Symmetry and Molecular Orbitals (I) - National Chiao...
Transcript of Symmetry and Molecular Orbitals (I) - National Chiao...
![Page 1: Symmetry and Molecular Orbitals (I) - National Chiao …ocw.nctu.edu.tw/upload/classbfs1209120524118880.pdfHF MO Energy Level Diagram AMO NBMO BMO H+ F-H :F::: Bond Order, Strength](https://reader031.fdocuments.in/reader031/viewer/2022030508/5ab74c607f8b9aa6018b4674/html5/thumbnails/1.jpg)
Symmetry and MolecularOrbitals (I)
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Simple Bonding Modelhttp://chiuserv.ac.nctu.edu.tw/~htchiu/Chemistry/Fall-2005/Chemical-Bonds.htm
Lewis StructuresOctet RuleResonanceFormal ChargeOxidation NumberHypervalence
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Resonance and Formal Charge
A0
A+1
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VSEPR Some Molecules
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VSEPR Some Molecules
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VSEPR Model
Bond LengthBond Strength
Less Repulsion More Repulsion
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Why Sharing Electron FormsCovalent Bond?
Without Electrons, Internuclei Repulsion Forces PushesNuclei Apart.
Sharing Electrons (in some area around the nuclei)Generates Attractive Force to Bind Nucleus Together.
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Why Sharing Electron Forms Anti-Bond?
In Some Area, Sharing Electrons Generates RepulsiveForce.
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Bonding and AntibondingRegion Around The Nuclei has Binding (bonding) andAntibinding (antibonding) Zones.
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Spherical Boundary Surface of s and pOrbitals
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Spherical BoundarySurface of dOrbitals
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Spherical Boundary Surface of fOrbitals
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Valence Bond Theory•VB Theory is a quantum mechanical model
describes the distribution of electrons in bonds.Developed from Lewis theory and the VSEPR model.
•Usually provides bonding picture with localized view.
•Simple VB theory cannot explain bonding inpolyatomic molecules. The concept of Hybridizationis developed to explain different geometry variations.Describes molecular geometry easier.
•Using Delocalization and Resonance to explainextended distribution of electrons over many atoms ina substance.
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Valence Bond Theory
s p
p p
N2
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Square of a Wavefunction isProbability Density
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Constructive and DestructiveInterference
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Hybridization•Linear Combination of Atomic Orbitals of an Atom
forms a new set of orbitals.•Hybridization divides the electron density distribution
of an atom into new areas.
• (sp)A = (1/2)1/2((s) + (p))
• (sp)B = (1/2)1/2((s) - (p))
• (sp2)A = (1/3)1/2(s) + (2/3)1/2(px)
• (sp2)B = (1/3)1/2(s) - (1/6)1/2(px) + (1/2)1/2(py)
• (sp2)C = (1/3)1/2(s) - (1/6)1/2(px) - (1/2)1/2(py)
• (sp3)A = (1/2)((s) + (px) + (py) + (pz))
• (sp3)B = (1/2)((s) + (px) - (py) - (pz))
• (sp3)C = (1/2)((s) - (px) + (py) - (pz))
• (sp3)D = (1/2)((s) - (px) - (py) + (pz))
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Hybridization sp
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Hybridization sp
+ -
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Hybridization sp2
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Hybridization sp2
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Hybridization sp2 + p
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Hybridization sp3
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Hybridization sp3
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Hybridization H2O Bonds
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Hybridization C2H2 Bonds
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Molecular Orbital Theory
•Electrons occupy orbitals that spread through the entiremolecule.
•Providing bonding pictures with non-localized view.•Deals with entire area surrounding a molecule.
