ABSTRACT

The FT-IR and FT Raman vibrational spectra of 1,4-Difluoro-2,5-

dimethoxybenzene (1,4-DF-2,5-DMB) was recorded in the region 3500-
100cm−1, respectively. Quantum chemical calculations of energies,
geometrical structure and vibrational wave numbers of 1,4-DF-2,5-DMB
was carried out by ab initio (HF) and density functional theory (DFT/B3LYP)
methods with 6-31+G(d,p) and 6-311++G(d,p) basis sets. To make
vibrational analysis, Gaussview03W software was used. Scaled frequencies
along with the IR, Raman intensities, reduced masses, depolarization ratios
and force constants are presented here. Finally, experimental vibrational
data is compared with the theoretical data. The difference between the
observed and scaled wavenumber values of most of the fundamentals is very
small.

Fig.2.2 Molecular structure of 1,4-Difluoro-2,5-dimethoxybenz

66
2.1 Introduction

Benzene and its derivatives has been the subject of investigation for many
reasons (1) . Aromatic compounds such as benzene derivatives are commonly
used to make plastics, resins, Nylon and synthetic fibers. Benzene is also
used to make some types of rubbers, lubricants, dyes, detergents, drugs and
pesticides (2, 3) . Furthermore the substitution of a functional group in benzene
ring changes the spectra markedly. Fluorine substituent can greatly increase
the fat solubility of molecules, which is particularly important in
pharmaceutical, where it can increase their bioavailability. Fluorine is a
common element in antibiotic molecules, too (1-4) . Various spectroscopic
studies of halogen substituted compounds have been reported in the literature
(5–15) from time to time. Vibrational spectra of fluorobenzene were studied
extensively (16–18) . The molecular structure of orthofluoronitrobenzene has
been investigated by gas-phase electron diffraction and ab-initio MO
calculations (19, 20) . Recent spectroscopic studies of the benzene and their
derivatives have been motivated because the vibrational spectra are very
useful for the understanding of specific biological process and in the analysis
of relatively complex systems (21) . Literature survey reveals that to the best of
my knowledge, the detailed HF/B3LYP/ comparative studies on the complete
FT-IR and FT-Raman spectra of 1,4-Difluoro-2,5-dimethoxybenzene have
not been reported so far.

The position of the substituents in the benzene ring plays a very important
role on the structural and electronic properties of the molecule. 1,4-DF-2,5-
DMB (two F atoms and two -OCH3 groups) molecule are tetra-substituted
benzenes. As a continuation of the interest in benzene derivative compounds,
experimental and theoretical analyses are made in the present study. In the
present investigation, the performance of HF theory, employing two basis
sets {6-31+G (d, p),6-311++G (d, p)} and Density functional theory with

67
same basis sets have been evaluated for above molecules. It has been felt that
proper knowledge of different normal modes of vibration could be of much
help in understanding the dynamical nature of these molecules. Comparative
studies of the vibrational spectra of 1,4-Difluoro-2,5-dimethoxybenzene have
been presented in this chapter at four different levels {HF/6-31+G (d, p),
HF/6-311++G (d, p), B3LYP/6-31+G (d, p), B3LYP/6-311++G (d, p)}. The
aim of the present investigation is three fold mainly:

1. To find the optimized geometrical parameters (bond length and bond

angles) of 1,4-Difluoro-2,5-dimethoxybenzene using HF and Density
Functional Theory.

2. To carry out the quantum mechanical calculations for vibrational

wavenumbers of the titled molecules.

3. To compare the experimental wavenumbers with the results of theoretical

calculations.

2.2 Experimental details

The Compounds under investigation namely 1,4-Difluoro-2,5-

dimethoxybenzene were purchased from M/S Aldrich chemicals, USA with
spectroscopic grade and it is used as such without any further purification.
The FT Raman spectra of 1,4-DF-2,5-DMB compounds was recorded on a
BRUKER IFS. 66V model interferometer equipped with an FRA-106 FT-
Raman accessory in the 3500–100 cm-1stokes region using 1064 nm line of a
Nd:YAG laser for excitation operating at 200mw power. The reported wave
numbers are believed to be accurate within ±1 cm-1.The infrared spectra of
above compounds were recorded on Perkin Elmer M-500 FTIR
spectrophotometer in the region 4000-400 cm-1 using KBr pellets.

