Modeling Stretching Modes of Common Organic Molecules with

the Quantum Mechanical Harmonic Oscillator (QMHO)

Oct. 11,
2016
Tanya Daher
Department of Chemistry, The Pennsylvania State University, University Park,
PA, 16802 CHEM 457, Section 4, Fall 2016

Abstract
Applying quantum mechanics to classical mechanics allows for
approximation of molecular vibrational frequencies of stretching modes for
common organic molecules comprised of C, H, O, and N atoms covalently
bonded. This is useful for obtaining these values in the absence of
appropriate instruments. Assuming only the two bonded atoms are involved
in stretching motion and that the force constant is directly proportional to the
bond order, a simple model was constructed such that a linear best fit
between observed frequency values (from FT IR spectrometer) and optimized
predicted frequency values resulted in a slope of 1.0
Introduction:
In physical chemistry, the application of quantum mechanics to
classical mechanics may allow for reasonable modeling of molecular
behavior, which may be useful if access to instruments is limited. 1,2 For

instance, given the classical model for spring potential (F = -k*x; where F is
the restoring force, k is the force constant, and x is the displacement from
the equilibrium point [F = 0] due to force applied along the spring axis) the
Schrdinger equation for a harmonic oscillator may be obtained. 1The
Schrdinger equation is the fundamental equation of physics for describing
quantum mechanical behavior, describing the behavior of a wavefunction
over time.3 Classically, a harmonic oscillator is a system that when displaced
from an equilibrium point, will experience a restoring force proportional to
the displacement.A quantum mechanical harmonic oscillator (QMHO) is the
quantum mechanical analog of the classical harmonic oscillator; it is one of
the principle model systems in quantum mechanics and has several useful
applications.1,2
To understand how approximation of vibrational spectra using the
QMHO might be accomplished, it is important to understand how these
spectra are formed. Molecules considered IR-active absorb infrared light by
undergoing a change in net dipole moment as a result of vibrational motion. 1
This motion is classified as stretching or bending. 1 Stretching is a change in
the distance between two bonded atoms, whereas bending is a change in the
angle between two bonds.
In this experiment, the QMHO will be used to produce a model for
predicting frequencies of absorption attributable to stretching modes, which
are observed as absorbance bands on an IR spectrum, between 4000 to
1450 cm-1.1 Subsequent comparison to experimentally determined spectra
2

will allow for comment on the validity and limitations of the modeling. 1 Given
that stretching motion may be described as a system comprised of two point
masses (atoms) connected by a bond of variable length that undergoes a
restoring force proportional to the displacement from stretching the bond, it
follows that it might be modeled using classical harmonic motion. 1,2 While in
classical mechanics any value of total energy of the oscillator may be used,
in quantum mechanics these energy levels are discrete.1
In using the QMHO to develop a model for predicting the vibrational
frequencies of stretching modes, two assumptions must be made. 1 The first
is that stretching motion effectively involves two atoms; while this is not
accurate in practice, it is reasonable to assume the contribution of molecules
further from the bond of interest is negligible. 1 The second is that the force
constant (k) is directly proportional to the order of the bond.1

m1 m 2
m 1+ m 2

(1)

where is the reduced mass, m 1 is the mass of the first atom atom in
the system, and m2 is the mass of the second atom in the system.
Given the assumptions noted above, it is possible to calculate a force
constant (k) from the vibrational frequency determined from the model

described (as wavenumber

-1
]; inverse wavelength (cm ); used for

convenience due to direct proportionality to energy). 1 These are obtained by

constructing the molecule in software (Gaussian 03), with parameters set
3

such that they are consistent with the assumptions made in the model, and
assessing a theoretical IR spectra.1 For calculations and comparison to
experimental values, these will be scaled with an appropriate scale factor, as
below In equation 2
Gaussian,corrected =0.897Gaussian

(2)

Given vibrational frequency as wavenumber and the reduced mass of the

diatomic system, the force constant (k) may be calculated using equation
2

2 c
k =( )

(3)

Given the assumption that the force constant is proportional to the bond
order, division of k by bond order yields the effective force constant k eff as in
equation 4.
k eff =

k
bond order

(4)

