Walsh diagrams

Walsh involve ``orbital binding energies'' plotted against bond angles. The basic idea is that
the total energy is the sum of all the orbital binding energies; therefore, by considering the
stabilization or destabilization of all the orbital by a change in the angle, one can predict
(roughly) the equilibrium bond angle for a given state of a molecule. Walsh diagrams, often
called angular coordinate diagrams or correlation diagrams, are representations of
calculated orbital energies of a molecule versus a distortion coordinate, used for making
quick predictions about the geometries of small molecules. By plotting the change in
molecular orbital levels of a molecule as a function of geometrical change, Walsh diagrams
explain why molecules are more stable in certain spatial configurations (i.e. why water
adopts a bent conformation)
Application to Triatomic Molecules
The coordinate system for the AB2 molecule is shown in Figure. The AB2 molecule has C2v
symmetry when it is bent and, when linear D∞h symmetry. To simplify notations, however,
the linear configuration is considered to be simply an extremum of the C 2v symmetry.
Therefore the labels given to the orbitals through the range 90o ≤ θ < 180o are retained even
when θ = 180o. The symbols used to label the orbitals are derived from the orbital symmetry
properties in a systematic way, but a detailed explanation is not given here. For present
purposes, these designations may be treated simply as labels.

A linear XH2 molecule belongs to the D∞h point group. A qualitative MO diagram for the
formation of linear XH2 from atom X and two H atoms is shown as follows.

1
A bent XH2 molecule belongs to the C2v point group. A qualitative MO diagram for the
formation of bent XH2 from atom X and two H atoms is shown as follows.

It is seen that an AB2 molecule (one with no lone pairs) is more stable when linear then
when bent. The 1b2 orbital drops steadily in energy form θ = 90o to 180o; while the energy of
the 1a1 orbitals is fairly insensitive to angle.
For an AB2E molecule the results are ambiguous, because the trend in the energy of the 2a 1
orbital approximately offsets that of the 1b2 orbiral.
For AB2E2 molecules, the result should be the same as for AB2E. Since the energy of b1
orbirtal is independent of the angle. Thus it is not clear in this approach that AB2E2
molecules should necessarily be bent, but all known ones are.
The H2O Molecule:
Let us consider a simple molecule, H2O. It has eight electrons in its valance shell and its
2
molecular configuration is (2g) 2, (1u) 2, (1πux) 2, (1πuy) 2 or (2a12 1b22 3a12 1b12). Because
the formerly nonbonding 1πux orbital is greatly stabilized to 3a1 on bending, the water has
bent shape. Because of its unique importance, this molecule has been subjected to more
detailed study than any other AB2E2 molecule. A correlation diagram calculated specially
for H2O is shown in the figure. Although it differs in detail for the general AB2E2 shown in
the figure it is encouraging to see that the important qualitative features are the same. The
general purpose diagram pertains to a situation in which there is only a small energy
difference between the ns and np orbitals of the central atom. As stated in discussing that
general purpose diagram, it is not clear whether an AB2E2 molecule ought necessarily to be
bent.
In the diagram calculated expressly for H2O the lowest level's is practically pure 2s and its
energy is essentially constant for all angles. It can be determined from this diagram that the
energy is minimized at an angle of 106o, essentially in accord with the experimental value of
104.5o.
For BeH2 molecule : For BeH2 molecule walsh diagram is shown below. Consider (2g)
orbiutal which is constructed from atomic wave function that are everywhere positive and
hence on bending there will be increase in overlap since the two H- atoms wave function
will overlap to slightly greater extent. The energy of 2g is lowered somewhat. It is now
labelled as 2a1. In contrast the energy of the 1u increases on bending. This is because the
sign of wave function changes and overlap of H- atoms will be to lesser extent. 1u is now
labelled as 1b2. Electronic configuration of BeH2 in linear form is (2g)2 ,(1u)2 whereas in
bent form it is (2a1)2,( 1b2)2.Since 1b2 loses more energy than 2a1 gains, BeH2 ois lineart , not
bent.

