CHAPTER IliA

NORMAL CO-ORDINATE ANALYSES OF

THREE ISOMERIC ACETYLPYRIDINES
AND ACETOPHENONE
IIIA.l INTRODUCTION

Proper assignments of the vibrational wavenumbers and determination of an accurate

force field for a molecule are of fundamental importance. As the number of force constant (FCs)
to be determined is usually greater than the number of experimental wavenumbers, it becomes
impossible to determine a reliable force field using the vibrational wavenumbers of a single
molecule alone. A force field may be considered to be more reliable when it reproduces the
observed wavenumbers of a number of similar types of_ molecules simultaneously. For this
purpose, consideration of the wavenumbers of a number of isotopically substituted molecules
along with the parent compound is a common procedure to augment the number of observed
wavenumbers. Thus a normal coordinate analysis (NCA) is carried out and a reliable force field
is obtained. Here, instead, we have determined a general valence force field which reproduces
satisfactorily the observed wavenumbers (obtained from Raman and IR spectra) of 2-, 3- and 4-
acetypyridine (2-, 3- and 4-APy) and acetophenone (APh) simultaneously.
Medhi [I] reported the IR and Raman spectra of the three isomeric APys and presented a
useful discussion on the assignments of different normal modes of vibration. Gambi et al. [2]
proposed the vibrational assignments of APh and a number of its deuterated analogues (along
with an NCA) on the basis of the IR spectrum. Now, consiqering the vibrational wavenumbers
of all the four molecules together, we have carried out an NCA and determined a general valence
force field (GVFF), which reproduces the observed wavenumbers of all the four aforesaid
molecules within an average error of 7.0cm·1 (0.82%) for the in-plane and 9.2cm·1 (1.60%) for
the out-of-plane modes. The final set of the force field consisted of 41 parameters (25 planar and
16 non-planar). It turned out that some ofthe assignments proposed earlier need to be revised in
the light of the potential energy distribution (PED) arising in the present calculation.
Boatz and Gorden [3] and Mallick et al. [4] determined the wavenumber contributions of
different internal coordinates to the fundamental normal modes of vibration and showed that the
results were very consistent when applied to different groups of isotopically ·substituted
molecules. Moreover, Mallick et al. [4] used this idea to determine the change in molecular
geometries for the bipyridine ligand of tris-(bipyridine)-ruthenium-(II) (and their different
isotopic analogues) very consistently in their respective MLCT excited electronic states [4].
Here we also used the same scheme to decompose the normal mode wavenumbers of the four
aforesaid molecules into those related to different internal Coordinates and good consistency of
the results was observed.

65
 Table- IliA. I
Force Constants (FC)

FC FC. Present For For For For For For

No Definition Value Benzene Pyridine Toluene Methylpyridim APh Acetaldehy~e
f-----

!Planar force constants

11
a) Diae:onal
1 R (CN) 6.5840 - 5.5530 - 5.5020 - -
2 R (CC) 6.4370 7 0067 5.5530 6.4133 5.8570 7.0940 -
3 R(CH) 5.0850 5.0220 5.0930 5.0664 5.1160 5.0280 -
4 R (CO) 9.9070 - - - - 8.7000 10.5280
5 R (CRCA) 4.7670 - - - - 4.8000 -
6 R (CACM) 4.7440 - - 4.6813 4.5110 4.3000 4.8200
7 H (a) 1.0650 1.4612 1.0310 1.0284 1.6520 0.5110 -
8 H (~) 0.5000 0.4956 0.8640 0.5154 0.5100 -
9 H (CCRCA/NCRCA) 1.4700 - - 0.7535 - 1.0050 -
10 H (CRCACM) 1.3810 - - - - 2.2260 -
11 H (CRCAO/ C~AO) 0.6360 - - - - 1.0860 -
b) OtT-diae:onal
12 r {1, 1) 0.6890 - 0.6330 0.7716 0.6870 - -
13 r (1, 2) 0.8160 - 0.6330 - - - -
14 r (2, 2) 0.6900 0.6432 0.6330 - - 0.8780 -
15 r(l/2,5) 0.3100 - - - - 0.8060 -
16 r (5, 6) 0.2320 - - - - 0.4240 -
17 r (4, 5/6) 0.2540 - - - - 0.6390 -
18 h (1/2, 8) 0.1090 0.2714 0.0430 0.0918 0.0380 0.0710 -
19 h (1/2, 9) 0.3270 - - 0.1860 - - -
20 h (112, 7) 0.0350 0.3439 0.1800 0.1187 -0.1660 0.4980 -
21 ~(CCR/NCR,CCRC/NCRC 0.1870 - - - - 0.3860 -
22 h (5/6, 10) 0.4510 - - - 0.5415 0.6080 -
23 h (5, 9) 0.8460 - - - - 0.5000 -
24 h (5/6, 11) 0.] ] 10 - - - - 0.0800 -
25 h(4, 11) 0.0210 - - - - 0.0800 -
Table- IliA. I (cotinued)

