Indian J Phys (March 2012) 86(3):209218

DOI 10.1007/s12648-012-0042-1

ORIGINAL PAPER

Isomeric identification of methylated naphthalenes using gas phase

infrared spectroscopy
S Chakraborty, P Das and P K Das*
Department of Inorganic and Physical Chemistry, Indian Institute of Science, Bangalore 560012, India
Received: 22 June 2011 / Accepted: 07 March 2012 / Published online: 18 April 2012

Abstract: We report gas phase mid-infrared spectra of 1- and 2- methyl naphthalenes at 0.2 cm-1 resolution. Assignment
of observed bands have been made using scaled quantum mechanical (SQM) calculations where the force fields rather the
frequencies are scaled to find a close fit between observed and calculated bands. The structure of the molecules has been
optimized using B3LYP level of theory in conjunction with standard 6-311G** basis set to obtain the harmonic frequencies. Using the force constants in Cartesian coordinates from the Gaussian output, scaled force field calculations are
carried out using a modified version of the UMAT program in the QCPE package. Potential energy distributions of the
normal modes obtained from such calculations helped us assign the observed bands and identify the unique features of the
spectra of 1- and 2-MNs which are important for their isomeric identification.
Keywords:

Infrared spectra; FT-IR spectrometer; Vibrational analysis; Density functional theory

PACS Nos.: 33.20.Ea; 07.57.-c; 33.20.Tp; 31.15.E-

1. Introduction
Naphthalene and its methylated isomers belong to the class
of polycyclic aromatic hydrocarbons (PAHs). Methylnaphthalenes (MNs) are formed in the environment due to
incomplete combustion of diesel, cigarette smoke, etc.
[13]. Diehl et al. [4] determined the amount of aromatic
hydrocarbons in gasolines by gas chromatography/fourier
transform infrared spectroscopy (GC/FT-IR) technique and
found that the amounts of 1- and 2-MN are *0.08 0.01
and 0.18 0.01 %, respectively in the total amount of
aromatic hydrocarbons present in gasoline. Chiu et al. [5]
performed structural characterization of polycyclic aromatic
compounds from a mixture of 20 authentic compounds that
have been identified in various combustion extracts
(including 1- and 2-MN) by GC/MS and GC/FT-IR techniques. They recorded the IR spectra at 8 cm-1 resolution
and concluded that FT-IR spectroscopy provides unambiguous differentiation between the structural isomers of MN.
The isomeric identification has been done based on qualitative assignment of aromatic CH out-of-plane bending
vibrations appearing in the region of 740830 cm-1.

*Corresponding author, E-mail: pkdas@ipc.iisc.ernet.in

Recently Iavicoli et al. [6] have determined the amounts of

airborne PAH contents at an airport by gas-chromatography/
mass spectrometry (GC/MS) and found that the concentrations of 1- and 2-MNs are high and vary in the range
2435,000 and 6428,500 ng/m3, respectively. We have
found that the NIST reported vapor phase infrared spectra of
1- and 2-MN were recorded at low resolution (23 cm-1)
and several peaks are not well resolved [7]. In this work we
have recorded the gas phase IR spectra of 1- and 2-MN with
high resolution and performed scaled force field calculations
to assign the spectra unambiguously. The aim of our work is
two-fold: (i) to record the gas phase IR spectra of 1- and
2-MN and assign the vibrational bands and (ii) to look for
unique regions of the spectra based on which fingerprinting
of the MN isomers can be done.

2. Experimental
MNs used in this study are 1-methyl naphthalene (95 %)
and 2-methyl naphthalene (97 %) were bought from
Aldrich, USA. The compounds were converted into gas
phase by heating and then were introduced into a multipass long-path gas cell (Model 7.2-V, REFLEX Analytical Corporation, path length 6.0 m) by mixing with UHP
 2012 IACS

210

argon as a carrier gas. All spectra were recorded in a

vertex-70 (Bruker Optik) FT-IR spectrometer. Details of
the experimental set-up have been described elsewhere
[8]. The long-path cell was wrapped with a heating tape
and a feedback heat sensor was kept on the cell to read
the temperature. The experimental temperature was set to
80 and 70 C for 1- and 2-MN, respectively. The gas cell
was kept inside a wooden box, whose inside portion was
covered with silicon sheet. This was done to protect the
spectrometer from the heat. During the experiments, the
spectrometer was purged constantly with UHP nitrogen
gas to keep moisture and carbon dioxide away. We have
recorded the spectra keeping the entrance slit width at
2 mm. The spectral resolution was set at 0.2 cm-1. The
R
integrated band area log I0 =I dm under a band was calculated by using the OPUS software provided by Bruker
Optik. The experimental intensity was calculated using
the relation [9]
Z
A 2:303 logI0 =I dm=pl
1
where A is the intensity in km mol-1, p is the partial
pressure (in atm) of the compound inside the gas cell and
l is the path length in cm. Since the compound is seeded
with argon, it is difficult to determine the partial pressure of
the compound inside the cell. From the DFT calculated
intensity and observed band area, the estimated vapor
pressures (pis) over all the bands of MN were obtained.
The vapor pressures from all the observed bands were then
averaged to get p. The same value of the partial pressure
was then plugged into Eq. (1) to obtain the experimental
band intensities. The details of the intensity calculation
have been discussed in our earlier papers [8, 10].

Fig. 1 Optimized geometry of 1- and 2-MN at the B3LYP level in

conjunction with 6-311G** basis set. The internal coordinates have
been shown in the picture. f0 1 defines one of the angle coordinates of

S. Chakraborty et al.

3. Computational method
The structures of 1- and 2-MN were optimized at the B3LYP/
6-311G** level of theory using Gaussian 03 [11] in a IBM-64
cluster. Harmonic frequencies and intensities of MNs were
calculated with the optimized structure. Figure 1 shows the
optimized structures of MNs. In our early work on dimethyl
naphthalenes [8], the harmonic frequencies from Gaussian
out-put were scaled with two different scaling factors for two
different regions of the spectrum as was suggested by Bauschlicher Jr. et al. [12] and a large discrepancy between the
theoretical and the experimental frequencies was observed. To
remove this discrepancy we have later adapted the scaled
quantum mechanical (SQM) procedure for obtaining experimental frequencies as proposed by Pulay et al. [13] using the
modified version of the UMAT program in the QCPE package
[14]. In this method force fields are scaled instead of frequencies by minimizing the fitting error between calculation
and experiment. The details of the force field calculation have
been discussed in ref [10]. The Cartesian force constant matrix
from the Gaussian output was transformed to the nonredundant local coordinate matrix of the MNs [15]. All the 57
nonredundant local coordinates of the MNs are shown in
Table 1. The experimental frequencies have been fitted with
the calculated frequencies through 100 iterations using algorithm given in [16]. Generally, the error in fitting is within a
few wavenumbers, in this method.

4. Results and discussion

The calculated spectra along with the experimental are
shown in Fig. 2. For the theoretical spectra the FWHM was

the methyl group. Twist coordinates, ss are designated as the same

way like CC bond coordinates, (bi) i=13 represents HCH angle
coordinates

Isomeric identification of methylated

211

Table 1 List of nonredundant local coordinates for 1- and 2-MN

Compounds

Nonredundant local coordinatesa

1-MN

S1 - S11 = (Ri)

i=111

(aromatic CC stretching)

S12 = R00 12 (aromatic-methyl, CC stretching)

S13 - S19 = (ri)

(aromatic CH stretching)

i=17

S20 - S22 = (r i)

i=13

(methyl CH stretching)

S23 = 2-1/2(A1 - A2) (b0 1) (aromatic C-methyl in-plane bending)

S24 - S30 = 2-1/2 (A3 - A4)(A15 - A16), (bi)

(aromatic CH in-plane bending)

9
S31;34
>
di i16
=
represent
S32;35 121=2 2a1  a2  a3 2a4  a5  a6 d2 ; d5
>
; ring deformations
S3336 0:5a2  a3 a5  a6 d3 ; d6
i=28

61=2 a1  a2 a3  a4 a5  a6 d1 ; d4

S37 = 6-1/2 (f0 1 ? f0 2 ? f0 3 - b1 - b2 - b3) (methyl sym. def.) (da)

9


S38 61=2 2f01  f02  f03 methyl antisym: def: >
>
=


ds
S39 21=2 f02  f03 methyl antisym: def:
>
>
;
S40 61=2 2b1  b2  b3 rocking methyl qCH3
S41 = 2-1/2 (b2 - b3) (rocking methyl) qCH3
S42 = c0 1 (aromatic C-methyl out-of-plane bending)
S43 - S49 = (c0 i)
S50;53
S51;54
S52;55

(aromatic CH out-of- plane bending)

9
6
s1  s2 s3  s4 s5  s6 s1 ; s4
>
= si i16
1=2s1  s3 s4  s6 s2 ; s5
represent
>
; ring torsions
1=2
2
s 2s  s  s 2s  s s ; s
i=28

1=2

S56 = 2-1/2(s10-9-21-1 - s7-9-21-19) (s0 7) s

ring

S57 = s1011 (aromaticmethyl twist) (s00 8)

2-MN

S1 - S11 = (Ri)
S13 = R

00

12

i=111

(aromatic CC stretching)

(aromatic-methyl, CC stretching)

S12, S14 - S19 = (ri)

S20 - S22 = (r0 i)

i=17

i=13

(aromatic CH stretching)

(methyl CH stretching)

S24 = 2-1/2 (A3 - A4) (b0 2) (aromatic C-methyl, in-plane bending)

= 2-1/2 (A1 - A2)(A15 - A16), (bi)i=1,38 (aromatic CH in-plane bending)
9
S31;34 61=2 a1  a2 a3  a4 a5  a6 d1 ; d4
>
di i16
=
1=2
represent
2a1  a2  a3 2a4  a5  a6 d2 ; d5
S32;35 12
>
; ring deformations
S3336 0:5a2  a3 a5  a6 d3 ; d6
S23, S

2530

S37 = 6-1/2 (f0 1 ? f0 2 ? f0 3 - b1 - b2 - b3) (methyl sym. def.) (da)

9


S38 61=2 2f01  f02  f03 methyl antisym: def: >
>
=


ds
S39 21=2 f02  f03 methyl antisym: def:
>
>
;
1=2
2b1  b2  b3 rocking methyl qCH3
S40 6
S41 = 2-1/2 (b2 - b3) (rocking methyl) qCH3
S42 = c0 1 (aromatic C-methyl out-of-plane bending)
S43 - S49 = (c0 i)

(aromatic CH out-of-plane bending)

9
>
= si i16
represent
>
;
21=2 s1 2s2  s3  s4 2s5  s6 s3 ; s6 ring torsions
i=28

S50;53 61=2 s1  s2 s3  s4 s5  s6 s1 ; s4
S51;54 1=2s1  s3 s4  s6 s2 ; s5
S52;55

S56 = 2-1/2(s109211 - s792119) (s0 7) s

ring

S57 = s1011 (aromaticmethyl twist) (s00 8)

a

See Fig. 1 for the internal coordinates

212

S. Chakraborty et al.
1.0

Theoretical

1-MN

0.6

0.0
3200

2900

2800

Experimental

1800

1600

-1

1000

565.6
531.3

727.4

853.6

1022.8

978.8

1077.2

1213.0
1167.7

1399.7

1267.7

1200

800

600

Wavenumber (cm )

1.0

0.9

2-MN

Theoretical
0.6

3000

2900

2800

2700

-1

Wavenumber(cm )

2000

1800

1400

1200

800

620.9

699.2

884.5

1000

777.0

849.5

737.9

812.1

1600

1014.5
952.2

1173.5
1942.2
1920.6

2744.5

2877.6

0.0
3100

1134.6

2934.7

2956.8

2979.9

3024.5

3095.6

Experimetal

0.4

0.0
3200

0.8

1211.5

Experimetal

0.6

0.0

1644.6
1604.6

3062.9

1271.6

0.0

0.3

1513.2
1468.1
1440.8
1383.6
1364.8

0.2

Relative Intensity

0.4

0.3

2-MN

Theoretical

0.6

Relative Intensity

1400

-1

Wavenumber (cm )

0.8

1053.1

0.6

0.0
2000

2700

788.9

0.9

770.9

0.0

0.3

2745.3

2916.5

3000

2876.7

3100

2956.1

2981.8

3015.6

0.2

Experimental

3108.9

0.4

0.2

1514.2
1472.8
1444.7

3076.9
3062.2
3048.6

0.0

0.4

1603.2

0.2

Relative Intensity

0.4

Relative Intensity

1-MN

Theoretical

0.8

1942.6
1926.3

0.6

600

-1

Wavenumber(cm )

Fig. 2 Normalized experimental and theoretical gas phase IR spectra of 1- and 2-MN. The spectra are normalized w. r. t. the intense band found
in the region of 785815 cm-1

assumed to be 15 cm-1 which is close to what is observed

experimentally. Tables 2 and 3 list the fundamental harmonic, observed, and force field fitted vibrational frequencies with the corresponding intensities for 1- and
2-MN, respectively. From experimental spectra we
found * 30 bands although, each MN has 57 fundamentals which correspond to irreducible representation
(38A0 ? 19A00 ) under the Cs point group. This is a significant improvement over the NIST reported spectra of the
MNs where only 21 bands are seen in the 1-MN and 22
bands in the 2-MN spectra. Observed band assignments
have been done based on the fitted frequencies and
potential energy distributions (PEDs) obtained from the
SQM calculation. The entire spectrum has been divided
into three regions. In the following section we have
discussed about the details of the band assignments in
each region and isomeric identification of MNs in the gas
phase.

4.1. Spectra in the region 3,2002,800 cm-1

This region contains two characteristic sets of bands corresponding to aromatic CH and methyl CH stretches. We
have found six bands at 3108.9, 3076.9, 3062.2, 3048.6,
3015.6, and 2981.8 cm-1 for 1-MN and five bands at
3095.6, 3062.9, 3024.5, 2979.9, and 2963.4 cm-1 for
2-MN. These bands are due to aromatic CH stretching
vibrations. The corresponding fitted frequencies are at
3108.9, 3076.9, 3062.2, 3048.6, 3015.6, and 2981.8 cm-1
for 1-MN and 3095.0, 3062.9, 3024.5, 2979.9, and
2963.5 cm-1 for 2-MN, respectively. In 1-MN DFT calculation predicts seven bands; however, we observed six
bands. One band at 3003.0 cm-1 is not observed perhaps
due to low intensity. The next three bands in this region
observed at 2956.1, 2916.5, and 2876.7 cm-1 for 1-MN
and 2956.8, 2934.7, and 2877.6 cm-1 for 2-MN have been
assigned to antisymmetric and symmetric CH stretching

Isomeric identification of methylated

213

Table 2 Calculated harmonic frequencies (cm-1) and intensities (km mol-1) at the B3LYP/6-311G** level, observed frequencies (cm-1) and
intensities (km mol-1), fitted frequencies (cm-1) and PED (%) of 1-MN
Sym
No

B3LYP/6-311G**

Observed
a

Force field
Fitted

PED

2.16 (0.044)

3108.9

r4 (97)

26.18 (0.544)
9.76 (0.203)

3076.9
3062.2

r6 (90)
r2 (95)

16.52 (0.344)

3048.6

r5 (89)

7.95 (0.165)

3015.6

r3 (93)

3003.0

r7 (95)

9.47 (0.197)

2981.8

r1 (97)

2956.1

16.94 (0.352)

2956.4

r20 (84) ? r10 (14)

29.355

2876.7

11.28 (0.234)

0.276

(1625.0)

Harm.

