon: s + H + C sp 3 gives a! bond. H C! H + C
24 Justification for Orbital Hybridization consistent with structure of methane allows for formation of 4 bonds rather than 2 bonds involving sp 3 hybrid orbitals are stronger than those involving s-s overlap or p-p overlap
25 18.2 sp 3 Hybridization and Bonding in Ethane
26 Structure of Ethane C 2 H 6 CH 3 CH 3 tetrahedral geometry at each carbon C H H bond distance = 110 pm C C C bond distance = 153 pm
27 The C C C! Bond in Ethane In-phase overlap of half-filled sp 3 hybrid orbital of one carbon with half-filled sp 3 hybrid orbital of another. Overlap is along internuclear axis to give a! bond.
28 The C C C! Bond in Ethane In-phase overlap of half-filled sp 3 hybrid orbital of one carbon with half-filled sp 3 hybrid orbital of another. Overlap is along internuclear axis to give a! bond.
29 18.2 sp 2 Hybridization and Bonding in Ethylene
30 Structure of Ethylene C 2 H 4 H 2 C=CH 2 planar bond angles: close to 120 bond distances: C H H = 110 pm C=C = 134 pm
31 sp 2 Orbital Hybridization 2p Promote an electron from the 2 2s to the 2 2p orbital 2s
32 sp 2 Orbital Hybridization 2p 2p 2s 2s
33 sp 2 Orbital Hybridization 2p Mix together (hybridize) the 2 2s orbital and two of the three 2 2p orbitals 2s
34 sp 2 Orbital Hybridization 2p 2 sp 2 3 equivalent half-filled sp 2 hybrid orbitals plus 1 p orbital left unhybridized 2s
35 sp 2 Orbital Hybridization p 2 sp 2 2 of the 3 sp 2 orbitals are involved in! bonds to hydrogens; the other is involved in a! bond to carbon
36 sp 2 Orbital Hybridization p!! 2 sp 2!!!
37 " Bonding in Ethylene p 2 sp 2 the unhybridized p orbital of carbon is involved in " bonding to the other carbon
38 " Bonding in Ethylene p 2 sp 2 each carbon has an unhybridized 2 2p orbital axis of orbital is perpendicular to the plane of the! bonds
39 " Bonding in Ethylene p 2 sp 2 side-by-side overlap of half-filled p orbitals gives a " bond double bond in ethylene has a! component and a " component
40 Hybridization and methane: CH4
41 sp3 hybridization and ethylene: H2C=CH2
42
43 Ground state > excite one electron > mix orbitals: one s orbital and one p orbital = two sp orbitals Acetylene H C C H H C N
44
45 Other examples of sp 2 and sp hybridized carbon Formaldehyde: H 2 C=O Carbon dioxide: O=C=O
46 d 2 sp 3 hybridization dsp 3 hybridization
47 SN = 2 SN = 3 SN = 4 Hybrid orbitals are constructed on an atom to reproduce the electronic arrangement characteristics that will yield the experimental shape of a molecule SN = 5 SN = 6
48 BeF 2 : SN = 2 = sp BF 3 : SN = 3 = sp 2 CH 4 : SN = 4 = sp 3 PF 5 : SN = 5 = sp 3 d SF 6 : SN = 6 = sp 3 d 2
49 Describe the bonding for ethane, ethene and acetylene in terms of overlap of hybridized orbitals Ethane: Ethylene: Acetylene:
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