68
2.3 Computational spectral studies of 1,4-DF-2,5-DMB

Many studies have shown that the DFT (B3LYP) method in combination
with the 6-31++G(d,p) basis set is able to give the accurate energies,
molecular structure , and infrared vibrational frequencies. The molecular
structure 1,4-DF-2,5-DMB in ground is computed by performing both ab
initio (HF) and DFT(B3LYP) with 6-31+G(d,p) and 6-311++G(d,p) basis
sets. Geometry optimization is one of the most important steps in the
theoretical calculations. The optimized structural parameters are used in the
vibrational frequency calculations at HF and DFT (B3LYP) levels. The
minimum energy of geometrical structure is obtained using level 6-31+G(d,p)
and 6-311++G(d,p) basis sets. At the optimized geometry for the titled
molecules no imaginary frequency modes were obtained, so there is a true
minimum on the potential energy surface was found. HF/DFT calculations
for 1,4-DF-2,5-DMB are performed using GAUSSIAN 03W(20, 22) program
package on Pentium IV processor personal computer without any constraint
on the geometry. The calculated frequencies are scaled by 0.8929 for HF/6-
31+G(d,p) and HF/6-311++G(d,p). For B3LYP/6-31+G(d,p) and B3LYP/6-
31++G(d,p) is scaled by 0.9613. The usefulness of vibrational spectroscopy
has expanded rapidly over the last decade with the development of FT-IR and
Raman instrumentation. Vibrational spectroscopy provides immensely
invaluable information about the structure and conformation of organic
compounds if used in synergy with quantum chemical calculations.
Predication of vibrational frequency of molecules by quantum chemical
computation has become very popular because of its accurate and consistent
description of the experimental data. In most of the studies simple substituted
benzene compounds are taken. The reason for this may be because the
complexity of the molecule increases with the increasing number of atoms in
it. It is well known that it is easier to deal with a molecule of lesser

69
complexity than that which is relatively more complex. This statement is
even true with the computational convenience offered by the present day
computers (23, 24).

2.4 Result and discussions

2.4.1 Molecular geometries

The molecule 1,4-DF-2,5-DMB has 20 atoms and belonging to the point

group CS. The three Cartesian displacements of the 20 atoms provide 54
internal modes, namely.
' ''
Γ internal =37 A +17 A

From the character table for the CS point group, since

' ''
Γ trans =2 A + A

and
' ''
Γ rot = A +2 A

We get,

Γ vib=Γ internal + Γ trans + Γ rot=37 A +17 A , 54 modes of vibrations.

' ''

All 54 fundamental vibrations are active in both IR & Raman. For an N-

atomic molecule, as already discussed, (2N-3) of all the vibrations are in
plane and (N-3) are out of plane (23) .Thus for 1,4-Difluoromo-2,5-
dimethoxybenzene; 37 of all the 54 vibrations are in-plane and 17 are out-of-
plane. The assignments are presented in the tables 2.1and 2.2 for 1,4-
Dibromo-2,5-dimethoxybenzene and 1,4-Difluoro-2,5-dimethoxybenzene
compounds respectively. Vibrational spectral investigation reveals that IR
and Raman spectra for most of the modes are complimentary (25) . The infrared
and Raman spectra of molecules contain a number of bonds of varying
intensity at specific wave numbers. The vibrational band assignments of the
molecules 1,4-DB-2,5-DMB and 1,4-DF-2,5-DMB have been made based on

70
the position, shape and relative intensity of the bands in the spectra in
correlation with the vibrational bands of structurally related molecules.
Optimized structures at the B3LYP/6-311++G(d,p) level for the molecules
1,4-DF-2,5-DMB are shown in figure 2.2. Experimental FT-IR and FT-
Raman spectra of 1,4-DF-2,5-DMB along with respective computed spectra
(HF/DFT) are shown in figures 2.4 and 2.6 respectively. The optimized
parameter (bond angles, bond lengths) for the compound is given in the table
2.4. Also the wave numbers, IR intensities, Raman activities, reduced masses
and force constants of 1,4-DF-2,5-DMB at B3LYP/6-311++G(d, p) levels are
given in table 2.6. Several Thermodynamic properties like the heat capacity,
zero point energy, entropy along with the minimum energy of 1,4-DF-2,5-
DMB have been obtained by ab initio HF and density functional theory
methods using 6-31+G(d,p) and 6-311++G(d,p) sets. The calculations are
presented in the table 2.8 for compound 1,4-DF-2,5-DMB respectively. The
difference in the values calculated by both the methods is only marginal. The
rotational constants and dipole moments for the titled compounds are also
listed in the tables.