Int.

Freq.

3193.8

15.807

3108.9

2
3

3183.1
3182.2

25.775
34.316

3076.9
3062.2

3167.5

12.869

3048.6

3163.7

19.376

3015.6

3157.2

1.117

(3003.0)

3155.3

2.495

2981.8

3104.7

19.117

3019.8

10

1664.8

Int. (Rel. Int.)

A0

11

1641.6

9.211

1603.2

12

1620.4

1.322

(1590.0)

13

1548.4

8.438

1514.2

14

1505.3

7.124

1472.8

15

1494.6

0.370

(1465.0)

16

1465.8

2.803

1444.7

17
18

1425.7
1416.2

12.718
1.479

1399.7
1383.3

19

1391.9

0.307

20

1376.0

0.963

21

1290.4

3.361

1267.7

22

1263.7

0.236

(1239.0)

23

1236.6

1.802

1213.0

24

1189.4

1.958

1167.9

25

1185.3

0.724

26

1168.5

27

4.96 (0.103)

2874.8

r10 (86) ? r20 (14)

1628.4

R8 (12) ? R10 (10)

1602.3

R2 (19) ? R4 (18) ? R8(12) ? R10 (11)

1586.8

R6 (15) ? R3 (12)

6.27 (0.130)

1517.0

R9 (20)

2.28 (0.047)

1474.1

dsCH3 (63)

1464.8

b2 (15) ? b5 (12) ? b10 (10)

6.13 (0.127)

1440.5

dsCH3 (20) ? b7 (17)

8.73 (0.181)
1.41 (0.029)

1398.0
1383.2

b4 (15) ? b6 (12)
d6 (85)

(1365.0)

1365.8

R6 (30)

(1349.0)

1347.7

R2 (13) ? R10 (12)

1268.1

b8 (23) ? b4 (19) ? b7 (17) ? R11 (10)

1239.7

b10 (28)

0.96 (0.020)

1212.6

R5 (23) ? R7 (15) ? R11 (13) ? b6 (11)

1.38 (0.028)

1168.6

b2 (40) ? b3 (15)

(1162.0)

1162.1

b5 (37) ? b4 (17) ? R8 (15)

0.754

(1146.0)

1147.3

b6 (24) ? R10 (19) ? b7 (17)

1098.8

3.526

1077.2

1076.9

R3 (40) ? b10 (12)

28

1078.8

0.041

(1058.0)

1057.7

d3 (30) ? R1200 (17) ? d8CH3 (14)

29

1045.4

5.824

1022.8

1022.4

R9 (54)

30

994.9

1.844

(975.0)

977.7

dsCH3 (28) ? d3 (16) ? b8 (15)

31

871.3

0.244

(854.0)

854.6

d3 (17) ? b8 (15) ? R1200 (14) ? d1 (11) ? R6 (11)

2.47 (0.051)

5.45 (0.113)
7.80 (0.162)

32

803.9

0.797

(792.0)

790.4

b8(21) ? d2 (17) ? d3(17) ? d5 (16)

33
34

712.4
577.4

1.569
1.491

(698.0)
565.6

698.4
565.3

d4 (36) ? R6 (13) ? R1200 (10)

d4 (38) ? d1 (18)

35

520.2

0.197

(510.0)

510.2

d5 (24) ? d2 (18) ? d1 (18) ? d4 (10)

36

483.9

0.878

(474.0)

474.1

d1 (28) ? d2 (24) ? d5 (20)

37

442.7

1.319

(434.0)

433.8

r30 (44) ? d2 (15) ? d5 (13)

38

278.5

0.445

(273.0)

273.1

r30 (55) ? d5 (16) ? d2 (14)

3065.7

20.366

2916.5

1.61 (0.033)

00

39

8.66 (0.180)

2918.2

r10 (100)

40

1487.7

7.900

1465.6

2.01 (0.041)

1459.4

qCH3 (92)

41

1061.7

1.590

1053.1

5.15 (0.107)

1048.4

daCH3 (50) ? dsCH3 (17) ? qCH3 (10)

4.20 (0.087)

42

996.2

0.510

978.8

978.6

c5(32) ? c6 (31) ? c7 (12) ? c4 (11) ? s3 (10)

43

983.5

0.700

(964.0)

963.3

c2(48) ? c10 (17) ? c3 (17)

44

964.0

0.873

(945.0)

944.1

c7 (29) ? c4 (25) ? c6 (18) ? c5 (16)

214

S. Chakraborty et al.

Table 2 continued
Sym

B3LYP/6-311G**
Int.

Observed
Freq.

No

Harm.

45

913.3

0.001

(895.0)

46

873.2

1.018

853.6

Force field
Int. (Rel. Int.)