Averaging the keff for each C, H, O, N, bond observed will produce the
effective, average force constant, which may be used with equation 5 to
predict the wavenumbers of stretching modes for C, H, O, N bonds, as per
the model described:

pred =

k
bond order
1
, eff , avg
2 c

(5)

To assess the performance of the model, a plot will be made of

predicted wavenumbers versus observed wavenumbers for the same bonds,
from spectra taken with an ATR-FT-IR spectrometer. 1 If the slope of the linear
best fit of this line is 1, then the validity of the model will be proven; if it is
not, optimization may be undertaken by multiplying predicted wavenumbers
by a the square root of a correction factor as in equations 6 and 7 until the
slope is found to be 1.0 0.01:

1
m2

(6)

opt
pred
pre =

(7)

An optimized force constant k opt,eff should be determined if optimization is

necessary equation 8
k opt
eff =k eff ,avg

(8)

It is hypothesized that the model will likely produce a reasonable

approximation of the wavenumbers of the stretching modes of covalent
bonds. However, it may not be able to distinguish between the difference in
frequency characterizes as asymmetric versus symmetric stretching, given
the simplicity and limitations of the model.1
Procedure:
In this experiment, predicted and experimental spectra are taken for
each of the following bonds, listed with their respective organic molecules
5

and their formulas: C=O (carbonyl,) acetone (C 3H6O); CN, acetonitrile

(C2H3N); O-H, n-butanol (C4H10O); C=C (alkene,) cyclohexene (C6H10); and NH, n-butylamine (C4H11N.)1 For brevitys sake, figures will reference the CN
bond.1
Experimental spectra are taken using a Thermo. Electron Crop Nicolet
6700 FT IR spectrometer; a background was obtained first, followed by the
sample spectrum. Both are taken in the absence of ambient light from the
room.1,15
Predicted spectra are taken by constructing the molecule in Gaussian
03 . The 3d structure was optimized and the spectrum calculated.
Results and Discussion
Observed wavenumbers for each stretching mode for each bond were
recorded. Predicted wavenumbers from the model described below were
scaled and used to determine the force constant k for each bond from
equations 1 and 3 mentioned in the introduction. 1. All the data observed and
calculated were tabulated below for each substance of interest.
Table 1: the special bonds in Acetone (bonds found in the IR region) with the
reduced mass of atoms sharing the bond in kg, the observed frequency in
cm-1, calculated (Gaussian) in cm-1, Keff in Nm-1, and Keff/ bond number in Nm-1.
Mod
e

bon
d
ord
er

m1
(amu)

m2
(amu)

reduced
mass
(10^-27
kg)

C=
O

12.01
07

15.99
94

0.1139

observ
ed
frequen
cy
(cm-1)
1717.6

calculat
ed
frequen
cy (cm1
)
1833.4

Keff
(Nm-1)

Keff/bond
order
(Nm-1)

1191.36

595.68
6

C-H
sp3

12.01
07

1.007
94

1.5441

3004.5

3215.2
2

468.65

468.65

Graphing these against the observed wavenumbers and assessing the

linear best fit line (y-int = 0) produced a linear slope of 1.03, outside the
target of 1.0 0.01.1 To accomplish this, one round of optimization was
assessed, by multiplying the un-optimized predicted wavenumbers by the
square root of the correction factor found from equation 6; graphing the
resulting optimized values produced the target slope for the linear fit, as
seen in figure 1

f(x) = 1x
R = 1

Figure 1: vobs vs vpre of Acetone

Producing predicted wavenumbers as in table 5 was accomplished by
constructing each molecule of interest in Gaussian. The appropriate
wavenumber was found by comparison to the various dipole moments

associated with each absorbance band frequency, until the target stretching
mode was located.
Table 2: A list of some of the bonds optimized wavenumber and the
correction factor for one bond of interest in each of the fife molecules used in
the experiment using equations 6 and 7 the corrected factor of each
molecule.
Compound

Correction Factor

Acetone (C=O)
Acetonitrile
(CN)
Cyclohexene
(C=C)
Methanol (C-O)
1-butanamine
(N-C)

1.0011
1.0082

1718.46
2262.6

1.0087

16659.24

1.0001
1.0001

1115.5
1378.77

opt
pre

(cm-1)

Division of k by each respective bond order and averaging of the

results yielded keff,avg = 529.74 N m-1, which was used with equation 8 to

produce

k opt
eff
= 530.27 that falls within 1% of keff,avg. Figures 2 and 3 show the

3D model constructed for methanol and cyclohexene.