71
Table 2.2: Comparison of the experimental (FT-IR and FT-RAMAN) and computed vibrational frequencies of
1,4-DF-2,5-DMB

COMPUTATIONAL
EXPERIMENTAL HF DFT VIBRATIONAL
HF/6-31+G( d, p) HF/6-311++G(d, p) B3LYP/6-31+G(d, p) B3LYP/6-31++G(d, p) ASSIGNMENTS
FT-IR FT-Raman Unscaled Scaled Unscaled Scaled Unscaled Scaled Unscaled Scaled
47 42 46 41 54 52 52 50 γ(O-C) in CH3
68 61 65 58 89 85 83 80 γ(O-C) in CH3
139 124 138 123 132 127 129 124 γ(O-C) in CH3
197 176 197 176 185 178 184 177 β(C-O-C)
205 183 206 184 186 179 185 178 γ(O-C) in CH3
225 201 225 201 209 201 208 200 β(C-O-C),β(C-F)
243 217 242 216 220 212 214 206 τ (CH3)
247(vw) 282 252 281 251 259 249 252 242 τ (CH3)
334 298 335 299 306 294 305 293 γ(C-O)
336 300 338 302 307 295 308 296 β(C-F)
318(w) 344 307 344 307 320 308 320 308 β(C-O-C),β(C-F),β(C-C-C)
349(w) β(C-O-C)
377(w) β(C-O-C)
418(w) 421(vw) 467 417 472 421 416 400 417 401 γ(C-C-C)
449(w) 487 435 488 436 451 434 453 435 β(C-C-C), β(C-O-C)
496 443 495 442 465 447 465 447 β(C-O-C)
516 461 520 464 469 451 469 451 γ(C-H)
501(vw) 545 487 546 487 505 485 506 486 β(C-C-C),β(C-O-C)
658(vs) 652(vw) 715 638 714 638 663 637 664 638 ν(C-F),β(C-O-C)
716 639 717 640 664 638 664 638 β(C-C-C),β(C-O-C)
673(vw) 758 677 782 698 674 648 701 674 Ring deformation,γ(C-F),γ(C-O)
764 682 800 715 688 661 707 680 γ(C-H)
743(s) 745(s) 821 733 818 730 761 731 759 729 γ(C-H)
72
Table 2.2 continued…
COMPUTATIONAL
EXPERIMENTAL HF DFT
VIBRATIONAL
HF/6-31+G( d, p) HF/6-311++G(d,p) B3LYP/6-31+G(d,p) B3LYP/6-31++G(d,
ASSIGNMENTS
FT-IR FT-Raman Unscaled Scaled Unscaled Scaled Unscaled Scaled Unscaledp) Scaled
780(s) 948 847 946 845 830 798 831 799 Asy. γ(C-H)
951 849 959 856 864 830 857 824 Sy. γ(C-H)
847(vs) 992 886 986 880 874 840 871 838 γ(C-H),β(C-O-C),ν(C-F)
865(w) Asy. γ(C-H), Ring breathing
995(vw) 1132 1011 1129 1008 1033 993 1026 986 ν(O-C), Asy. γ(C-H)
1018(w) 1176 1050 1172 1047 1071 1030 1065 1023 ν(C-F), ν(O-C), ν(C-O), β(C-
1096(s) 1221 1090 1205 1076 1160 1115 1149 1105 H),β(C-C-C)
t(C-H) in CH3
1123(w) 1116(vw) 1279 1142 1274 1138 1172 1127 1168 1123 ν(O-C), Asy. γ(C-H)
1281 1144 1279 1142 1172 1127 1169 1123 t(C-H) in CH3
1281 1144 1279 1142 1194 1148 1187 1141 β(C-H)
1313 1172 1307 1167 1212 1165 1207 1160 β(C-H),ν(C-F),β(C-C-C)
1334 1191 1330 1188 1220 1172 1215 1168 β(C-H) in CH3, t(C-H),β(C-O-C)
1196(vw) 1338 1194 1334 1191 1256 1207 1246 1198 ν(C-O),β(C-H),ν(C-F),ν(O-C),β(C-
1247(vw) 1370 1224 1367 1220 1260 1211 1256 1207 C-C)
β(C-H)
1382 1234 1374 1227 1351 1299 1335 1284 Asy. ν(C-C-C),β(C-O-C)
1523 1360 1515 1353 1388 1334 1377 1323 Ring breathing,ν(C-C-C),ν(C-
1363(m) 1556 1390 1549 1383 1433 1378 1426 1371 F),ν(C-O)
ν(C-C-C), Sy. β(O-CH3)
1388(s) Sy. β(O-CH3)
1409(vs) 1618 1445 1612 1439 1486 1428 1481 1423 ν(C-C-C)
1622 1449 1616 1443 1489 1431 1483 1426 ν(C-C-C), τ(CH3),β(C-H)
1629 1454 1621 1448 1498 1440 1493 1435 τ(CH3)
1629 1454 1621 1448 1498 1440 1493 1435 τ(CH3)
1450(w) 1636 1460 1629 1454 1508 1449 1503 1445 Asy. β(O-CH3)
1460(w) 1636 1461 1629 1455 1509 1450 1504 1446 Asy. β(O-CH3)
1473(m) Asy. β(O-CH3)

