GLOBAL JOURNAL OF ANALYTICAL CHEMISTRY

Vibrational analysis of 4, 4-methylene diphenyl diisocyanate

G. А. Pitsevicha,*, Maksim Shundalaua, М. А. Ksenofontovb, D. S. Umreikob

a
Physics Faculty, Belarusian State University (BSU) Minsk, Belarus
b
A.N. Sevchenko Research Institute for Applied Physical Problems of BSU, Minsk, Belarus
*
Author for correspondence: G. А. Pitsevich, email: pitsevich@bsu.by
Received 24 Sep 2010; Accepted 22 Dec 2010; Available Online 21 Jan 2011

Abstract

Vibrational Raman and FT-IR absorption spectra of 4,4-methylene diphenyl diisocyanate (MDI) have
been recorded. The ab initio and density functional theory calculations (B3LYP/cc-pVDZ) have been performed
for the MDI geometric structure and force field. The fully optimized structure has been obtained using Quadratic
Approximation gradient method and is proved by its Hessian. Vibrational spectra have been simulated; bands and
lines in IR or Raman spectra of the MDI molecule have been identified and attributed.

Keywords: IR and Raman spectra; 4,4-methylene diphenyl diisocyanate; Ab initio computations; DFT; Force
field scaling

1. Introduction molecular spectral analysis may be supported by

Modern segmented polyurethanes
represent a class of various polymeric materials
finding extensive applications in different
branches owing to their ability to form the
macromolecular structures of a specific
architecture [1]. Being synthesized on the basis
of the reaction between the hydroxyl-containing
derivatives and isocyanates, the structure of
linear segmented urethane polymers includes
flexible and inflexible segments. Flexible
segments, as a rule, containing ether and ester
groups provide high elasticity of polyurethane.
The structure of inflexible segments is
determined by the composition of the initial di-
and polyisocyanates [2].
The vibrational spectroscopy methods
are highly efficient in studies of the structural
and physical properties of urethane polymers [3-
5]. Owing to great advances in the field of
computer science, the experimental methods of
the results of ab initio computations, whose level
has been markedly upgraded in the last years [6-
8].
One of the diisocyanates most
commonly used in the production of
polyurethanes is 4,4'-methylene diphenyl
diisocyanate (4,4'-diphenylmethane diisocyanate,
MDI) [9] (Figure 1) the structure of which
includes two isocyanate, two phenyl, and one
methylene groups. By the present time no detail
interpretation of vibrational IR [10] and Raman
spectra of this compound has been performed;
no high-level ab initio computations using the
extended bases and methods of a density
functional theory (DFT) are known. Proceeding
from the afore-said, it seems interesting to find
the spectral and structural features of the above-
mentioned compound for their further analytical
application.
This work presents the structural
computations and results interpreting the

Figure 1. Equilibrium structure of MDI molecule according to the results of B3LYPcc-pVDZ computations.

