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In NMR spectroscopy, coupling is due to non-zero spin atoms coupling with each other.

A
spin up coupling will reinforce the external magnetic field, hence increasing the shift.
Conversely, a spin down will act against the magnetic field, hence weakening it, hence
leading to a smaller shift. This will produce two or more peaks, rather than just on.
In NMR spectroscopy, lower temperatures lead to a more detailed spectrum. Coupling that
at room temperature would be too fast, hence average out to be zero, are slowed down and
can be measured.
To determine whether a molecule is paramagnetic or not, simply find unpaired electrons in
the MO diagram. If theyre present, than the molecule is paramagnetic.
In the presence of an acyl chloride, in IR spectroscopy, the C=O bond is strengthened, hence
giving a larger shift.
To determine the quantum number I, nuclei with odd mass number have half-integral spin
(e.g. 1H, 35Cl), nuclei with odd number of protons and odd number of neutrons have integral
spin (De, 14N) and nuclei with even number of protons and neutrons have zero spin (12C, 16O).
Solvents in NMR are chosen such that they do not give out a misleading signal, and such
that the NMR machine can lock onto its signal and stabilise the magnetic field.
Exchange interaction states that due to quantum mechanical effects, the electrons tend to
have parallel spins in degenerate orbitals, to achieve the lowest energy state possible.
Coupling constants in 1H NMR are in ascending order of magnitude: cis same carbon, cis
different carbons, trans different carbons. This is due to the dihedral angle.
Broadband proton decoupling removes all the splitting caused by C-H coupling. Allows
clearer spectra for large molecules.
Attached proton test allows determination of the number of hydrogen atoms attached to a
carbon. Even #=same side as the solvent, even#=opposite side of solvent.
Satellites in NMR spectra appear clearly in 1H NMR as a wide doublet about the main peak
and are due to coupling between the lowly abundant 13C and 1H. They are very low in
intensity and hence appear as very small peaks, due to the low abundance of 13C.

The contribution in MO can be determined by using the MO diagrams, by determining how


close the MO is to the AO of the atoms forming it. For instance, in a C=O, C has a larger
contribution to the * as the C 2p AO is closer to this than the O 2p. Conversely, the same
argument is valid for the oxygen and the bond. The larger the separation of the atoms, the
smaller the interaction.
In heteronuclear diatomics, the more electronegative atom contributes more to the
bonding MO, whereas the less electronegative atom contributes more to the antibonding
MO. Heteronuclear bonds are polar.
Looking at HF, the H 1s has a
similar symmetry to 2pz, so 3
(bonding) and 4 (antibonding)
bonds form; however, the px
and py AOs are not involved in
the formation of MOs, and thus
are called non bonding orbitals
(commonly lone pairs). These
are termed 1. The F 1s and 2s
are way too low in energy to
interact, so they just form 1
and 2.

The isoelectronic principle states that molecules with the same number of electrons and
atoms will have similar structures and chemical properties. Most generally, the valence
electrons of molecules are considered isoelectronic. However, the principle can also apply
only to the inner electrons of molecules, or both. CO and N2 are isoelectronic molecules and
their properties are remarkably similar.
The wavefunction gives the probability of an electron being in a volume v, whereas the
radial distribution function give the probability of finding an electron in a small shall of
thickness r.
The total number of radial and angular nodes is given by n-1. The number of angular nodes
is given by l, where l=0 for s, 1 for p, 2 for d and 3 for f orbitals. The number of radial nodes
is given by (n-1- l).
You may have to discuss about penetration of orbitals relative to each other. For instance,
state that the 2s orbital penetrates to the nucleus, more than the 2p orbital. This can be
justified by analysing the radial distribution function.
Zeff is a measure of the effective nuclear charge. Since multi-electron systems have factors
like screening that cause a reduction of nuclear charge experienced by the electrons as we
move further away from the nucleus, Zeff gives a more accurate value for the energy level.
Bond order= (# of bonding-# of antibonding). If bond order>0 then the molecule is stable
with respect to dissociation and the effects of antibonding MOs are outweighed by the
effects of bonding. A good example is H2, H2+, He2 and He2+:

As bond order increases the bond enthalpy increases and the bond length decreases.

MOs are formed from the linear combination of atomic orbitals; bonding MOs show a
minimum at a certain separation (energy due to the arrangement of electrons overweighs
the energy of nuclear repulsion), whereas antibonding MOs increase in energy as separation
decrease. Remember that bonding is due to an in-phase overlap of AOs and electron density
is highest between the atoms and antibonding is due to an out-of-phase overlap and
electron density is highest at the peripheries of the atoms.
Traversing a circular path in a plane perpendicular to the internuclear axis, if there are no
nodal planes, then the MO is defined as , if one nodal plane is present than its called .
By looking at the centre of inversion:

Figure 1 (a) is defined as g, as "gerade" in German for even and (b) as u, for "ungerade" in German
for odd.

Rules for MO forming: 1. #of AOs=#of MOs


2. Overlap can occur with AOs with the same symmetry. Extensive
mixing occurs and crossing is not permitted
3. The smaller the energy difference between the AOs, the larger
the interaction
s-p mixing occurs extensively in atoms smaller than oxygen excluded. 2s-2pz mixing
(remember: same symmetry), leads to a decrease in 2g and 2u and in increase in 3g and
3u.
Be2 has such a low dissociation energy as its bond order is zero. However, due to s-p mixing
the dissociation energy is still >0, as the antibonding do not outweigh the effects of bonding.
The higher Z, the greater the separation between s and p orbitals.

Reduction of ketones/aldehydes cant happen with H-, as it has a very high charge density
and it only reacts as a base (proton acceptor). The filled 1s of H is similarly matched with the
* of H-X, rather than * in C=O.