73
Table 2.2 continued…
COMPUTATIONAL
EXPERIMENTAL HF DFT
VIBRATIONAL
HF/6- HF/6- B3LYP/6- B3LYP/6-
ASSIGNMENTS
FT-IR FT-Raman 31+G( d,
Unscaled 311+
Scaled 31+G(d,p)
Unscaled 31++G(d,
Scaled Unscaled Scaled Unscaled Scaled
1490(m) 1718 1534 1710 1527 1566 1505 1556 1496 ν(C-C-C), β(C-H),ν(C-O)
1507(s) Asy. β(O-CH3)
1588(vs) 1587(vw) 1802 1609 1797 1605 1637 1574 1629 1566 ν(C-C-C),ν(C-F),Ring deformation
1635(m) ν(C-C-C),β(C-F),β(C-H)
1653(m) 1650(w) 1843 1646 1836 1639 1687 1621 1677 1612 ν(C-C-C),β(C-F),β(C-H)
1684(m) β(C-H)
1700(m) β(C-H)
2831(s) Sy ν(C-H) in CH3
2847(s) Sy ν(C-H) in CH3
2860(m) 3182 2842 3164 2825 3017 2900 3005 2888 Sy ν(C-H) in CH3
3183 2842 3164 2825 3018 2901 3005 2889 Sy ν(C-H) in CH3
2927(s) Sy ν(C-H) in CH3
2948(s) 3248 2900 3225 2879 3082 2962 3064 2946 Asy ν(C-H) in CH3
2960(s) 2953(m) 3248 2900 3225 2879 3082 2962 3064 2946 Asy ν(C-H) in CH3
3027(vs) 3314 2959 3290 2938 3158 3036 3140 3018 Asy ν(C-H) in CH3
3314 2959 3290 2938 3158 3036 3140 3018 ν(C-H)
3074(vs) 3406
1
3041 3382 3020 3240 3114 3220 3095 ν(C-H)
3112(s) 3101(vs) 3408 3043 3384 3022 3241 3116 3222 3097 ν(C-H)
3567(vs) Abs
ν(C-H)
3587(vs) 0.75
ν(C-H)
3629(vs) ν(C-H)
3647(vs) ν(C-H)
0.5

0.25 74

3750 2250 1500 750

 Fig. 2.5 (a) Experimental FT-IR spectra of 1,4-Difluoro-2,5-dimethoxybenzene

Vibrational spectrum

550

500

450

400

350
IR intensity

300

250

200

150

100

50

0 200 400 600 800 1,000 1,200 1,400 1,600 1,800 2,000 2,200 2,400 2,600 2,800 3,000 3,200 3,400
Frequency, cm**-1

Fig. 2.5 (b) Computed HF/6-311G(d,p) FT-IR spectra of 1,4-Difluoro-2,5-dimethoxybenzene

75
 Vibrational spectrum
460
440
420
400
380
360
340
320
300
280
260

IR intensity
240
220
200
180
160
140
120
100
80
60
40
20

0 500 1,000 1,500 2,000 2,500 3,000

Frequency, cm**-1

Fig. 2.5 (c) Computed [B3LYP/6-311++G(d,p)] FT-IR spectra of 1,4-Difluoro-2,5-dimethoxybenzene

