No Slide Title - The Edelstein Center for the Analysis of ... · Introduction to Valence Bond...
Transcript of No Slide Title - The Edelstein Center for the Analysis of ... · Introduction to Valence Bond...
© Prof. Zvi C. Koren1 19.07.10
Bonding OrbitalsBonding Orbitals
Models of Chemical Bonding
Valence Bond (VB) Theory Molecular Orbital (MO) Theory
Simplest Complex
© Prof. Zvi C. Koren2 19.07.10
Constructive Interference
Overlap Sum
התאבכות בונה
Consider two simple waves:
A
“in-phase”
Introduction to Valence Bond (VB) Theory
A
2A
© Prof. Zvi C. Koren3 19.07.10
Valence Bond (VB) Theory
• As two atoms approach each other, an orbital (wave) that describes
the motions of the valence e in an atom constructively interacts with an
orbital (wave) of an e on another atom.
• This constructive interference between two orbitals is called an
“overlap” of orbitals.
• The overlap region is between the two nuclei and leads to an increase
in “amplitude” of the orbital (wave) in that internuclear regon.
• This results in the “growth” of the orbital in the overlap region.
• This means that there is now an increase in the probability of finding
the e between the two nuclei
• This effectively means that there is an increase of electron density
(negative charge) between the two nuclei.
• Hence, this reduces the internuclear repulsion and stabilizes the
system.
• This stabilization is considered a chemical bond between two atoms.
• Conclusion: Overlap of valence orbitals Valence Bond (VB)
© Prof. Zvi C. Koren4 19.07.10
s-s bond
Notes about the Sigma Bond (overlapping region is what constitutes The Bond):• Constructive Interference increases e-density in the region between the 2 nuclei,
leading to stabilization. • The orbital overlap region is localized between the 2 nuclei.• bond (orbital overlap) is on the internuclear axis.
Sigma () Bonds
+
s s
H2H H
+
px px
F F
px-px bond(head-on approach)
:F:F:::
H:H
::
+
s
H
px
FH:F::
:
F2
x
HF
s-px bond
© Prof. Zvi C. Koren5 19.07.10
+
py
O
Pi () Bonds
py-py bond
x
y
z
O::O:::
:
O2
Note about the Pi Bond:
• bond (orbital overlap) is above and below the internuclear axis, but it’s still
localized between the 2 nuclei.
• One bond has two overlapping regions.
• A second bond is sometimes possible, pz-pz. This would then yield a total of 3
bonds (triple bond): 1 + 2.
py
O
(side-by-sideapproach)
© Prof. Zvi C. Koren6 19.07.10
Consider the Case of C + 4H CH4
Some of the bond angles would be 90o. Why?
Introduction to Hybridization Theory
Hybridization explains the molecular shapes of polyatomic molecules
Hybridization Theory:
• Pure Atomic Orbitals (AO’s), such as s, p, d, ..., belonging to a central
atom, “mix” to produce new Hybrid Orbitals (HO’s) on that atom.
• Each HO is composed of a Big Head(s), and a small tail(s), where the
“head” is oriented to produce the correct molecular geometry.
• Each single e-pair needs to be accomodated, at least partly, by an HO.
• The # of HO’s about a central atom = # of single e-pairs about it.
Hence, :NH3 and CH4 will each have 4 HO’s about the central atom.
• The # of HO’s = # of AO’s used in the “mixing” or hybridization.
• The orbitals used for hybridization are the s and p orbitals, and then the
d orbitals, etc.
the hybridization types, in order of increasing complexity, are:
sp (2 HO’s), sp2 (3), sp3 (4), sp3d or dsp3 (5), sp3d2 or d2sp3 (6).
(see the Table – next slide)
© Prof. Zvi C. Koren7 19.07.10
TOTAL # of Single E-Pairs
(bonding + lone)about the
Central Atom
ELECTRONIC
GEOMETRY
of the Single E-Pairs
about the Central Atom
# ofAtoms
Bondedto the
Central Atom
MOLECULAR
GEOMETRY
of the Atoms about
the Central Atom
2 Linear (180o) Linear2
3
TrigonalPlanar(120o)
3 Trigonal Planar
2 Bent (Angular)
4
Tetrahedral
(109.5o)
cos(tet)=–⅓
Tetrahedral4
3
2
Trigonal Pyramidal
Bent (Angular)
5
Trigonal
Bipyramidal
(120o, 90o)4
5 Trigonal Bipyramidal(lone e-pairs on equator)Bent Seesaw
3
2
Bent “T”
Linear
6Octahedral
(90o)
6 Octahedral
5
4
Bent-Square Pyramidal
Square Planar
Hybridization Types and Electronic & Molecular Geometries
axial
sp2
sp3
sp3d
or*
dsp3
sp3d2
or*
d2sp3
sp
Hybrid-ization
about theCentralAtom
equa-torial
* sp3d, sp3d2: all from same shell; dsp3, d2sp3: d from shell below.