•Hyperchem Litehttp://www.hyper.com/sales/electronic/electronic-lite.htm
•CACAO98 (Beta Version)http://www.chembio.uoguelph.ca/oakley/310/cacao/cacao.htm
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Rules of Molecular Orbitals
Rules for forming bonding and antibonding MOsnumber of total molecular orbitals = number of total atomic orbitalsatomic orbitals have the right symmetryatomic orbitals overlap wellatomic orbitals have similar energy
Rules for filling electrons are the same for MOs and AOs.start filling from the lowest energy orbitalfollows Pauli exclusion principle and Hund's rule
Provides molecular energy informationExplains magnetic behaviorCan provide molecular structural explanation, but moredifficult to comprehend than VB theory
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Bonding Molecular Orbitals
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Bonding Molecular Orbitals
Constructive InterferenceSymmetric: i
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Antibonding MolecularOrbitals
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Antibonding Molecular Orbitals
Destructive Interference
Anti-symmetric: i
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Molecular Orbital Energy Level Diagram•Better Overlap => Higher E•Bond Order = ½(# of B.O. e - - # of A.O. e -)•Diamagnetic: all e- paired•Paramagnetic: with e- unpaired
EE
0
½
1
½
B.O.
-He2
PH2-
DH2
PH2+
MagneticProperty
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Overlap of MOs
Wrong symmetry
Right symmetryBad OverlapGood Overlap
Wrong symmetry
+
+
+
+
+
+
+
+
++
-
-
-
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MO Symmetrybond: no nodal plane passing through internuclear axisbond: 1 nodal plane passing through internuclear axisbond: 2 nodal planes passing through internuclear axis
+ +
+ +
+ +
+ +
-
++
+-
-
--
-- -
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P Orbitals
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P Orbitals
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MO Symmetry
B.MO
A.MO
g: geradeu: ungerade
+ +
+ +
+
+ +-
- -
-
-
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MO Energies of Period 2 M2 Molecules
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Energy Levels ofMany ElectronAtoms in PeriodicTable
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M2 MO Energy Level Diagrams
Higher Zeff2s 2p more separated2s e- closer to nuclei2s MOs more like 2s AOss-s overlap not effective
2s and 2pz in same spacebetween nucleiGreater 1 u –2 g repulsion2s 2pz MOs same symmetryMore mixing
1g
1u
1g
1u
1g
1g
O2 –F2 Li2 –N2
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MO of Period 2 M2 Molecules
LUMOLowestUnoccupiedMolecularOrbital
HOMOHighestOccupiedMolecularOrbital
DPDDPDDMagnet.
1232101B.O.
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PhotoelectronSpectroscopy
•Ek = h–I
measured known calculated E(MO)
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UV photoelectron Spectrum of N2
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Heteronuclear Diatomic Molecules
•A more electronegative•B less electronegative
+
+
+ +
+ -
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CO MO Energy Level Diagram
2
1
3
2
1u
1g
1g
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CO MO Energy Level Diagram
2
1
3
2
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CO MO Energy Level Diagram
2
1
3
2
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ICl MO Energy Level Diagram
1g
1u
1g
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HF MO Energy Level Diagram
AMO
NBMO
BMO
H+ F-
H :F:::
![Page 51: Symmetry and Molecular Orbitals (I) - National Chiao …ocw.nctu.edu.tw/upload/classbfs1209120524118880.pdfHF MO Energy Level Diagram AMO NBMO BMO H+ F-H :F::: Bond Order, Strength](https://reader031.fdocuments.in/reader031/viewer/2022030508/5ab74c607f8b9aa6018b4674/html5/thumbnails/51.jpg)
Bond Order, Strength and Length
![Page 52: Symmetry and Molecular Orbitals (I) - National Chiao …ocw.nctu.edu.tw/upload/classbfs1209120524118880.pdfHF MO Energy Level Diagram AMO NBMO BMO H+ F-H :F::: Bond Order, Strength](https://reader031.fdocuments.in/reader031/viewer/2022030508/5ab74c607f8b9aa6018b4674/html5/thumbnails/52.jpg)
Bond Strength and Length
O-O
N-NC-N,C-O
C-C