1.48 (0.030)

Fitted

PED

895.2

c10 (46) ? c3 (33)

855.6

c7 (25) ? c4 (23) ? c8 (11) ? s3 (11)

47

808.1

55.563

788.9

48.04 (1.000)

790.6

c3 (22) ? c8 (17) ? c5 (14) ? s3 (14) ? c2 (10)

48

790.2

41.776

770.9

21.19 (0.441)

773.1

s3 (27) ? c8 (26) ? c6 (18)

49

744.1

3.062

727.4

0.59 (0.012)

727.6

c2 (17) ? c5 (17) ? c3 (16) ? c7 (15) ? c4(11)

50

638.4

0.009

(626.0)

51

545.6

6.371

531.3

6.47 (0.134)

624.9

s3 (36) ? c8 (30)

532.1

s2 (22) ? qCH3 (20) ? s6 (20) ? s1(11)

52

479.6

0.035

(470.0)

469.6

s1 (28) ? s4 (28) ? s2 (10)

53
54

419.0
248.8

4.802
2.828

(410.0)
(244.0)

410.3
244.2

s5 (49) ? s4 (11) ? qCH3 (10)

s2 (36) ? s4 (19) ? qCH3 (14) ? c10 (10)

55

183.8

2.621

(180.0)

180.1

s70 (50) ? s6 (16) ? qCH3 (12)

56

166.5

0.310

(163.0)

162.7

s70 (25) ? s2 (22) ? s5 (21) ? s6 (19)

57

132.6

0.191

(130.0)

130.1

s1 (44) ? s4 (24)

Since the fitting algorithm requires all the experimental frequencies in the SQM calculation, the number in the parentheses is introduced as a
good guess for 1-MN and do not have any other significance. RMS error is 1.4 cm-1 for the fitting of the experimental frequencies with the
calculated frequencies

Relative intensity has been calculated w. r. t. the highest intense band found at 788.9 cm-1 having an absolute intensity of 48.04 km mol-1

vibrations of the methyl group. The corresponding force

field fitted frequencies are calculated at 2956.4, 2918.2,
and 2874.8 cm-1 for 1-MN and 2955.0, 2930.4, and
2883.3 cm-1 for 2-MN, respectively. In the aromatic and
methyl CH stretching region the mean deviation between
the observed band intensity and the calculated one is large
and is found to be *11 km mol-1. This large deviation
may be due to overlapping of bands or to the occurrence of
Fermi resonances.

1-MN and (m28 ? m43) in 2-MN, respectively. These two

bands are correlated with the force field fitted frequency at
2001.1 cm-1 in 1-MN and at 1968.7 cm-1 in 2-MN. The
next nonfundamental low intensity vibrational band
observed at 1926.3 and at 1920.6 cm-1 for 1- and 2-MN,
respectively, is assigned as a combination of fundamentals
(m17 ? m51) in 1-MN and (m26 ? m47) in 2-MN. Bands
observed in this region deviate by *50 cm-1 from their
corresponding force field fitted frequency.

4.2. Spectra in the region 2,8001,800 cm-1

4.3. Spectra in the region 1,800500 cm-1
From Fig. 2 we note that there are a few bands in this region
in the observed spectra but they are absent in the calculated
spectra for both the MNs. They are nonfundamental bands
since they do not correspond to any of the fundamental calculated frequencies of the MNs. They are either overtone or
combination bands [10]. The band observed in the spectra of
1-MN at 2745.3 cm-1 having an absolute intensity of
0.484 km mol-1 is assigned as the first overtone of the
aromatic CH in-plane bending vibration, m17 by comparing
with the force field fitted frequency at 2795.4 cm-1 (see
Table 4). In 2-MN one nonfundamental band found at
2744.5 cm-1 having an absolute intensity of 0.462
km mol-1 has been assigned as the first overtone of the
aromatic ring deformation, m18 with the help of the calculated
force field fitted frequency at 2766.8 cm-1. A low intensity
band observed at 1942.6 cm-1 in 1-MN and at 1942.2 cm-1
in 2-MN is assigned as a combination band of (m29 ? m42) in

Methyl substitution leads to many intense bands in this

region of the spectra, which were not prominent in naphthalene. In the spectra of 1-MN there is one band at
1603.2 cm-1 whereas in 2-MN there are two clearly visible
bands of moderate intensity at 1644.6 and 1604.6 cm-1.
From Table 2 it is seen that in 1-MN the corresponding force
field fitted frequency is calculated at 1602.3 cm-1. From
PEDs it has been found that for this vibration more than two
aromatic CC bond motions are involved. In 2-MN, the
aromatic CC stretching vibration appears at the fitted frequency of 1609.2 cm-1 where only two different aromatic
CC bond motions are involved. The other peak calculated at
1643.5 cm-1 in 2-MN consists of a mixture of aromatic CC
stretching and aromatic ring deformation. This band found at
1628.4 cm-1 in the calculation in 1-MN is not seen in the
experimental spectra either due to very low intensity which is

Isomeric identification of methylated

215

Table 3 Calculated harmonic frequencies (in cm-1) and intensities (in km mol-1) at the B3LYP/6-311G** level, observed frequencies (in
cm-1) and intensities (in km mol-1), fitted frequencies (in cm-1) and PED (%) of 2-MN
Sym

B3LYP/6-311G**

Observed

Force field
a

Int. (Rel. Int.)