© Prof. Zvi C. Koren8 19.07.10
Examples of Hybridization Types
NH3
Draw Lewis Electron-Dot Diagram (ן"שמ. ם.ח. ש.א): N
H
:HH
Total # of Single e-Pairs (bonding + lone) about the Central Atom = 4
Total # of Hybrid Orbitals (HO’s) formed about the Central Atom = 4
Total # of Pure Atomic Orbitals (AO’s) needed for Hybridization = 4
Pure Atomic Orbitals (AO’s) mixed in the Hybridization process: s + px, py, pz
Name of each HO produced =
Name of the type of hybridization = sp3
Show the Hybridization process:
Free N (Group 5A):
2s22p3
s2
p3
sp3 sp3 sp3 sp3
Bonding N:
(sp3)2 (sp3)1 (sp3)1 (sp3)1
(continued)
Hund’s Rule: 5 e’s in 4 degenerate orbitals
sp3 hybridization
© Prof. Zvi C. Koren9 19.07.10
(continued)
Draw the Electronic Geometry
about the Central Atom:
N
NH3
(tetrahedral)
N
Draw the HO’s
about the Central Atom
And place the e’s in the HO’s:
sp3
Show each Bond resulting from the
Orbital Overlap of the relevant orbitals:
N
sp3
sp3sp3
sp3
Question: What would CH4 look like?
sp3-ssp3-s
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4. Draw the HO’s about central atom and the AO’s about the
terminal atoms (draw in class)
Examples with Hybrid Atomic Orbitals
Consider CH4
1. Draw Lewis Structure: H–C–H
H
HThis structure does not
indicate the actual
geometry, at this point.
2. Determine Hybridization Type AND Electronic Geometry
about Central Atom:
# of e-pairs about central C = 4:
4 HO’s 4 (sp3) HO’s sp3-hybridization
Electronic Geometry = Tetrahedral
(“Step-by-Step”)
3. Determine the Molecular Geometry about Central Atom:
# of e-pairs about central C = 4; # of atoms about central C = 4
Molecular Geometry = Tetrahedral (Bond Angles = ____)
© Prof. Zvi C. Koren11 19.07.10
4. Draw the HO’s about each central atom and the AO’s about the
terminal atoms (draw in class)
Examples with Hybrid Atomic Orbitals
Consider C2H4 (ethylene, ethene)
1. Draw Lewis Structure: H–C=C–H
HThis structure does not
indicate the actual
geometry, at this point.
2. Determine Hybridization Type AND Electronic Geometry about
Central Atom:
# of SINGLE e-pairs about EACH central C = 3:
3 HO’s 3 (sp2) HO’s sp2-hybridization (one p unused)
Electronic Geometry = Trigonal Planar
(“Step-by-Step”)
3. Determine the Molecular Geometry about EACH Central Atom:
# of e-pairs about each C = 3; # of atoms about each C = 3
Molecular Geometry = Trigonal Planar (Bond Angles = ____)
H
© Prof. Zvi C. Koren12 19.07.10
Do the following molecules:
HCCH acetylene, ethyne
PF5 phosphorus pentachloride
SF6 sulfur hexafluoride
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So, what’s in the Hybrid Orbitals?
• Lone (non-bonding) e’s – one or two.
• Future Sharing (Bonding) e’s,
which will be used in the formation of bonds –
one e (for a regular covalent bond)
or two e’s (for a coordinate covalent bond).
How can we automatically determine the number of HO’s about a
central nonmetallic atom in a covalent compound?
# of HO’s = # of single e-pairs about the central atom in the
Lewis structure, i.e., “ + lone” pairs.
So What’s in the Hybrid Orbitals?(Summary)
© Prof. Zvi C. Koren14 19.07.10
Recall:
Pure Atomic Orbitals can overlap to produce σ bonds:
s overlapping s σs-s Example: H–H
s overlapping p σs-p Example: H–F
p overlapping p (head-on) σp-p Example: F–F
Now,
Hybrid AO’s can also form σ-bonds through overlapping::
• a pure AO and a hybrid AO
• a hybrid AO with another hybrid AO
Examples follow …
© Prof. Zvi C. Koren15 19.07.10
bond sp2-s
Sigma Bonds in Ethylene, C2H4
sp2-sp2 bond
C C+ C–C
px px πpx-px
π-Bonding
Note:
One π bond with 2
overlapping regions
© Prof. Zvi C. Koren16 19.07.10
© Prof. Zvi C. Koren17 19.07.10
H–CC–H acetylene, ethyne
© Prof. Zvi C. Koren18 19.07.10
Explain why the 2 methylene groups (-CH2) are in perpendicular planes
© Prof. Zvi C. Koren19 19.07.10
© Prof. Zvi C. Koren20 19.07.10
Summary of Valence Bond (VB) Theory
A Chemical Bond ( or or ) consists of:
• an overlap of two (pure or hybrid) atomic orbitals, as in
the constructive interference (התאבכות בונה) of two waves
• this overlap increases the electron density between the two
atoms (nuclei), which
• decreases the internuclear repulsion, and increases the
attraction between each nuclei and the resulting new
electron “cloud”
• Note: the overlap is localized between the atoms
What is a Chemical Bond?