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Figure 2. Experimental (1) and simulated (B3LYP/cc-pVDZ with the force field scaling) (2) Raman spectra
of MDI.
experimental IR absorption and Raman spectra
derived with the use of ab initio computations of
the electronic structure, Hessian, intensities in IR
and Raman spectra by DFT methods.
2. Experimental
The investigated material produced by
the Alfa Aesar (Germany) with the assured 98%
purity is a solid white-colored odorless
substance.
Raman spectra of MDI in the region
20–4000 cm–1 were recorded in the dc mode by
the SPEX–RAMALOG device with a
spectrometer slit bandwidth of 2 cm–1. Excitation
by an argon laser with the wavelength 514.5 nm
was provided at the power 0.3 W. The sample
under study was a solid-phase pure material. The
recorded Raman spectrum is shown in Figure 2.
IR absorption spectra in the region 400–
4000 cm–1 were recorded by the Specord 75 IR
spectrophotometer with a slit bandwidth of 3
cm–1, and also by the Bruker Tensor 27 FT-IR
spectrometer (Figure 3) with a slit bandwidth of
1 cm–1. The sample prepared as a MDI solution
in ССl4 with the concentration 0.1 mol/l was
placed into a cell of NaCl 0.267 mm thick. In the
Figure 3. Experimental (1) and simulated (B3LYP/cc-pVDZ with the force field scaling) (2) IR spectra of
MDI over the region 500-3 300 cm-1
low-intensity region 50—400 cm–1 (Figure 4),
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the spectra were recorded by the Bruker Vertex
70 FT-IR spectrometer using a cell with
polyethylene windows.
3. Computation method
Computations of the structural and
spectral characteristics of MDI molecule were
realized with the use of the quantum-chemical
package GAMESS [11, 12]. The obtained results
were visualized with the help of MacMolPlt
program [13]. Optimization of the equilibrium
structure; computations of a force field, normal
coordinates analysis and intensities for IR and
Raman spectra in the harmonic approximation
were performed using the standard cc-pVDZ
basis [14] by DFT methods with the help of the
hybrid B3LYP functional [15-17]. This
approximation widely applied in simulations of
the structure and vibrational spectra for organic
compounds [18-20] is also a good practice when
interpreting the IR and Raman spectra of methyl
carbamate [21] and methyl phenyl carbamate
[22] molecules.
Hessian derived as a result of the initial
computations was used further in the following
series of computational procedures for
vibrational frequencies of MDI:
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 GLOBAL JOURNAL OF ANALYTICAL CHEMISTRY
Figure 4. Experimental (1) and simulated (B3LYP/cc-pVDZ with the force field scaling) (2) IR spectra of
MDI over the region 50-350 cm-1.
– with the use of the hydrogen atomic
weight 1.0078 а. w. u.;
– with the use of the ―spectroscopic‖ atomic
weight of hydrogen that is equal to 1.088 а. w. u.
and partially allows for the effect of anharmonic
vibrations [23];
– with scaling of a force field.
In the process of the latter, the initial
force field obtained in computations with the
help of the package GAMESS has been
recalculated from mdyne/Å, mdyne·Å/rad2 and
mdyne/rad (for force constants of bond-bond,
bond-angle, angle-angle coupling, respectively)
to 106 cm–2 using the factors 1.5601, 1.4313, and
1.3131. Next a partial force-field scaling has
been performed. A scaling factor for the
derivatives of energy with respect to bond
lengths was equal to 0.93 . The force field thus
derived was further used in computations of the
frequencies in accordance with the program
described in [24]. The IR and Raman spectra of
MDI calculated in the approximation B3LYP/cc-
pVDZ with regard to scaling of a force field are
given in Figures 2, 3 and 4.
4. Results and Discussion
4.1. Structure
Even though C2v is the highest point
symmetry group of the equilibrium configuration
for a molecule of MDI, it is unlikely that such a
symmetry is characteristic for the molecule in its
condensed phase. Because of this, the geometry
has been optimized for C1 symmetry. The
optimized equilibrium structure of MDI
molecule is shown in Figure 1. Table 1 lists the
computed structural parameters of MDI. All
bond lengths are given in Angströms, Å; angles
— in degrees.
To check adequacy of the computed
geometric parameters in the approximation
B3LYP/cc-pVDZ used, it has been calculated
the equilibrium structure for a molecule of
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phenyl isocyanate, whose structural parameters
have been found from analysis of a microwave
spectrum [25]. The results obtained and
experimental data are also presented in Table 1.
As seen from Table 1, computation in
the approximation B3LYP/cc-pVDZ most
adequately presents the bond lengths and valence
angle values for phenyl isocyanate. It should be
noted, however, that in [25] the authors have
used a planar model of phenyl isocyanate
molecule with Cs symmetry. In the process
N=C=O was considered to be linear, whereas the
bond lengths C–C and C–H of a phenyl ring
were fixed (amounting to 1.399 Ǻ and 1.084 Ǻ,
respectively) the phenyl ring itself being in the
form of a regular hexagon.
Deviations of the bond lengths
computed for O=C, C=N, and C–C from the
experimental ones are within 0.5%, for C–H they
come to 0.8%, and only for N–C the computed
length is higher by 2.2% than the experimental
one. An error in the angle for C=N–C is also
0.5%. According to the computations, the group
N=C=O turns to be nonlinear. Due to
monosubstitution by the isocyanate group,
distortions of a phenyl ring are insignificant. As
demonstrated by the computations performed,
the equilibrium configuration of phenyl
isocyanate molecule is nonplanar, deviation of
the isocyanate group from the phenyl ring plane
being about 6º.
Important criteria for the represented
geometry are rotational constants which are
listed in Table 2 for phenyl isocyanate in
comparison with the experimental values.
Besides, this Table presents the deviations
A = (Aexp – Acalc)/Aexp (as a percentage) from the
experimental values (B and C are found in a
similar way). It is seen that the computations in
the approximation B3LYP/cc-pVDZ give highly
accurate rotational constants for a molecule of
phenyl isocyanate.
In case of MDI molecule the computed
structural parameters both of the isocyanate and
phenyl groups are slightly different from the
corresponding values for a molecule of phenyl
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Table 1. Structural parameters of MDI and phenyl isocyanate molecules calculated using B3LYP/cc-pVDZ
approximation.