Fitted

3095.0

r6 (92)

3062.9
(3059.0)

61.93 (1.771)

3062.9
3059.0

r5 (88)
r3 (98)

1.485

3024.5

11.76 (0.336)

3024.5

r4 (93)

3154.3

10.741

(3010.0)

3010.0

r7 (97)

3151.8

10.853

2979.9

14.94 (0.427)

2979.9

r2 (97)

3151.5

5.004

2963.4

0.82 (0.023)

2963.5

r1 (92)

3105.2

17.231

2956.8

0.51 (0.014)

2955.0

r20 (72) ? r10 (20)

3021.1

38.027

2877.6

12.38 (0.354)

2883.3

r10 (79) ? r20 (21)

10

1673.5

9.919

1644.6

7.21 (0.206)

1643.5

R4 (19) ? R2 (18) ? R1 (10) ? d2(10)

7.73 (0.221)

No

Harm

Int.

Freq.

3185.3

25.505

3095.6

2
3

3172.4
3170.8

45.568
14.763

3159.5

5
6

PED

A0

11

1647.1

9.205

1604.6

12

1612.0

0.079

(1580.0)

13

1545.1

12.568

1513.2

14

1505.0

1.934

(1476.0)

13.05 (0.373)

15

1497.7

3.757

1468.1

2.51 (0.071)

1609.2

R8 (20) ? R10 (19)

1579.6

R6 (16) ? R2 (12) ? R3 (10)

1515.6

R9 (16) ? b6 (11)

1476.2

dsCH3 (60)

1469.2

b5 (15) ? b4 (10)

16

1464.1

4.288

1440.8

3.36 (0.096)

1439.2

b6 (16) ? dsCH3 (14)

17
18

1416.0
1404.5

0.528
3.267

(1388.0)
1383.6

2.63 (0.075)

1389.0
1383.4

R4 (17) ? R6 (15) ? R2 (14) ? d6(12)

d6 (72)

19

1395.5

0.411

1364.8

1.30 (0.037)

1361.7

r30 (17) ? b20 (14)

20

1384.6

2.664

(1357.0)

1354.0

R8 (20) ? R10 (15) ? R6 (12)

21

1289.3

5.222

1271.6

3.40 (0.097)

1271.2

b8 (22) ? b7 (21) ?b4 (17) ? R7(11)

22

1276.5

0.324

1231.3

1.08 (0.031)

1234.4

r30 (20) ? b3 (20) ? R1(15) ? d3 (15)

23

1233.5

0.937

1211.5

1.22 (0.034)

1211.7

R5 (20) ? R11 (15) ? b5 (10) ? b6 (10)

24

1194.1

1.927

1173.5

1.70 (0.048)

1173.3

r30 (26) ? R1200 (17)

25

1179.6

0.955

(1160.0)

26

1171.8

1.532

1134.6

27

1148.5

2.607

(1126.0)

28

1041.9

2.074

1014.5

1159.9

b5 (17) ? b6 (17) ? b7 (12)

5.30 (0.151)

1133.7

b3 (41) ? b20 (16) ? R4 (12)

1125.3

b5 (13) ? R8 (12)

6.31 (0.180)

1014.1

R9 (53)
dsCH3 (46) ? daCH3 (15)

29

1023.9

7.355

(1004.0)

1004.2

30

967.7

0.897

(949.0)

949.1

b8 (31) ? d3 (21) ? R3 (16)

31

896.0

0.151

(878.0)

877.6

d3 (43) ? R1200 (11)

32

781.4

0.147

(766.0)

33
34

711.8
636.6

0.390
2.540

699.2
620.9

1.30 (0.037)
2.97 (0.085)

766.3

R6 (34) ? R5 (12) ? R11(12) ? d1(10)

699.3
621.2

b8 (25) ? R1200 (19) ? d1 (16) ? d5(14)

d4 (53) ? d1 (30)

35

527.7

0.064

(517.0)

516.5

d5 (35) ? d2 (24) ? d4 (13)

36

453.3

0.050

(444.0)

443.9

d1 (26)? d5 (16)

37

412.7

1.509

(404.0)

404.1

d2 (50) ? b1 (28)

38

264.1

0.824

(259.0)

259.0

b1 (55) ? d5 (16)

3068.1

21.084

2934.7

A00
39

23.74 (0.679)

2930.4

r10 (100)

40

1486.1

6.885

1453.1

2.26 (0.064)

1453.1

qCH3 (92)

41

1063.2

3.568

1040.2

2.88 (0.082)

1039.8

daCH3 (51) ? dsCH3 (17)

42

994.8

0.003

(975.0)

43

975.4

1.253

952.2

44

961.3

0.969

(942.0)

5.31 (0.152)

974.7

c6 (36) ? c7(29) ? c5(14) ? s3(10)

954.6

c3 (36) ? c20 (28) ? c4 (11) ? c5(11)

943.1

c4 (28) ? c5 (21) ? c7 (16) ? c20 (12)

216

S. Chakraborty et al.

Table 3 continued
Sym
No

B3LYP/6-311G**
Harm

Observed

Int.