76
Table 2.4: Optimized geometrical parameters for 1,4-Difluoro-2,5-dimethoxybenzene computed at HF/6-31+G(d, p),
HF/6-311++G (d, p), B3LYP/6-31+G (d, p) and B3LYP/6-311++G(d, p) basis sets.
Bond Length HF/6-31G HF/6-311G B3LYP/6-31G B3LYP/6-311G Bond Angle HF/6-31G HF/6-311G B3LYP/6-31G B3LYP/6-311G
(Å) (d, p) (d, p) (d, p) (d, p) (®) (d, p) (d, p) (d, p) (d, p)
C1-C2 1.383 1.377 1.382 1.399 1.399 C2-C1-C6 122.6 122.5 122.7 122.7
C1-C6 1.329 1.375 1.388 1.389 C2-C1-F19 119 119.1 118.7 118.7
C1-F19 1.389 1.323 1.355 1.909 C6-C1-F19 118.2 118.3 118.4 118.4
C2-C3 1.344 1.387 1.402 1.398 C1-C2-C3 117.1 117.1 117.2 117.2
C2-O9 1.377 1.342 1.361 1.358 C1-C2-O9 117.4 117.4 117.2 117.2
C3-C4 1.071 1.375 1.388 1.389 C3-C2-O9 125.3 125.3 125.4 125.4
C3-H7 1.383 1.071 1.082 1.08 C2-C3-C4 120.1 120.2 119.9 119.9
C4-C5 1.329 1.382 1.399 1.399 C2-C3-H7 121.9 121.8 121.9 121.9
C4-F20 1.389 1.323 1.355 1.909 C4-C3-H7 117.8 117.8 118.1 118.1
C5-C6 1.343 1.387 1.402 1.398 C3-C4-C5 122.6 122.5 122.7 122.7
C5-O10 1.071 1.342 1.361 1.358 C3-C4-F20 118.2 118.3 118.4 118.4
C6-H8 1.402 1.071 1.082 1.08 C5-C4-F20 119 119.1 118.7 118.7
O9-C15 1.401 1.4 1.423 1.422 C4-C5-C6 117.1 117.1 117.2 117.2
O10-C11 1.085 1.4 1.423 1.422 C4-C5-O10 117.4 117.4 117.2 117.2
C11-H12 1.085 1.086 1.097 1.095 C6-C5-O10 125.3 125.3 125.4 125.4
C11-H13 1.079 1.086 1.097 1.095 C1-C6-C5 120.1 121 119.9 119.9
C11-H14 1.085 1.079 1.09 1.088 C1-C6-H8 117.8 117.8 118.1 118.1
C15-H16 1.085 1.086 1.097 1.095 C5-C6-H8 121.9 121.8 121.9 121.9
C15-H17 1.079 1.086 1.097 1.095 C2-O9-C15 119.5 119.5 117.9 117.9
C15-H18 1.079 1.09 1.088 C5-O10-C11 119.5 119.5 117.9 117.9
O10-C11-H12 111.2 111.3 111.3 111.3
O10-C11-H13 111.2 111.3 111.3 111.3
O10-C11-H14 105.9 106.1 105.6 105.6
H12-C11-H13 109.6 109.5 109.5 109.5
H12-C11-H14 109.2 109.2 109.4 109.4
H13-C11-H14 109.2 109.2 109.4 109.4
77
Table 2.4 continued….
Bond Length HF/6-31G HF/6-311G B3LYP/6-31G B3LYP/6-311G Bond Angle HF/6-31G HF/6-311G B3LYP/6-31G B3LYP/6-311G
(Å) (d, p) (d, p) (d, p) (d, p) (®) (d, p) (d, p) (d, p) (d, p)
O9-C15-H16 111.2 111.3 111.3 111.3
O9-C15-H17 111.2 111.3 111.3 111.3
O9-C15-H18 106 106.1 105.6 105.6
H16-C15-H17 109.6 109.5 109.5 109.5
H16-C15-H18 109.2 109.2 109.4 109.4
H17-C15-H18 109.2 109.2 109.4 109.4

78
Table 2.6: Vibrational wave numbers obtained for 1,4-DF-2,5-DMB at
B3LYP/6-311++G(d,p) [harmonic frequency (cm-1), IR intensities (Km mol-1),
Raman scattering activities (Å4amu-1), Raman depolarization ratio and
reduced masses (amu), force constants (m dyne Å-1)]
S. No. Species Wave number IR intensity Raman intensity Depolarization Reduced Force
Unscaled Scaled Abs Rel Abs Rel Ratio mass Constant
1 A" 52 50 7 2 0 0 0.69 3.03 0.00
2 A" 83 80 0 0 0 0 0.75 3.54 0.01
3 A" 129 124 1 0 0 0 0.67 6.74 0.07
4 A' 184 177 6 1 0 0 0.28 3.57 0.07
5 A" 185 178 2 0 0 0 0.69 2.78 0.06
6 A' 208 200 0 0 2 1 0.34 4.67 0.12
7 A" 214 206 0 0 2 1 0.75 1.15 0.03
8 A" 252 242 2 1 0 0 0.75 1.48 0.06
9 A" 305 293 0 0 1 0 0.75 4.03 0.22
10 A' 308 296 5 1 0 0 0.58 11.09 0.62
11 A' 320 308 0 0 6 2 0.23 5.05 0.31
12 A" 417 401 0 0 3 1 0.75 10.46 1.07
13 A' 453 435 0 0 6 2 0.17 10.75 1.30
14 A' 465 447 5 1 0 0 0.12 4.50 0.57
15 A" 469 451 3 1 0 0 0.53 2.91 0.38
16 A' 506 486 0 0 7 2 0.45 7.71 1.16
17 A' 664 638 0 0 5 1 0.44 4.41 1.15
18 A' 664 638 12 3 0 0 0.46 8.82 2.29
19 A" 701 674 0 0 0 0 0.33 11.95 3.46
20 A" 707 680 0 0 0 0 0.75 2.40 0.71
21 A' 759 729 0 0 31 9 0.09 6.25 2.12
22 A" 831 799 0 0 0 0 0.75 1.86 0.76
23 A" 857 824 56 12 0 0 0.36 1.42 0.61
24 A' 871 838 135 28 0 0 0.18 3.60 1.61
25 A' 1026 986 0 0 1 0 0.66 8.05 4.99
26 A' 1065 1023 152 32 0 0 0.31 5.69 3.80
27 A' 1149 1105 0 0 4 1 0.73 4.65 3.61
28 A' 1168 1123 1 0 0 0 0.75 1.27 1.02
29 A' 1169 1123 0 0 5 2 0.75 1.27 1.02
30 A' 1187 1141 107 22 0 0 0.35 1.64 1.36
31 A' 1207 1160 110 23 0 0 0.37 1.75 1.50
32 A' 1215 1168 0 0 4 1 0.29 1.59 1.38
33 A' 1246 1198 423 89 0 0 0.45 5.13 4.69
34 A' 1256 1207 0 0 3 1 0.07 1.35 1.26
35 A' 1335 1284 50 11 0 0 0.05 8.70 9.14
36 A' 1377 1323 0 0 25 7 0.06 6.49 7.25
37 A' 1426 1371 89 19 0 0 0.62 3.93 4.71
38 A' 1481 1423 0 0 10 3 0.49 1.23 1.59
Table 2.6 continued…
S. No. Species Wave number IR intensity Raman intensity Depolarization Reduced Force
 Unscaled Scaled Abs Rel Abs Rel Ratio Mass Constant

39 A' 1483 1426 40 8 0 0 0.40 1.41 1.83

40 A" 1493 1435 17 4 4 1 0.75 1.05 1.37
41 A" 1493 1435 3 1 24 7 0.75 1.05 1.37
42 A" 1503 1445 98 21 0 0 0.70 1.07 1.43
43 A" 1504 1446 0 0 11 3 0.69 1.05 1.40
44 A' 1556 1496 476 100 0 0 0.20 3.63 5.18
45 A' 1629 1566 0 0 15 4 0.58 8.20 12.82
46 A' 1677 1612 0 0 53 15 0.47 8.69 14.41
47 A' 3005 2888 109 23 0 0 0.03 1.03 5.50
48 A' 3005 2889 0 0 353 100 0.03 1.03 5.51
49 A' 3064 2946 1 0 119 34 0.75 1.11 6.12
50 A' 3064 2946 72 15 1 0 0.75 1.11 6.12
51 A' 3140 3018 34 7 1 0 0.45 1.10 6.38
52 A' 3140 3018 0 0 254 72 0.45 1.10 6.38
53 A' 3220 3095 0 0 0 0 0.25 1.09 6.66
54 A' 3222 3097 0 0 149 42 0.25 1.09 6.67

80
Table 2.8: Theoretically computed energies (a. u.), zero point vibrational
energies (kcal/ mol), rotational constants (GHz), entropies (cal/mol-
Kelvin),dipole moment (Debyes), thermal energy(kcal/mol) and specific
heat(cal/mol-Kelvin) for 1,4-DF-2,5-DMB
HF DFT
Parameter HF/6-31+G HF/6-311++G B3LYP/6-31+G B3LYP/6-31++G
(d, p) (d, p) (d, p) (d, p)
Total Energy -656.183927 -656.326916 -659.792638 -659.947123
Zero-Point Energy 100.38533 100.03001 93.46830 93.07651
Rotational Constants 1.54837 1.55315 1.50420 1.50974
0.65395 0.65595 0.64467 0.64719
0.46244 0.46387 0.45389 0.45564
Dipole Moment 0.0011 0.0007 0.0009 0.0003