MDI Phenyl isocyanate

Parameter
B3LYP/cc-pVDZ B3LYP/cc-pVDZ Experiment [25]
O=C 1.175 1.176 1.171
C=N 1.214 1.212 1.207
N–C 1.401 1.400 1.370
C4–C5, C20–C21 1.407 1.406 1.399
C5–C6, C21–C22 1.392 1.397 1.399
C6–C7, C22–C17 1.406 1.398 1.399
C7–C8, C17–C18 1.401 1.399 1.399
C8–C9, C18–C19 1.397 1.396 1.399
C9–C4, C19–C20 1.400 1.395 1.399
C7–C14, C17–C14 1.519 — —
C5–H10, C21–H25 1.093 1.093 1.084
C6–H11, C22–H26 1.093 1.093 1.084
C8–H12, C18–H23 1.093 1.093 1.084
C9–H13, C19–H24 1.091 1.092 1.084
C14–H15, C14–H16 1.103 — —
O=C=N 172.82 172.45 180.0
C=N–C 137.62 139.91 140.6
N3–C4–C5, N27–C20–C21 122.35 122.67 120.0
C4–C5–C6, C20–C21–C22 119.98 119.66 120.0
C5–C6–C7, C21–C22–C17 121.38 120.60 120.0
C6–C7–C8, C22–C17–C18 117.91 119.53 120.0
C9–C8–C7, C17–C18–C19 121.42 120.40 120.0
C8–C9–C4, C18–C19–C20 119.99 120.00 120.0
H10–C5–C4, H25–C21–C20 119.75 119.71 120.0
H11–C6–C5, H26–C22–C21 119.11 119.27 120.0
H13–C9–C4, H24–C19–C20 119.02 118.94 120.0
C6–C7–C14, C22–C17–C14 120.77 — —
C7–C14–C17 114.92 — —
H15–C14–C7, H16–C14–C17 108.56 — —
H15–C14–H16 105.94 — —
C–N=C=O 180.00 180.00 180.0
C–C–N=C 178.86 174.05 180.0
C14–C7–C8–C9, C14–C17–C18–C19 178.80 — —
Interplane angle of phenyl rings 91.15 — —
Table 2. Calculated (B3LYP/cc-pVDZ) and experimental rotational constants of phenyl isocyanate molecule.

B3LYP/cc-pVDZ Experiment [25]

A, MHz 5285.45 5202.3
B, MHz 941.84 972.685
C, MHz 799.41 819.623
ΔA, % –1.60
ΔB, % 3.17
ΔC, % 2.53

isocyanate. Most marked distortions are To assess potentialities of the proposed

observed only for the sections of phenyl rings
directly adjoining a methylene group, whereas
the deviations of isocyanate groups from the
planes of phenyl rings are reduced down to ~ 1º
(see Table 1).
4.2. Vibrational spectra
4.2.1. Phenyl-group vibrations
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approximation in computations of the
frequencies and vibration forms for the
functional groups involved in the molecular
system under consideration, at the first stage it
has been performed computations of the
structure and of vibrational spectra for a
molecule of benzene without regard to symmetry
(I) and with the symmetry D6h (II). In case of the
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 GLOBAL JOURNAL OF ANALYTICAL CHEMISTRY
latter the frequencies and forms of normal
vibrations were additionally computed, with the
atomic weight of hydrogen replaced by the
―spectroscopic‖ one (1.088) (III) with scaling of
the whole calculated force field (scaling factor
0.93) and with real atomic weight of hydrogen
(1.0079) (IV).
As demonstrated by the results, the
optimized molecular geometries for
computations I and II are fairly close: in the
second case the bond lengths С–С, on average,
are lower by 0.00014 Å and those of С–Н, on
average, are greater by 0.0008 Å than in the first
case, whereas deviation in the angle values from
120º in the first case is below 0.04º. At the same
time, errors in the computed geometry of
benzene in the first case lead to differences in
the computed force constants for С–Н bonds
(from 0.3515 to 0.3619 Hartree/Bohr 2) and also
in the coupling constants for these bonds,
causing considerable distinctions between the
forms of stretching vibrations for С–Н bonds
and the real ones. In the second case all forms of
normal vibrations are in line with Wilson’s
system of classification [26]. In the first case
forms of the vibrations involving the carbon
ring, out-of-plane, and deformation vibrations of
С–Н are easily identified and close to the
second. Obviously, the use of symmetry in
computations is very expedient but it is clear that
identification of the forms for normal vibrations
of a benzene ring with the frequencies below
1700 cm–1 is possible in quantum-chemical
computations of spectra for aromatic compounds
without allowances for a total or local symmetry.
The computed frequencies in case II are
overestimated with respect to the experimental
ones, Δν = νcom – νexp growing with the
frequency, while the ratio νexp/νcom remains
practically invariable (0.968). As a whole, the
computations in case II represent well the
experimental frequencies, whereas the computed
intensities in IR and Raman spectra are
proportional to the experimental intensities of
spectral bands and lines in the majority of cases.
Unfortunately, sometimes the computed values
of a depolarization degree for asymmetric
vibrations are considerably lower than 0.75.
Note also that due to the computations, the А1g,
E1u – type stretching vibrations (No. 2 and No.
20 by Wilson) and E2g, B1u – type stretching
vibrations (No. 7 and No. 13 by Wilson) of С–Н
bonds are interchanged. Actually, in the region
below 1700 cm–1 a sequence of the computed
frequencies is completely in line with the
experiment, except for the B1u – type vibration
No. 12 whose computed frequency value is
1001.6 cm–1. To be in agreement with a
sequence of the computed and experimental
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frequencies, this vibration should be positioned
in the region 1057–1027 cm–1.
For computations III and IV the
vibrational frequencies associated with hydrogen
are very close, whereas the frequency values
associated with a carbon ring are practically
coincident with case II. As a whole, the
experimental absorption bands and Raman lines
of IR and Raman spectra for benzene are much
better represented in computations III and IV. It
should noted, however, that the use of a
spectroscopic weight results in the interchanged
spectral positions of two more vibrations: No. 3
(A2g) and No. 14 (B2u) as well as No. 15 (B2u)
and No. 18 (E1u). No such interchange is
observed in case IV and hence the use of a
scaling factor is preferable.
Since the molecule under study contain
a para-substituted phenyl rings, we tested
B3LYP/cc-pVDZ approximation to perform the
calculation of the structure and vibrational
spectra of p-xylene (С2h symmetry) and 4-methyl
phenyl isocyanate molecules. IR and Raman
spectra of p-xylene molecule and their
interpretations are given in [27], IR spectrum of
4-methyl phenyl isocyanate molecule is given in
[28]. As demonstrated by analysis of the
obtained results, the vibrations due to a phenyl
fragment over the spectral intervals 1650–1300
am–1 and 800–450 cm–1 retain the form described
by Wilson, being practically immiscible with
vibrations of the substitutes. The vibrations
originating from nondegenerate vibrations of
benzene in these intervals lead to insignificant
changes in the molecular frequencies of p-xylene
and methyl phenyl isocyanate. Sometimes this is
the case for the vibrations associated with
degenerate vibrations of benzene as well.
Over the interval 1250–800 cm–1
coupling of the vibrations due to a benzene ring
and to substitutes becomes more sufficient but
still the vibration number of a benzene ring in
some cases may be reliably identified according
to Wilson’s system. As a whole, the computation
results for a molecule of p-xylene are in a good
agreement with the experimental data, despite
the fact that more disorders in a sequence of the
computed and experimental frequencies are
found compared to a molecule of benzene. This
is mainly due to the increased total number of
vibrations of p-xylene molecule caused by an
increase in the number of atoms, by the relieved
degeneracy in comparison with benzene and
hence decreased frequency range between the
absorption bands and Raman lines in IR and
Raman spectra of p-xylene.
A detailed comparative analysis of the
computation results for normal vibrations of p-
xylene and methyl phenyl isocyanate molecules
reveals some vibrations of a benzene ring,
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coincident in their form and frequency,
identification of the numbers of which by
Wilson’s system is unquestionable. Besides, for
these vibrations there is correlation between the
bands and lines in IR and Raman spectra as
regards their intensity and polarization degree.
Some of them must be exhibited with a
considerable intensity in both spectra, others 
predominantly in IR spectra or exclusively in
Raman spectra. For the vibrations 8а, 8b, 6а
attributed to the first group the frequencies were
computed as 1673, 1625, 642 cm–1 in a molecule
of p-xylene and as 1667, 1623, 665 cm–1 in
methyl phenyl isocyanate, respectively. For the
second group vibrations 19а, 19b, 18а, 17b, 17а
the frequencies were computed as 1571, 1470,
1031, 1049, 831 cm–1 in a molecule of p-xylene
and as 1573, 1436, 1034, 1048, 828 cm–1 in a
molecule of methyl phenyl isocyanate,
respectively. And, finally, for the vibrations 7а,
10а, 1, 6b, 10b attributed to the third group the
frequencies were calculated as 1230, 874, 846,
466, 311 cm–1 in a molecule of p-xylene and as
1231, 840, 833, 396, 342 cm–1 in phenyl methyl
isocyanate, respectively. It should be noted that
the first and the third vibrations of the latter may
be rather conventionally assigned to breathing
vibration of a benzene ring No. 1 because a
contribution of the substitutes is significant. No
doubt that the vibrations of the first group are
most characteristic. As is known [27], the
molecules containing a parasubstituted benzene
group are characterized by a doublet of
absorption bands and Raman lines over the
spectral interval 1600–1640 cm–1, and also by a
single band and a line over the interval 610–660
cm–1. Note that all the above-mentioned
vibrations, excepting the first and the third
vibrations of the third group, are presented in
[27] as characteristic of the frequency and form
for the atomic group С6Н4 with substitutes in the
para-position. Despite the indicated
conventionality in assignment of the first and
third vibrations in the third group as a vibration
No. 1 in a molecule of benzene, it is expected
that these vibrations may be exhibited with a
high relative intensity in Raman spectra of the
compounds containing a parasubstituted benzene
ring.
Based on analysis of the spectra for a
molecule of p-xylene [27] as well as IR and
Raman spectra of many peroxide compounds
including benzene rings with different
substitutes in para-positions [29], it is inferred
that vibration No. 19b in IR spectra is, as a rule,
exhibited with a low relative intensity. At the
same time, in IR spectra of some compounds its
intensity is close to zero and hence it must be
excluded from the second group list of
characteristic vibrations. Note that the absorption
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band due to vibration No. 18а in IR spectra of
the compounds containing a parasubstituted
benzene ring is characterized by a small half-
width and high relative intensity, being exhibited
in a very narrow spectral interval of 1020–1030
cm–1. Vibration No. 6b in the third group must
be also excluded from the list of characteristic
vibrations. The line intensities in a Raman
spectrum associated with this vibration are
usually very low. Moreover, in Raman spectra of
some compounds it is not exhibited at all.
Next identifications for the computed
vibrations of MDI molecule were as follows:
vibrations 8а,b and 6а in the first group; 19а,
18а, and 17а,b in the second group; 7а, 10а, 1
and 10b in the third group. It has been
impossible to identify vibration 17b. Because of
this, vibrations 19а, 18а, 17а remain in the
second group. The computed values of these
frequencies, for the sake of convenience given
here taking no account of scaling (find the
frequencies computed with scaling of a force
field in Table 2) are the following: 1664 and
1661, 1619 and 1614, 654 and 646 cm–1 for the
first group; 1566 and 1565, 1029 and 1028, 847
and 843 cm–1 for the second group; 1151 and
1149, 879 and 847, 851 and 822, 338 and 329
cm–1 for the third group. Based on the performed
analysis, they are correlated with the following
bands and lines of IR and Raman spectra: 1612
and 1610, 1577, 642, and 621 сm-1 — for the
first group; 1527 and 1513, 1018 and 1012, 825
and 822 cm-1 — for the second; 1196, 858, 806,
341, and 336 cm–1 — for the third. Doubling of
nearly each of the vibrations studied in a
molecule of MDI is determined by the presence
of two identical substituted benzene rings, a pair
of frequencies in the majority of cases being
associated with symmetric and antisymmetric
vibrations with respect to the assumed binary
axis. In some cases one of the frequencies is
associated with a vibration having a greater
contribution of one of the rings to the potential
energy distribution (PED) whereas the other—
with a vibration having a greater contribution of
the other ring to PED. It is assumed that the
second situation is rather untrue, being caused by
the neglect of symmetry properties in the process
of quantum-chemical computations. A fairly
satisfactory agreement between the computed
and experimental frequencies, even without the
introduction of scaling factors, points to the fact
that an adequate interpretation of other
vibrations based on the data about the vibration
frequency, its relative intensity in IR and Raman
spectra is highly probable.
4.2.2. Methylene-group vibrations
It is well known that to describe the
deformation vibrations of С–Н bonds in a
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 GLOBAL JOURNAL OF ANALYTICAL CHEMISTRY
methylene group, the valence angle of Н–С–Н
and four valence angles of С–С–Н are used. The
first coordinate is associated with scissoring
vibration but, as for four natural coordinates of
С–С–Н there is a linear coupling equation, they
are also associated with three more deformation
vibrations of a methylene group: wagging,
twisting, and rocking. The potentialities of
B3LYP/cc-pVDZ approximation in
computations of vibrations for a methylene
group have been evaluated in the process of
simulation of the vibrational spectra for
molecules of diphenylmethane [9] and propane,
whose interpretation of IR and Raman spectra is
undoubtful [27].
Despite the fact that values of the
computed frequencies are predictably
overestimated relative the experimental ones, the
computation results are in a perfect agreement
with data of [27] as regards the symmetry types
and assignments. They offer an adequate
sequence of the frequencies in IR and Raman
spectra of propane molecule, excluding two
vibrations: 1394 and 1383 cm–1, the first of
which is a totally symmetric deformation
vibration of С–Н bonds in methylene groups,
and the second (В1 symmetry) — has a
contribution of wagging vibrations from a
methylene group amounting up to 22%.
According to the data of [27], these vibrations
are associated with the IR absorption bands at
1372 and 1390 cm–1. In agreement with [27], the
computation results show that in a molecule of
propane only scissoring (1488 cm–1) and twisting
(1305 cm–1) vibrations may be considered to be
localized (their contributions to PED being 67
and 80 %, respectively) whereas in other cases
deformation vibrations of a methylene group are
considerably combined with vibrations of methyl
groups and С–С bonds. To illustrate, the
contributions to PED made by rocking vibrations
of СН2 group at the frequencies 1195 and 742
cm–1 come to 36 and 54%, respectively; the
contributions made by wagging vibrations of a
methylene group at 1383 and 1354 cm–1 amount
to 22 and 56%. Also, note that the absorption
bands and Raman lines in IR and Raman spectra
associated with deformation vibrations of
methylene group in propane are characterized by
low intensity. According to the computation
results for IR and Raman spectra of
diphenylmethane и MDI molecules, only a
scissoring vibration of a methylene group in
these molecules (1419 and 1470 cm–1) remains
localized (contributions to PED coming to 96
and 95 %, respectively). As seen, the frequency
value is greatly dependent on the orientation of
benzene rings with respect to the methylene
group. Twisting vibrations of СН2 group in a
molecule of MDI contribute to PED at three
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frequencies: 1354, 1196 and 1188 cm–1 (13, 17,
and 51%, respectively) and scissoring — at two
frequencies: 1360 and 1301 cm–1 (41 and 27%).
A contribution of rocking vibrations is
considerable only at the frequency 913 cm–1
coming to 51%, and below 900 сm–1, according
to the computations, there is practically no
contribution from deformation vibrations of СН 2
group. In this way, based on the computations of
IR and Raman spectra for molecules of propane,
diphenylmethane, and MDI, only scissoring
vibrations of methylene group may be
considered to be characteristic as regards their
frequency and form. A scissoring vibration in IR
spectrum of MDI molecule may be attributed to
the low-intensity absorption band at 1465 cm-1.
The remaining methylene-group vibrations are
neither localized nor characteristic.
4.2.3. Isocyanate-group vibrations
Assignment of the isocyanate-group
vibrations was realized on the basis of the results
obtained in computations of IR and Raman
spectra of methyl phenyl isocyanate. Moreover,
in the approximation B3LYP/cc-pVDZ the
computations have been performed for IR and
Raman spectra of a molecule of phenyl
isocyanate, the interpretation of which is given
in [30]. The calculated frequency of an
antisymmetric stretching vibration of N=C=O
group (2365 cm–1) in a molecule of phenyl
isocyanate turns to be overestimated by more
than 100 cm–1 as compared to the experimental
one (2260 cm-1). A symmetric stretching
vibration of this group is associated in [30] with
the band at 1445 cm–1 but, according to the
computations, a contribution of this vibration
(that is not localized) to PED is about 30% at the
frequencies 1560 and 1481 cm–1. By [30], plane
deformation vibrations of N=C=O are
responsible for the absorption band at 567 cm–1,
whereas out-of-plane vibrations — for the band
at 631 cm–1. Based on the computations, these
vibrations in phenyl isocyanate and methyl
phenyl isocyanate molecules are localized, while
frequencies of in-plane deformation vibrations
are higher (637 and 621 cm–1) than those of out-
of-plane vibrations (559 and 558 cm–1). It should
be noted that in this case the computed and
experimental frequencies are practically
coincident. And, finally, a wide moderate-
intensity absorption band with a maximum near
100 cm–1 the authors of [30] attribute to the
plane and out-of-plane vibrations of N=C=O
group as a whole. Correspondingly, the
computed frequencies for these localized
vibrations of phenyl isocyanate and methyl
phenyl isocyanate molecules are: 83, 102 and 53,
54 cm–1. As the computed frequencies of plane
and out-of-plane deformation vibrations for
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isocyanate group (637, 630 and 562, 560 cm–1)
in a molecule of MDI are actually coincident
with those in phenyl isocyanate and methyl
isocyanate molecules, the broadened absorption
bands at 621 and 567.5 cm–1, respectively,
should be attributed to these vibrations. The
high-intensity broadened Raman lines with the
frequencies 77 and 92.5 cm–1 may be attributed
to low-intensity deformation vibrations of
N=C=O groups in a molecule of MDI.
A complete interpretation of the
experimental IR and Raman spectra for MDI
together with the frequencies and intensities
computed in the approximation B3LYP/cc-
pVDZ without (A) and with scaling (B) of a
force field is given in Table 3. The experimental
intensities in IR and Raman spectra are given in
relative units and the calculated intensities — in
D2/(a. w. u.·Å2) for IR spectrum or Å4/a. w. u.
for Raman spectrum.

Table 3. Frequencies and intensities in IR and Raman vibrational spectra of MDI.

№ Attribution Experiment B3LYP/cc-pVDZ

computation
IR Raman ν, cm–1 I
–1
ν, cm I ν, cm–1 I A B IR Rama
n
1 νCH(Ph) 99% 3066 8 — — 3216 3101 0.14 163.5
2 νCH(Ph) 99% — — 3072 0.08 3195 3081 0.07 151.2
3 νCH(Ph) 99% 3045 3 3045 0.05 3192 3078 0.22 123.2
4 νCH(Ph) 99% — — 3039 0.10 3182 3069 0.22 100.2
5 νCH(Ph) 99% 3025 12 3023 0.03 3177 3063 0.17 52.5
6 νCH(Ph) 99% 3025 12 3023 0.03 3176 3063 0.21 78.0
7 νCH(Ph) 92% + δCCC(Ph) 7% 3006 11 — — 3169 3056 0.28 67.9
8 νCH(Ph) 92% + δCCC(Ph) 5% 2985 10 — — 3158 3046 0.20 43.9
9 νCH(CH2) 99% (as) — — 2947 0.06 3058 2948 0.26 82.3
10 νCH(CH2) 99% (s) — — 2931 0.10 3025 2917 0.60 183.9
11 νNCO 100% (s) 2240 88 2240 0.08 2358 2274 31.34 82.6
12 νNCO 100% (as) 2260 100 — — 2352 2268 50.69 29.4
13 8a (s) 1612 65 1611 1.10 1664 1623 0.63 514.8
14 8a (as) 1610 77 1609 0.70 1661 1620 0.94 213.4
15 8b (s) 1577 55 1577 0.01 1619 1577 0.44 2.2
16 8b (as) 1577 55 1577 0.01 1614 1572 0.37 2.2
17 19a (s) 1513 8 — — 1566 1531 0.82 191.2
18 19a (as) 1513 8 — — 1565 1528 4.39 97.8
19 νNCOs 43% (―left‖ ring) + ν NPh 16% +
νCC(Ph) 5% + δCCC(Ph) 12% + δCCH(Ph) 1456 1 1455 0.05 1484 1445 0.05 115.5
17%
20 νNCOs 43% (―right‖ ring) + νNPh 16% +
νCC(Ph) 5% + δCCC(Ph) 6% + δCCH(Ph) 1450 3 1450 0.10 1482 1444 0.04 142.2
18%
21 Scissoring CH2 95% 1465 1 — — 1469 1469 0.11 17.6
22 νCC(Ph) 61% + δCCC(Ph) 25% + δCCH(Ph)
1443 8 1443 0.30 1447 1416 0.01 6.7
26% (s)
23 νCC(Ph) 61% + δCCC(Ph) 24% + δCCH(Ph)
1435 21 1434 0.03 1446 1414 0.07 2.2
27% (as)
24 Wagging CH2 42% + νCC(Ph) 16% +
1336 3 — — 1360 1345 0.51 9.8
δCCH(Ph) 12% + νCC(CH2) 7%
25 Torsional CH2 12% + δCCH(Ph) 40% +
— — 1321 0.01 1354 1329 0.01 4.8
νCC(Ph) 37%
26 νCC(Ph) 29% + δCCH(Ph) 64% — — 1300 0.01 1320 1304 0.08 1.2
27 νCC(Ph) 67% + δCCH(Ph) 24% 1297 20 — — 1317 1298 0.05 1.5
28 Wagging CH2 30% + νСС(CH2) 8% +
1286 12 — — 1301 1276 0.08 11.7
νСС(Ph) 62%
29 νCC(CH2) (as) 35% + δCCC(Ph) 64% 1232 14 — — 1226 1202 0.10 5.9
30 νCC(CH2) (s) 35% + δCCC(Ph) 70% 1206 18 — — 1215 1193 0.03 24.9

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 GLOBAL JOURNAL OF ANALYTICAL CHEMISTRY

31 7a — — 1196 0.13 1197 1184 0.10 10.6

32 7a — — 1196 0.13 1193 1182 0.02 3.2
33 Torsional CH2 51% + νCC(Ph) 15% +
δCCC(Ph) 10% + δCCH(Ph) 12% 1182 16 1184 0.01 1189 1179 0.03 36.2
34 νNCOs 24% + νNPh 16% + νCC(Ph) 36% +
δCCC(Ph) 10%+ δCCH(Ph) 13% (―right‖ 1146 50 — — 1151 1122 1.52 43.6
ring)
35 νNCOs 23% + νNPh 17% + νCC(Ph) 27%+
δCCC(Ph) 22%+ δCCH(Ph) 10% (―left‖ — — 1141 0.02 1149 1119 1.43 49.3
ring)
36 νCC(Ph) 39% + δCCC(Ph) 34% +
1109 90 1109 0.15 1125 1115 0.43 0.5
δCCH(Ph) 36% (as)
37 νCC(Ph) 36% + δCCC(Ph) 25% +
1051 5 1053 0.05 1119 1108 0.18 1.0
δCCH(Ph) 31% (s)
38 18a 1018 65 — — 1029 1010 0.15 0.4
39 18a 1012 5 — — 1028 1009 0.17 0.4
40 ρCH 86% + ρCC 10% (―left‖ ring) 966 2 — — 985 986 0.00 1.3
41 ρCH 78% + ρCC 12% (―right‖ ring) 952 2 — — 982 983 0.01 0.7
42 ρCH 72% + ρCC 14% (―left‖ ring) 943 5 — — 971 971 0.00 2.3
43 ρCH 76% + ρCC 16% (―right‖ ring) 943 5 — — 970 970 0.02 3.2
44 Rocking CH2 51% + ρCH 21% 915 22 — — 913 911 0.12 0.4
45 17a 855 45 — — 879 876 0.25 8.9
46 1 (as) — — 858 0.08 851 847 0.05 6.1
47 10a — — 859 0.06 847 844 0.33 5.7
48 10a 855 44 856 0.04 843 835 0.01 3.5
49 17а 822 46 — — 835 827 0.84 3.1
50 1 (s) — — 806 0.3 822 807 0.39 47.1
51 δCCC (CH2) 10% + ρCC 43% + ρCH 22% — — 752 0.05 773 769 0.15 3.6
52 νNPh 21% + νCC(CH2) 12% + δCCC(Ph)
703 3 703 0.01 743 730 0.42 1.2
41%
53 4 691 10 — — 728 728 0.01 0.3
54 4 667 20 — — 708 702 0.24 3.1
55 6a 642 10 642 0.06 654 651 0.06 4.0
56 6a 642 10 642 0.06 646 643 0.01 11.6
57 δNCO (s) 52% (in-plane) 621 38 621 0.10 638 637 0.10 0.2
58 δNCO (as) 62% (in-plane) 621 38 621 0.10 631 629 0.50 0.0
59 ωNCO 96% (out-of-plane) 567 67 — — 563 563 0.73 2.8
60 ωNCO 99% (out-of-plane) 567 67 — — 560 559 0.55 0.6
61 δNCO 6% + δCCC(Ph) 16% + ρOCNC 22%
+ ρCCNC 30% — — 562 0.05 546 542 0.08 0.9
62 ρCCNC 68% + ρCCCC 30% — — — — 521 521 0.13 0.0
63 νNPh 9% + δCCC(Ph) 20% + δCCC (CH2)
7% + ρCCNC 22% + ρCCCC 8% + ρCCCN — — 470 0.05 475 472 0.00 4.7
29%
64 νNPh 11% + δNCO 12% + δCCN 20% +
δCCC(Ph) 37% + δCCC(Ph–CH2) 12% — — 467 0.02 455 452 0.02 0.1
65 δCCN 13% + ρCCCN 52% + ρCCCH 12% — — 416 0.01 425 425 0.04 0.5
66 ρCCC-C (Ph–CH2) 82% — — 416 0.01 423 423 0.01 0.2
67 δCCN 41% + δCCC(Ph) 10% + δCCC(Ph–
CH2) 8% + ρCCCN 12% — — — — 418 418 0.15 1.1
68 δCCN 35% + δCCC(Ph) 32% + δCCH(Ph)
— — 387 0.01 387 384 0.27 4.1
8%
69 10b — — 341 0.15 338 338 0.02 2.0
70 10b 333 3 336 0.35 329 328 0.03 10.9

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 GLOBAL JOURNAL OF ANALYTICAL CHEMISTRY

71 Rocking (СH2 as a whole) 50% +

deformations of NCO as a whole 310 7 — — 289 289 0.11 0.7

72 Relative deformation vibrations of

benzene rings as a whole 225 1 234 0.04 228 227 0.04 4.1

73 Relative deformation vibrations of

benzene rings as a whole — — 177 0.03 168 167 0.00 1.2

74 ρCCC-C (Ph-CH2) 40% + ρCCNС 35% +

— — — — 139 139 0.01 0.3
ρCCCN 30%
75 Plane deformations of NCO groups as
— — 92 1.10 90 90 0.03 4.0
a whole
76 Plane deformations of NCO groups as
— — 92 1.10 83 83 0.04 3.7
a whole
77 Out-of-plane deformations of NCO
groups as a whole — — 77 1.00 69 69 0.01 0.4

78 Out-of-plane deformations of NCO

groups as a whole — — 77 1.00 54 54 0.00 1.5

79 Relative torsional vibrations of benzene

rings as a whole — — 41 2.00 29 29 0.00 13.8

80 Relative torsional vibrations of benzene

rings as a whole — — — — 21 21 0.00 6.4

81 Relative translational vibrations of

benzene rings as a whole — — — — 20 20 0.00 9.5

computations but also additional arguments. A

5. Conclusions
Using B3LYP/cc-pVDZ approximation,
the ab initio and DFT computations of an
equilibrium geometry and of IR, Raman spectral
characteristics have been performed for a
molecule of 4,4-methylene diphenyl
diisocyanate as well as for molecules of benzene,
p-xylene, methyl phenyl isocyanate, phenyl
isocyanate, diphenylmethane and propane
simulating molecular fragments of the
compound under study. A good agreement
between the results of quantum-chemical
computations and the data used for attribution of
the bands and lines in IR and Raman spectra of
benzene, p-xylene, and propane molecules,
obtained previously from the computations of
normal vibrations for the molecules and their
isotopically-substituted analogs, has
demonstrated that, owing to the functional of
B3LYP in combination with cc-pVDZ basis, the
structure, frequencies, and forms of normal
vibrations may be reliably computed for small
molecules containing hydrogen and carbon
atoms only. For molecules including the atoms
of oxygen and nitrogen deviations between the
computed and experimental frequencies are
somewhat greater. Because of this, interpretation
of spectra, with the increased molecular sizes
and with involvement of oxygen and nitrogen
atoms in their structure, necessitates not only the
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comparative analysis of the vibration modes
obtained by quantum-chemical computations for
all the above-mentioned molecules and of their
spectra, together with a detail analysis of IR and
Raman spectra for numerous peroxide
compounds containing parasubstituted benzene
rings has enabled a reliable interpretation of IR
and Raman spectra for a molecule of MDI. The
computed characteristics of the vibrational
spectra of MDI exhibit a good agreement with
the experimental data.
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