Figure 2: A model of Methanol

Figure 3: A model of cyclohexene

Transmittance

IR

spectrum

for

each

molecule

was

obtained

experimentally using the FT-IR spectroscope. Figure 4 is the experimentally

obtained IR spectrum for acetonitrile:

Figure 4: The experimentally obtained FTIR spectrum for acetone.

The main implication of figure 1 is related to the slope, which (at 1.0)
indicates that the model discussed, while not exact, is certainly capable of
producing a reasonable approximation of the vibrational frequency of
stretching modes for C, H, O, N comprised, covalently bonded-molecules. 1
The most obvious application is naturally the ability to predict with
reasonable accuracy the frequency of these bands in the absence of the
necessary instruments. Given the models relative simplicity, this is may
prove useful, as spectroscopy instrumentation is often absurdly priced. 1
Given the simplicity of the model, and the ability to obtain this result
from more sophisticated model, an interesting topic to explore for further
research might be how to modify the model and its assumptions such that a
degree of relative simplicity is maintained while still enabling the calculation
of different values for asymmetric and symmetric stretching. In any case,
given figure 1 it may be said that this experiment has shown the validity of
using the quantum mechanical harmonic oscillator to model stretching
modes of common organic molecules.1

Conclusion:
In this experiment, the quantum mechanical harmonic oscillator was
used to produce a model for predicting the vibrational frequency of
stretching modes of covalent bonds of organic molecules comprised of C, H,
10

O, and N atoms. Application of this model might include use in approximating

these values in the absence of access to the appropriate spectroscopic
instrumentation. Assumptions made in producing and using this model
include that only the two bonded atoms are involved in stretching motion
and that the force constant k is directly proportional to the bond order. Using
Gaussian

modeling

software,

frequency

(wavenumber;

cm -1)

was

calculated. Averaging and optimizing this value allowed for calculation of

predicted

wavenumbers

that,

when

graphed

against

experimental

wavenumbers, yielded a slope of 1.0, demonstrating the usefulness of the

model described in approximating vibrational frequency of stretching modes
of common organic molecules.
Acknowledgement
We thank Mr. Kyle Munson and Mr. Jovan Livada for their assistance through
the experiment.
References
(1)Milosavljevic, B. Lab Packet for Chem 457: Experimental Physical
Chemistry, Fall 2016 ed.; Penn State Department of Chemistry: State
College, 2016.
(2)Georgia State Univerity: Department of Physics. Quantum Harmonic
Oscillator: Schrodinger Equation. http://hyperphysics.phyastr.gsu.edu/hbase/quantum/hosc2.html. (accessed Oct 9, 2016).
(3)Wolfram Research. Quantum Mechanics: Schrodinger Equation.
http://scienceworld.wolfram.com/physics/SchroedingerEquation.html
(accessed Oct 9, 2016).
(4)California Institute of Technology. Feynman Lectures: The Harmonic
Oscillator. http://www.feynmanlectures.caltech.edu/I_21.html (accessed
Oct 9, 2016).

11

(5)Satori Seal. Vibrational Motion Figure.

http://www.satoriseal.com/technical/technical_articles/Untitled
%201_html_7da6d277.png (accessed October 9, 2016).
Supporting Information
Sample Calculation:
The correction factor
=

1
1
=
=0.9935
2
1.0065
m

Optimized keff
opt

k eff =k eff ,avg

0.9935529.74
526.29

Optimized Predicted Wavenumber

opt
pred
pre =

0.99351717.6
1712.01cm1

Supporting Data and Figures

12

Table 1s: the special bonds in Acetonitrile (bonds found in the IR region) with
the reduced mass of atoms sharing the bond in kg, the observed frequency
in cm-1, calculated (Gaussian) in cm-1, Keff in Nm-1, and Keff/ bond number in
Nm-1.
mo
de

bon
d
ord
er

m1
(amu
)

m2
(amu)

reduced
mass
(10^-27
kg)

C
N
C-H
sp3

12.0
10
12.0
10

14.00
67
1.007
94

calculate
d
frequenc
y (cm-1)

Keff
(Nm-1)

Keff/bond
order
(Nm-1)

0.1073

observ
ed
frequen
cy
(cm-1)
2253.3

2260.61

1932.5

595.6

1.5441

2950

2983

476.45

476.45

Figure 1s: vobs vs vpre of Acetonitrile

13

3500
3000
2500

f(x) = 0.99x
R = 1

2000

v obs (cm-1)
1500
1000
500
0

Figure 2s: The experimentally obtained FTIR spectrum for acetonitrile. The
vibrational frequency of the stretching mode of the bond of interest CN is
indicated by the arrow
(v = 2253.3 cm-1).

Table 2s: the special bonds in Cyclohexene (bonds found in the IR region)
with the reduced mass of atoms sharing the bond in kg, the observed
14

frequency in cm-1, calculated (Gaussian) in cm-1, Keff in Nm-1, and Keff/ bond
number in Nm-1.
mod
e
C=C

bo

m1

m2

redm

obs freq

2
1

12.01
07
1.007
94
1.007
94

9.97227
E-27
1.54416
E-27
1.54416
E-27

1652.3

C-H
sp3
C-H
sp2

12.01
07
12.01
07
12.01
07

2926.1
3062.4

calc
freq
1863.6
7
2950.5
4
3341.5
9

keff

964.71

482.35

469.85

469.85

513.3

513.3

f(x) = 0.99x
R = 1

1400

1600

1800

2000

2200

2400

2600

2800

3000

3200

v pre(cm-1)

15

Figure 3s: vobs vs vpre of Cyclohexene

Figure 4s: The experimentally obtained FTIR spectrum for acetonitrile. The
vibrational frequency of the stretching mode of the bond of interest CC is
indicated by the arrow (v = 1652.3 cm-1).

Table 3s: the special bonds in Methanol (bonds found in the IR region) with
the reduced mass of atoms sharing the bond in kg, the observed frequency
in cm-1, calculated (Gaussian) in cm-1, Keff in Nm-1, and Keff/ bond number in
Nm-1.

mod
e
C-O

bo

m1

m2

redm

C-H
sp3
O-H

12.01
07
12.01
07
15.99
94

15.99
94
1.007
94
1.007
94

1.13923
E-26
1.54416
E-27
1.57456
E-27

obs
freq
1115.5
2831.4
3321.7

calc
freq
1068.5
4
2845.4
7
4029.5
9

keff

502.49

251.24

439.55

439.55

654.6

654.6

16

3500
3000

f(x) = 0.99x
R = 1

2500
2000

v obs (cm-1)
1500
1000
500
0

Figure 5s: vobs vs vpre of methanol

17

Figure 6s: The experimentally obtained FTIR spectrum for acetonitrile. The
vibrational frequency of the stretching mode of the bond of interest C-O is
indicated by the arrow (v = 1652.3 cm-1), and O-H (v= 3321.7 cm-1)

Table 4s: the special bonds in 1-Butanamine (bonds found in the IR region)
with the reduced mass of atoms sharing the bond in kg, the observed
frequency in cm-1, calculated (Gaussian) in cm-1, Keff in Nm-1, and Keff/ bond
number in Nm-1.
mod
e
C-N

bo

m1

m2

redm

obs freq

C-H
sp3
H-N

12.01
07
12.01
07
1.007
94

14.006
74
1.0079
4
14.006
74

1.54416
E-27
1.07373
E-26
1.56139
E-27

keff

1378.7

calc
freq
1163.8

104.04

104.04

2957.8

2970

479.7

479.7

3368.2

3783.5
9

627.90

627.90

18

4000
3500
3000

f(x) = 1.01x
R = 1

2500

v obs (cm-1) 2000

1500
1000
500
0

Figure 7s: vobs vs vpre of 1-butanamine

19

Figure 8s: The experimentally obtained FTIR spectrum for acetonitrile.

The vibrational frequency of the stretching mode of the bond of
interest C-N is indicated by the arrow (v = 1378.7cm-1), and N-H (v =
3368.2 cm-1)

20