ENTROPY

Total 102.621 102.683 104.465 104.784

Translational 41.370 41.370 41.370 41.370
Rotational 30.907 30.898 30.969 30.958
Vibrational 30.344 30.415 32.126 32.456

ENERGY (THERMAL ENERGY)

Total 107.109 106.745 100.584 100.211

Translational 0.889 0.889 0.889 0.889
Rotational 0.889 0.889 0.889
0.889
Vibrational 105.331 104.968 98.806 98.434

SPECIFIC HEAT (CV)

Total 38.988 38.909 41.694 41.714

Translational 2.981 2.981 2.981 2.981
Rotational 2.981 2.981 2.981 2.981
Vibrational 33.027 32.948 35.732s 35.752

81
2.4.2 Methoxy group vibrations

The wave numbers of the vibrational modes of methoxy group are known to
be influenced by a variety of interesting interactions such as electronic
effects, inter-molecular hydrogen bond and Fermi resonance (26-28) . Electronic
effects such as back donation and induction, mainly caused by the presence
of oxygen atom adjacent to methyl group, can shift the position of CH
stretching and bending modes (29-30) . In the present molecules, there are two
methoxy groups at the 2nd and 5th positions. To study the spectra of methoxy
group first we will study the dynamics of methyl group (31-33) . In aromatic
compounds the symmetric stretching mode for methyl group is expected in
the region (2920 ± 80) cm-1 in which all the three C-H bonds of methyl group
extend and contract in phase (34-36) . The asymmetric stretching mode of the
methyl group is expected in the region (3020 ± 30) cm -1. In asymmetric CH3
stretching two C-H bonds are extending while the third one is contracting (37-

39) . Related vibrations of the OCH3 group are also presented in the table 2.9.

2.4.3 C-C vibrations

The ring carbon-carbon stretching vibrations occur in the region 1625-1430
cm-1 (40-42) . In general the bands are of variable intensity and according to
Varsanyi (43) , the five bands in the region are observed at 1625-1590, 1590-
1575, 1540-1470, 1465-1430 and 1380-1280 cm-1. In the present work, the
frequencies observed for 1,4-DB-2,5-DMB in the Raman spectrum at 1550
cm-1 and 1594 cm-1 are assigned to C-C stretching vibrations. Also the IR
bands observed at 1460 and 1493 cm-1 is also assigned to C-C stretching
vibrations for the same compound. The C-C stretching vibrations for 1,4-DF-
2,5-DMB in IR bands observed at 1409, 1490, 1588 and 1635 cm -1 and in
Raman bands C-C stretching vibrations observed at 1587 and 1650 cm -1. In
the benzene, fundamental (992 cm -1) and (1010 cm-1) represent the ring
breathing mode and carbon trigonal bending mode. Under the CS point group,

82
Table 2.9: Assignments of methoxy group vibrations in 1,4-DF-2,5-DMB
Assignment Predicted region 1,4-DF-2,5-DMB /(cm-1)

(cm-1) IR Raman

O-C stretching of (975 ± 125) 1018 995

-OCH3 group 1096 1196

Asymmetric bending (1460 ± 25), 1473 1450

of -OCH3 group
(1450 ± 15) 1507 1460

Symmetric bending (1435 ± 15) - -

of -OCH3 group

Asymmetric -CH3 (3020 ± 30 ) 2960 2948

group stretching
3027

Symmetric -CH3 2920 ± 80 2831 2948

group stretching
2927 2953

83
both the vibrations are very close to each other, there is an appreciable
interaction between these vibrations and consequently their energies will be
modified (42-44) . In the present investigation for molecule 1,4-DF-2,5-DMB,
the IR band at 865 cm-1 and the Raman band at 995 cm-1 correspond to the
ring breathing mode.

2.4.4 C-H vibrations

In the present molecules, there are substituents at the 1 st, 2nd, 4th and 5th
position. So, there are only two hydrogen atoms left around the aromatic ring
at the 3rd and 6th position. Due to the presence of these two hydrogen atoms
there will be two C-H stretching vibrations, C-H in-plane and C-H out-of-
plane bending vibrations (45, 46).