Force field
a

Freq.

Int. (Rel. Int.)

Fitted

PED

45

903.6

3.356

884.5

5.38 (0.154)

885.4

qCH3 (43) ? c8 (14)

46

864.6

14.635

849.5

9.91 (0.283)

849.4

qCH3 (34) ? c7 (18) ? c6 (17) ? c4 (16)

47

826.7

43.520

812.1

34.96 (1.000)

808.4

c20 (32) ? c3 (32) ? c5 (13)

48

783.7

1.884

777.0

0.81 (0.023)

772.7

s3(45) ? c8 (33)

49

753.0

26.090

737.9

21.27 (0.608)

738.0

c5 (23) ? c4 (19) ? c6 (19) ?c7 (15)

50

642.3

1.372

(629.0)

631.9

c8 (35) ? s3 (28) ? c1 (14)

51

516.1

0.060

(506.0)

506.0

s1 (21) ? s5 (20) ? c1 (18) ? s4 (13)

52

486.0

19.449

(476.0)

475.7

s6 (26) ? s2 (25) ? s5 (15) ? s4 (13)

53
54

402.2
280.5

0.196
0.313

(394.0)
(275.0)

393.4
274.9

s2 (25) ? s1 (18) ? s5 (18) ? s4 (16)

s5 (35) ? c1 (25) ? c8 (12)

55

180.1

0.773

(176.0)

176.0

s1 (38) ? s4 (31) ?s6 (13)

56

119.1

1.079

(116.0)

116.2

s2 (32) ? s6 (17) ? s5 (12)

57

87.7

0.547

(86.0)

86.0

s70 (73) ? c1 (13)

RMS error is 1.8 cm-1 for the fitting of the experimental frequencies with calculated frequencies
a

Relative intensity has been calculated w. r. t. the highest intense band found at 812.1 cm-1 having an absolute intensity of 34.96 km mol-1

The band is not resolved well except for a small shoulder appearing with the 3062.9 cm-1 band. Therefore, individual band intensity is not
reported

Table 4 Experimental and force field fitted nonfundamental bands in

MNs
Molecule

1-MN

2-MN

Observed
nonfundamental
bands

Force field fitted

nonfundamental bands

Freq.

Int.

Overtone

2745.3

0.484

2795.4 (2m17)

1942.6

0.282

1926.3

1.527

2744.5

0.462

1942.2

1.011

1968.7 (m28 ? m43)

1920.6

0.703

1942.1 (m26 ? m47)

Combination

2001.1 (m29 ? m42)

1929.8 (m17 ? m51)
2766.8 (m18)

Frequencies are in cm-1 and corresponding absolute intensities in

km mol-1

Table 5 A few characteristic and unique bands of MNs

Mode of vibration

1-MN

2-MN

Aromatic CH stretching

3076.9 (0.544)

3062.9 (1.771)

Aromatic CC stretching

1077.2 (0.113)

1644.6 (0.206)

Aromatic CH in-plane bending

1399.7 (0.181)

1134.6 (0.151)

Aromatic CH out-of-plane

978.8 (0.087)

952.2 (0.152)

Bending

788.9 (1.000)

812.1 (1.000)

Frequency values are in cm-1. In parenthesis, relative intensities are

given

apparent from calculation or it is masked by the more intense

band observed at 1603.2 cm-1. The observed band at
1644.6 cm-1 in 2-MN can be used for the isomeric identification of MN in a mixture since it is clearly resolved from
the adjacent band at 1604.6 cm-1 and is not seen in 1-MN. A
low intensity band observed at 1514.2 and 1513.2 cm-1 for
1- and 2-MN, respectively, is assigned as another aromatic
CC stretching vibration in 1-MN whereas in 2-MN this
band is a mixture of aromatic CC stretching and aromatic
CH in-plane bending vibrations. A band observed at 1465.6
and 1453.1 cm-1 for 1- and 2-MN, respectively, is of low
intensity and belongs to A00 symmetry. From calculation this
band at 1459.4 cm-1 in 1-MN and 1453.1 cm-1 in 2-MN is
assigned as a rocking vibration of the methyl group. A low
intensity band is observed in the spectra of MNs at
1444.7 cm-1 for 1-MN and 1440.8 cm-1 for 2-MN. This
band is assigned to a mixture of methyl antisymmetric
deformation and aromatic CH in-plane bending motion
from the calculated PEDs.
A unique band seen at 1399.7 cm-1 in the recorded
spectra of 1-MN, is assigned to an aromatic CH in-plane
bending vibration by comparing with the fitted frequency at
1398.0 cm-1 and its PED. This band can be used as a
marker for isomeric identification of 1-MN. There is no
band in the neighborhood of 1,390 cm-1 in 2-MN. A very
low intensity band is seen at 1383.3 and 1383.6 cm-1 for
1- and 2-MN, respectively, which is correlated with the
aromatic ring deformation vibration from calculated frequencies at 1383.2 cm-1 in 1-MN and 1383.4 cm-1 in

Isomeric identification of methylated

2-MN. A band appearing at 1267.7 and 1271.6 cm-1 for

1-and 2-MN, respectively, has been assigned to a mixture
of aromatic in-plane bending and aromatic CC stretching
vibrations based on PEDs. A band found at 1134.6 cm-1 in
2-MN is of low intensity and assigned as aromatic CH inplane bending vibration by comparing with the force field
fitted frequency at 1133.7 cm-1. This band is unique and
absent in 1-MN which perhaps is helpful for its identification. Another unique band seen at 1077.2 cm-1 in 1-MN
corresponds to the fitted frequency at 1076.9 cm-1. This
band is assigned to an aromatic CC stretching vibration
where only one CC bond is involved (Table 2). Next to
this a low intensity band observed at 1053.1 and
1040.2 cm-1 for 1- and 2-MN, respectively, has been
assigned to a mixture of methyl antisymmetric and symmetric deformations based on the PEDs of the fitted band
at 1048.4 cm-1 in 1-MN and 1039.8 cm-1 in 2-MN,
respectively. For both the 1- and 2-MNs a low intensity
band observed at 1022.8 and 1014.5 cm-1, respectively, is
correlated with the force field fitted frequency at 1022.4
and 1014.1 cm-1. This band has been assigned as a pure
aromatic CC stretching vibration. One low intensity band
seen at 978.8 cm-1 in 1-MN is unique and is assigned as
aromatic CH out-of-plane bending vibration after comparing with the fitted frequency at 978.6 cm-1. The same
band is shifted to 952.2 cm-1 in 2-MN. Two highly intense
bands are seen at 788.9 and 770.9 cm-1 in 1-MN and at
812.1 and 737.9 cm-1 in 2-MN which correspond to aromatic CH out-of-plane bending vibrations. The respective
fitted frequencies are 790.6 and 773.1 cm-1 in 1-MN and
808.4 and 738.0 cm-1 in 2-MN. This band is clearly distinct for different isomers of MN. The position 1 on
naphthalene is very reactive in comparison to position 2.
This leads to a drastic change in the vibrational frequencies on changing the substitution, and in fact this
happened. Two bands seen at 565.6 and 531.3 cm-1 in
1-MN are assigned to aromatic in-plane ring deformation
and out-of-plane vibration whereas in 2-MN two bands
observed at 699.2 and 620.2 cm-1 correspond to aromatic
CH out-of-plane and aromatic in-plane ring deformation
vibrations. In naphthalene p-electron localization occurs
and all the CC bonds are not of equal length [17]. A
methyl substitution will exert more influence on the CC
bond distances depending on where it is substituted. The
influence is greater when it is in 1 position than when it is
in position 2. This influence has been seen in the aromatic
CH out-of-plane bending frequencies of 1- and 2-MN. In
1-MN, both the frequency and intensity are less compared
to those in 2-MN. The mean deviation between the calculated and experimental intensities in the non CH
stretching region is much better compared to that in the
aromatic and methyl CH stretching region and found to
be *3 km mol-1.

217

4.4. Identification of isomers

Many aromatic CH stretching and aromatic CH out-ofplane bending vibrations have been identified in the experimental spectra of MNs. Out of these we have chosen a few
either intense or unique bands, as listed in Table 5, for the
isomeric identification. An intense aromatic CH stretch has
been identified at 3076.9 and 3062.9 cm-1, respectively in 1and 2-MN. This band is separated by 14 cm-1 from one
isomer to the other. Therefore, this band can be used for
isomeric identification of MN in a complex mixture. One
unique band observed at 1644.6 cm-1 in 2-MN and another
at 1077.2 cm-1 in 1-MN. These bands are unique to those
isomers and are not observed in the other isomer. Another
unique band seen in the experimental spectra of 1- and 2-MN
at 1399.7 and 1134.6 cm-1, respectively, for aromatic CH
in-plane bending vibration. This band is of low intensity and
clearly visible in the recorded spectra of MNs. Two sets of
bands have been identified for aromatic CH out-of-plane
bending vibrations at 788.9 and 978.8 cm-1 in 1-MN and
812.1 and 952.2 cm-1 in 2-MN. The first set of bands is
highly intense and the second set is of low intensity. These
bands are clearly distinguishable for different isomers of
MN. Therefore, spectral bands in the 1,800500 cm-1
region will be helpful for isomeric identification of MNs in a
complex mixture.
5. Conclusion
The gas phase IR spectra of 1- and 2-MN at 0.2 cm-1 have
been reported in this study which is a clear improvement on
the NIST reported spectra of these molecules. The fitted frequencies and their corresponding PEDs of different mode of
vibrations obtained from SQM calculation helped us do the
unambiguous assignment of the observed bands. By looking at
the highly intense aromatic CH out-of-plane bending vibrations in the region 1,800500 cm-1 and at the aromatic CH
stretching vibrations in the region 3,2002,800 cm-1, it is
possible to distinguish between the MNs. The isomeric identification through infrared spectra of these two compounds as
suggested here will perhaps be relevant in the field of the
environmental and atmospheric chemistry.
Acknowledgments The FT-IR spectrometer is supported by the
FIST program of the Department of Science and Technology, Govt.
of India. We thank CSIR, Govt. of India for supporting this research.
Many helpful discussions with E. Arunan and S. Manogaran are
gratefully acknowledged.

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