What is the nature of the “Chemical Glue” that binds two atoms
together?
© Prof. Zvi C. Koren21 19.07.10
Bonding OrbitalsBonding Orbitals
Models of Chemical Bonding
Valence Bond (VB) Theory Molecular Orbital (MO) Theory
Simplest Complex
Part 2
© Prof. Zvi C. Koren22 19.07.10
Destructive InterferenceConstructive Interference
בונההתאבכות הורסתהתאבכות
Consider two EXTREME simple-wave profiles
Introduction to Molecular Orbital Theory
“in-phase”“out-of-phase”
2A
© Prof. Zvi C. Koren23 19.07.10
bonding
antibonding
nodal plane
Atomic electronic configuration for H: 1s1
Molecular electronic configuration for H2:2s1
(Do: H2–, H2
+, He2, He2+)
Bond Order:
Net # of bonding pairs
Recall:
Diamagnetism
vs.
Paramagnetisms1σ
*1
σs
© Prof. Zvi C. Koren24 19.07.10
*
pσ
pσ
pxπ
pxpx
pz
σ and π Bonding and Antibonding MO’s from AO’s
pz
py π:Also
*py π:Also*
pxπ
© Prof. Zvi C. Koren25 19.07.10
MO electronic configuration of B2:
Why is π2plower in energy
than σ2p?
Molecular Orbital Energy Level Diagram
1s – – 1s*s1
σ
s1σ
2s – – 2s*
s2σ
s2σ
2p – – – – – – 2p
p2π
*p2
π
p2σ
*p2
σ–
–
–
–
–
– –
–
– –
AO’s AO’sMO’s
En
ergy
Do also:
C2, N2, O2,
F2, Ne2;
NO, OF;
O2–, O2
+
2
2p
2*s2
2
2sπσ σ
© Prof. Zvi C. Koren26 19.07.10
According to VB Theory
(Lewis Electron-Dot Diagram):
According to MO Theory:
O=O
The Truth!
Is O2 Diamagnetic or Paramagnetic?
O=O. .
© Prof. Zvi C. Koren27 19.07.10
Molecular Orbitals and Vision
© Prof. Zvi C. Koren28 19.07.10
Summary of Molecular Orbital (MO) Theory
What is a Chemical Bond?
What is the nature of the Chemical Glue that binds two atoms
together?
A Chemical Bond (, * or , *) consists of:
• an overlap of two OR MORE (pure or hybrid) atomic orbitals;
• TWO types of overlaps (wave interactions) are considered:
constructive interference bonding <-- (התאבכות בונה) MO,
destructive interference antibonding <-- (התאבכות הורסת) MO
• the constructive overlap increases the electron density between the two
atoms (nuclei), which
• decreases the internuclear repulsion, and increases the attraction
between each nuclei and the resulting new electron “cloud”
• Note: Each overlap (MO) is delocalized, and is spread over two OR
MORE atoms
Summary of Molecular Orbital (MO) Theory
© Prof. Zvi C. Koren29 19.07.10
A Comparison of Chemical Bonding Theories
Lewis E-Dot
Structures
Valence-Bond
(VB) Theory
Molecular-Orbital
(MO) Theory
Is the bond localized
between the 2 nuclei?
Yes: e-particles are positioned in-between the 2 nuclei.
Yes: overlap is
fixed to a region
between nuclei.
NO!!!. It’s delocalized.2 AO’s fuse together to form the MO that is spread over the entiremolecule.
Type and Name
of Bonds
single, double,
and triple bonds
σ and π bonds σ and π bonding
molecular orbitals
(MO’s), and σ* and
π* antibonding MO’s
Type of
interactions
between e’s
pairing-up of lone
(unpaired) e’s:
Koren’s Principle
of Lonely e-Hearts
Club
Constructive
Interference
between atomic
orbitals (AO’s)
Constructive
AND
Destructive
Interferences
between AO’s
Nature of the
Chemical Bond(-) e-particles
between (+) nuclei
overlap between e-waves (orbitals)
increases (-) e-density between (+) nuclei