Walsh Diagrams for Tetra-atomic molecules:-Walsh diagrams in conjunction with

molecular orbital theory can also be used as a tool to predict reactivity. By generating a
Walsh Diagram and then determining the HOMO/LUMO of that molecule, it can be
determined how the molecule is likely to react. In the following example, using a group
theoretical approach, MO energy level diagram for trigonal planar BH3 (D3h) is constructed.

3
Looking in the character table, we see that: 2s has a1’ symmetry; 2px and 2py have e’
symmetry; 2pz has a2”symmetry

If BH3 is assumed to be pyramidal (C3v) its MOEL diagram can be shown as:

From the character table, Boron 2s has a1 symmetry; 2px and 2py have e symmetry; 2pz has
a1 symmetry. Thus, we get:

4
Walsh diagram for AH3 can be represented as:

Since the 1a2" orbital is essentially pz orbital in D3h symmetry, overlap with hydrogen 1s
orbitals increase as they move off the nodal plane. Thus, bending the molecule results in a
5
sharp drop in the energy of 1a2", it drops much faster than the two 1e orbitals which rise
beneath it.

Problem: Using your Walsh (orbital correlation) diagram, predict the structure of
H3O+ and NH3. {Hint} H3O+ has eight valence electrons; it is isoelectronic with NH3. The
overall energy of the molecule will be lower upon adopting trigonal pyramidal geometry as
the Walsh diagram indicates.
Lewis acidic character of BF3 and CH3+: Six electron AH3 molecules should have a planar
conformation. It can be seen that the HOMO, 1e-, of planar AH3 is destabilized upon
bending of the A-H bonds to form a pyramid shape, due to disruption of bonding. The
LUMO, which is concentrated on one atomic center, is a good electron acceptor and
explains the Lewis acid character of BH3 and CH3+.Walsh correlation diagrams can also be
used to predict relative molecular orbital energy levels. The distortion of the hydrogen atoms
from the planar CH3+ to the tetrahedral CH3-Nu causes a stabilization of the C-Nu bonding
orbital, σ.

Walsh Diagrams for Penta-atomic molecules:-

Using a group theoretical approach, MO energy level diagram for tetrahedral NH4+ is
constructed. Include appropriate symmetry labels and the logic used as well as any
assumptions made in the construction of the MO diagram, bond order is predicted for
tetrahedral NH4+ on the basis of your MO energy level diagram. First, identified the valence
orbitals of the atoms involved in the bonding: the valence orbitals of the nitrogen atom are
2s, 2px, 2py, and 2pz orbitals while each hydrogen atom has a 1s orbital and figured out the
symmetry of the orbitals involved. Thus, we make SALC’s of the hydrogen 1s orbitals

Recognizing that nitrogen is more electronegative that hydrogen, we can suspect that the
hydrogen SALC’s will have the higher energy and that the a1 SALC is slightly lower than
the t2 SALC’s because of the nodal surfaces that exist although the atoms are not formally
bonded. Thus, we get the diagram below:

6
Using a group theoretical approach, a MO energy level diagram for square planar NH4+ is
constructed. Include appropriate symmetry labels and the logic used as well as any
assumptions made in the construction of the MO diagram, bond order is predicted for square
planar NH4+ on the basis of your MO energy level diagram. First, we find the symmetry
point group for square planar NH4+:

7
A Walsh diagram correlating the bonding molecular orbitals of tetrahedral NH4+ with those
of square planar NH4+ can be conctructed. The nodeless a1 - a1g orbital does not influence
shape of the molecule since it is cylindrically symmetrical. As we can see the t 2 set of
molecular orbitals in tetrahedral geometry splits into the a2u and eu set in the square planar
8
structure. The a2u MO is primarily N 3pz in character and the overlap with the hydrogen
SALC’s decreases to essentially zero, producing a large rise in its energy. Though overlap
between the eu (px and py ) orbitals and the hydrogen orbitals increase slighty, it’s is not
enough to compensate this increase in energy of the a2u orbital because the PX and py
orbitals were already in good overlap in tetrahedral geometry. Thus, when a molecule
possesses a total of eight electrons, tetrahedral structure will be preferred.

Problem:- Construct (draw) a Walsh diagram correlating the bonding molecular

orbitals of tetrahedral CH4 with those of square planar CH4.