The C-H stretching modes usually appear with strong Raman intensity and
are highly polarized (46, 47) . The substituted aromatic compounds shows the
presence of C-H stretching vibrations in the region 3100-3000 cm -1 which is
the characteristic region for the ready identification of C-H stretching
vibrations. In this region these bands are not affected appreciably by the
nature of substituent. Hence the weak IR bands observed at 3023 cm -1 (3024
cm-1 in FT Raman) and 3068 cm -1 (3069 cm-1 in FT Raman) for 1,4-DB-2,5-
DMB. Similarly, for 1,4-DF-2,5-DMB C-H stretching vibrations of the two
hydrogen atoms observed at 3074 (in FT-IR) cm-1 and 3100 cm-1 (in FT-
Raman). In most of the substituted benzenes, C-H out-of-plane bending
vibrations for are observed in the region between750-1000 cm -1(47-51). So IR
bands observed for 1,4-DB-2,5-DMB at 760, 861 and 1022 cm-1 are assigned
to the C-H out-of-plane bending vibrations. Similarly, the Raman bands at
904 and 1033 cm-1 are assigned for C-H out-of-plane bending vibrations. C-H
out-of-plane bending vibrations for 1,4-DF-2,5-DMB are observed at
743,780,847,865 and 1018 for IR bands and at 745,995 for Raman bands. C-
H in plane bending mode is generally observed in the region, 1000-1300

84
cm-1 (51). The IR bands observed at 1185 and 1214 cm -1 and the Raman bands
at 1180 and 1293 cm-1 are associated with the C-H in plane bending mode for
1,4-DB-2,5-DMB. C-H in plane bending mode for 1,4-DF-2,5-DMB in IR
bands observed at 1018,1096 and the Raman bands at 1116,1196 and 1247
cm-1. All the assignments for the titled molecules are given in the table 2.1.

2.4.5 C-F vibrations

In second compound (1,4-DF-2,5-DMB), there is a substitution of two F

atoms at 1st and 4th positions in the benzene ring (having two methoxy
substituent’s at 2nd and 5th positions). Assignments of the C–F stretching
modes are very difficult as these vibrations are strongly coupled with the
other in plane bending vibrations of several modes. Normally, the observed
bands of the C–F stretching vibrations have been found to be very strong in
the IR spectra and these appear in the range 1000–1300 cm −1 for several
fluoro-benzenes. And also the C–F stretching vibrations strongly coupled
with the C–H in-plane bending vibrations in the mono fluorinated benzene
and is observed in the region 1100–1000 cm −1 (52–54). Sundaraganesan et al. (53)
observed two strong bands at 1279 and 1331 cm−1 in IR and at 1280 and 1332
cm−1 in Raman were assigned to C–F stretching mode for 2,3-difluoro phenol
molecule. Karabacak et al. (55) have assigned the strong bands at 1254 and
1222 cm−1 in the IR spectrum due to the C–F stretching mode. Their
counterpart in the Raman spectrum is at 1274 and 1245 cm −1. The
corresponding C–F stretching vibration observed at 1096 cm −1 in IR band and
at 1587 cm−1 in Raman band. The C–F in-plane bending and out-of-plane
bending wavenumbers are assigned at 402 cm−1 and 377 cm−1 in Raman,
respectively (56-57) . In the present case, a band assigned to C–F in-plane
bending at 318 cm−1 in Raman. According to the reported values, this
assignment is in line with the literature.

85
2.5 Conclusion

The FT-IR and FT-Raman Spectra have been recorded and the detailed
vibrational assignments for 1,4-Difluoro -2,5-dimethoxybernzene is
presented for the first time. The harmonic vibrational frequencies, IR
intensities and Raman scattering activities of above compound was
determined and analyzed both at HF and DFT levels of theory. Most of the
modes have wave numbers in the expected range and are also in good
agreement with computed scaled values. The difference between the
observed and calculated wave numbers is very small for most of the
fundamentals. Therefore the results presented in this chapter for 1,4-Difluoro-
2,5-dimethoxybernzene indicate that these theoretical calculations are reliable
for the prediction of both infrared and Raman spectra of the medium sized
organic compounds. The comparative study of 1,4-DF-2,5-DMB is proof
that the substitution of H atom by the F atom distorts the geometries to small
extent and the planarity of the molecule. This study demonstrates that scaled
DFT (B3LYP) calculations are powerful approach for the understanding the
vibrational spectra of medium sized organic compounds.

86
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