IR Notes

• IR spectroscopy, or simply IR, is a form of spectroscopy

using infrared light to vibrate atomic bonds. This
stretching and contracting corresponds to bond strength,
and is useful in identifying non-carbon bonds. IR
frequency to transmission (%) is used to measure the type
of bond being measured.

◦ Infrared light is a much higher frequency than the

radio waves previously used for NMR.
◦ The frequency of vibration can we found using a
familiar formula:

Recall (2 pi, mmmmmm kay):

T ( period)=2 π (
√ M
K
)

and

1
T ( period)=
f (frequency )

Thus:

f (frequency )=
1 K
( )
2π M √
All of the above applying to a SHO (simple harmonic oscillator)

Fortunately for us, the contraction between atoms functions in much the same way as a SHO, and as
such the frequency of vibration can be found with a similar formula. Namely:

f B=
1 f
√
( )
2πc μ

• Where fB is the bond vibration frequency

• f is the force constant, which is approximately equal to bond strength (like spring constant/
ridgidity)

• μ is the reduced mass, which is equal to:

 m1 m2
m1 +m2

With the above knowledge, we can now approximate what sort of bonds would appear where on an IR
sheet:

As the x-axis is 1/f, and smaller frequencies equal higher energy values, we can read necessary energy
as increasing from right to left.
The structure is given for this IR sheet, the strongest bond is likely the triple bonded cyano- group. As
such, we should expect the peak near 3,400 to be it. You’d be wrong to think this.

Applying the formula:

f B=
1
√ f
( )
2πc μ
with μ=
m1 m 2
m1+ m 2

Despite the large f value for triple bonds, we must also pay attention to the reduced mass. Hydrogen
has an atomic mass of 1, which is 12x smaller than carbon.

Compared to a carbon-carbon bond of any sort:

C-C C-H
2
12 /24=6 (12*1)/(13)=.92

This is 6.5 times smaller! Which has a dramatic effect on the frequency, much more so than the force
constant will. Force constant scale to roughly the same degree as bond type (as in, the value doubles
from a single bond to a double bond and so on). So even with the approximate tripling of f seen
between a C≡C and C-H bond, we still get a 6.5x increase by the reduction of the mass quantity. His
makes X-H bonds the highest frequency, and thus the furthest on the left, followed by triple bonds.
The full ordering is below:

The single bond quadrant is referred to as the fingerprint region. It’s given this name because it’s
unique to each molecule, and can be used to differentiate between two similar molecules that are
difficult to solve otherwise. This region is typically not interpreted, rather it is compared with sample
‘fingerprints’. NMR may be more useful for single carbon bond identification.

---

• The 3000-4000 region can be used to help identify the sort of single hydrogen bond present. As
the reduced masses are all vary similar (each element within 1 amu of carbon), the force
constant becomes more predictive of the presented values.
◦ Here are the ‘general ranges’ for IR in this region, in actuality these ranges can bleed into
each other, more specific considerations will follow.
If you recall from your orgo days, hydroxy groups (O-H) for large deep troughs. Why is this?

Both of these show absorption over 80%. This is because of O-H’s unique tendency to hydrogen bond,
which means resonance can be distributed among neighboring hydroxy groups.

This effect is more obvious when it is losr, as is seen with BHT:

Width can we inferred to correlated with degree of hydrogen bonding.

• Strength of absorption (% absorption) correlates with differences in electronegativity of atoms

involved in a bond/ dipole moment of an atom. The gist of why this is that bonds with greater
polarity have a greater electric field generated due to differences in charge between the
participating atoms. This magnetic field will interact with the infrared light (resonating with the
field), and the radiation will be absorbed (assuming resonance). This will change the electron
density from it’s default or ground state, I’m not sure what the nature of that change is.

To summarize: