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b = a(h1) + b(h2)
where h1 and h2 are HAOs on adjacent atoms pointing towards each other.
Bond strength = f(overlap integral S), i.e. the constructive overlap between h1 and h2.
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The more s-character, the larger
the overlap integral (up to a point).
In general:
Shorter bonds are stronger bonds
(which does not necessarily correlate
with overall reactivity!!!).
Positive overlap continuously increases for s-orbitals, but goes through a maximum for p-orbitals!
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Concept of isovalent hybdridization: BENTS RULES
The more electronegative an atom X or Y bound to a central atom E, the greater will be its
demand for electron density from the central atom.
From the concept of orbital electronegativity: EN(s) > EN(p) > EN(d)
the more the s-character in a hybrid orbital, the greater its electronegativity.
Central atom E will direct more p (and less s) character towards the more electronegative atom
(and vice versa)
e.g. PCl5:
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b) Molecular Dipole Moments Rationalized by VB Theory
Need to find the centers of electronic (-ve) and nuclear (+ve) charge in the molecule as
determined by the molecular structure and e--distribution.
( hmm, wasnt there another concept that we used for this as well?)
lp = 2e<r>
Example: Two charges equal in magnitude to the charge of an electron (4.8 x 10-10 electrostatic
units esu) and separated by a distance of 91.7 pm (interatomic distance of HF molecule) give a
dipole of 4.4 Debye.
The value 4.4 Debye represents the expected dipole moment for 100% ionic H+F-.
Okay, now lets look at how HAOs are useful for explaining lone pair dipole moments
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One of the quantum mechanical postulates is that the average or expectation value of any
observable property O is given by:
where is the operator that corresponds to the property O (e.g. the Hamiltonian for the energy of
the system, or the distance between charge centroids)
and is the state function (i.e. wavefunction) of the system.
Thus:
Because the s-orbital is centrosymmetric (i.e., <rs> = 0), the only dipole contribution comes
from the hybrid orbital and the dipole is simply
i.e., only the interference integral that describes the hybrid contributes to the dipole.
POINT: s and p orbitals are centrosymmetric. HAOs are not and therefore can be invoked in the
explanation of dipoles.
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Bond pair dipoles: more difficult to estimate
-ve: Need to know the electron density distribution along the bond as f(r)
; Eh = sp-hybrid orbital on E
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From figure:
- The electron density center for the hybrid orbital is at (using the result for rsp from the
derivatization for the lone pair):
In summary:
2ab<r>HE contribution from the overlap density of both atoms in the bond to the center of
negative charge along the bond
2b2cscp<r>sp contribution from the hybrid orbital itself on E to the charge center; orientation
depends on the radial distribution of electron density in E.
(non-existent for 1s because of radial symmetry)
The orientation and size of a bond-dipole moment cannot solely be predicted on the basis
of the difference in EN values of the two atoms involved !!!
Have to consider the charge distribution contributions from the orbitals involved, which
can lead to a dipole that is reversed from the one expected based on EN!!!
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In general: LP dipole moments >> BP dipole moments
In bonds of the type E1-E2 (E1 E2) with hybrid orbitals from both atoms forming the bond,
the hybrid contributions to the dipole moment tend to cancel.
Examples:
= 1.5 D = 0.2 D
N > H N < F
no hybrid dipole moment on H Bents rule requires more s-character on NLP
Carbon monoxide: measured dipole moment = 0.1 D, i.e. very small, but slightly toward C !
From Bents rule: both sp lone pairs have more Dominated by EN: More compact oxygen
than 50 % s-character with carbon more so than orbitals dipole towards oxygen
oxygen dipole towards carbon (slightly)
(cf. sp > sp2 > sp3, slightly) but:
net effect very small toward C net effect 0, perhaps slightly toward O
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c) Bond Energies and VB theory
VB Theory Thermodynamics
Diatomic molecules: Experimentally, bond energy (D) is simply the internal energy change
required to separate the gas phase molecule into its two constituent atoms (also in the gas phase.)
Polyatomic molecules: 1) Removal of one terminal atom to leave a fragment ABn-1 alters the
bonding between A and the remaining B atoms (changes hybridization / multiple bonding).
2) Ground state electron configuration of the dissociated B atom may be quite different from its
valence state when bound to A. The valence state promotion energy for B may make a significant
contribution to the bond energy D. Consider a simple binary compound ABn.
Electrostatic configuration of B alone vs. B in ABn (in particular of the promotion energy
Bgroundstate Bhybrid).
In step 2: Breaking of second bond and relaxation of both atoms into g. s. atomic configuration
DO THIS FOR YOURSELF AT HOME
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A reverse example:
Important conclusion: Average bond energies and individual bond energies in ABn systems
are not the same!!!
Thought experiment: No matter which P-Cl is broken E is always the same. This is a
requirement of the macroscopically observed real experimental value but how can that be??
In summary:
Experimental bond energies are composed of the actual bond dissociation energy and the
energy terms that account for changes in the electronic configurations of the participating
atoms and/or molecular fragments.
( to be really correct would also have to consider vibrational and rotational states )
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More examples:
4 <ECH> = 4 99 = 4 E*CH PC
The C-H bond is truly stronger than the Si-H bond. Also true for N/P and O/S pairs.
Why? Because of greater diffuseness of the atomic orbitals of heavier elementssee below!
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4.3 Concept of Isolobality (Nobel laureate Roald Hoffman)
Studying isolobal molecular fragments can help suggest patterns of bonding / reactivity.
Def. Two molecular fragments are said to isolobal if the number, symmetry properties,
approximated energy and shape of the frontier orbitals and the number of electrons in them are
similar (NOT identical, but similar).
Example: The following orbitals have -type symmetry, are similar in energy, and are occupied
by one electrontherefore we can expect analogous bonding properties.
We can also make the isolobal analogy with the following two and three orbitals examples:
NOTE: Although the isolobal analogy can give clues about what kind of compounds might be
expected to exist, it is only a useful tool and not a hard and fast rule.
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4.4. Limitations of VB Theory
Valence shell expansion is often required to draw satisfactory Lewis diagrams, e.g. for PCl5
and SF6, even though the incorporation of d-orbitals does energetically not make sense the
process:
s2pnd0 s2pn-mdm
Costs too much hybridization energy. So how can it be that e.g. sulfur can bind six fluorine
atoms???
How can we describe the bonding in B2H6 using only H1s orbitals?
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