FC FC Present For For For For For For

No. Definition Value Benzene IPyridine Toluene Metl!Ylpyridin4 APh Acetaldehydf
Non-planar force constants
~a) Diag:onal

1 y (CH) 0.3181 0.3237 0.3780 0.4319 0.4230 0.3050 -

2 y (CRCA) 0.4206 - - 0.5016 0.5170 0.6100 -
3 y (CO) 0.2565 - - - - 0.6100 0.3170
I

4 t (CRCA) 0.0025 - - 0.0001 - 0.4100 -

5 q> (CC) 0.1030 0.1190 0.1180 0.2717 0.2100 0.0100 -
6 q> (CN) 0.1090 - 0.1180 - 0.1750 0.3470 -
lrb) Off~diag:onal
0
7 F (1, 1) 0.0256 0.0184 -0.0570 -0.0723 -0.0390 0.0260 -
8 Fm (1, 1) -0.0235 -0.0235 0.0070 0.0003 -0.0180 -0.026( -
9 fP (I' l) -0.0107 -0.0227 -0.0260 -0.0143 -0.0100 -0.005( -
10 F (2, 3) -0.1158 - - - - - -
II T" (q>,q> ) -0.0139 -0.0388 -0.0840 -0.0579 -0.0690 -0.02 ]( -
0
12 K (l,q>) 0.0362 0.0273 - -0.1589 -0.1220 -0.039( -
13 Km 0: q>) 0.0017 -0.0263 - 0.0281 0.0260 -0.0010 -
0
14 K (2,q>) 0.0517 - - -0.1589 - -0.0550 -
15 Km (2, q>) 0.0802 - - -0.2810 - - -
16 K (3 cp) 0.0022 - - - - - -

a
R, H, rand h denote stretching , in-plane angle bending, stretch-stretch interaction and stretch
-bend (in-plane) interaction, respectively; y, -r, <p, F,T, and K denote waging, x-sensitive torsion, ring
torsion, wag-wag interaction, torsion-torsion interaction and wag-torsion interaction, respectively, A
and M represent the acetyl part and methyl group, respectively. The numbers in parentheses in the
defmition of off diagonal FCs indicate the internal coordinates associated with the respective diagonal
FCs. The superscripts o, m and p correspond to ortho, meta and para position, respectively.

b
Bond stretching FCs are in units of mdyn A- 1, stretch-bend interaction FCs in mdyn rad- 1 and
bending, wagging and torsion. FCs in mdyn A rad -z.

67
IIIA.2 FORCE FIELD CALCULATIONS

The Raman and IR spectra of the three isomeric APys are taken from reference (1]. Also
the Raman and IR spectra of APh are the same as those observed by Mross and Zundel [5] and
Gambi et al. [2] respectively. Some previous assignments of those molecules are modified in the
present investigation as described below.
Internal coordinates and force fields :- The molecular geometries of the pyridyl ring and
acetyl group are depicted in figure IliA. I and the internal coordinates are defined in table IliA. I.
The pyridyl ring geometry is taken as described by Bak et al. [6] and Soremen et al. [7]. The
phenyl ring of APh is considered to have a perfect hexagonal ring geometry as described in
previous work [2]. The geometries of the pyridyl and phenyl rings are assumed to remain
unaffected by acetyl substitution. The validity of this assumption has been shown by Del Bene
[8]. The structural parameters (i.e. bond lengths and bond angles) are also shown in figure IliA. I
and the masses of the atoms have been taken from Weast [9].

(i) (ii)

Figure IDA.l (i) Pyridyl ring, (ii) Acetyl group; R =phenyl I pyridyl ring; CM =methyl part;
CA = carbon of the acetyl group. The molecular structure of APh is taken as
described by Gambi et. al.

Since the methyl group is far from the phenyl/pyridyl ring and the methyl group
wavenumbers are very well known, we considered the methyl part of the acetyl group as a point
mass, which will help to simplify the calculation. Thus all the four molecules possess Cs
symmetry. Strictly, the symmetry of the substituted benzene or pyridine is dependent on the
orientation of this methyl group relative to the ring plane. This manifests itself only in the FC
matrix through non-equivalent interaction constants between coordinates associated with the
hydrozens of the methyl group and those of the ring and others part of the acetyl group. All such
interactions are omitted in the present work, as this perturbation hardly improves the calculated
wavenumbers, but increases the number of FCs. Internal rotational coordinates of the methyl
group are not included in the vibration analysis since a similar study [10] of all methyl-
substituted benzenes showed that they do not mix appreciably with other modes.
The standard Wilson GF matrix approach [11, 12] is employed using the familiar normal
coordinate program originally developed by Schachtschneider [ 13]. The GVFF, employed in this
calculation, is more appropriate than a Urey-Bradly-type field for large polyatornic aromatic
molecules such as those of interest here. The rationale for this choice has been clearly explained
by others [14, 15]. The vibrational problem is set up in terms of internal coordinates. ln
constructing the F matrix, 25 planar ( 11 diagonal and 14 off-diagonal) and 16 non-planar (6
diagonal and 10 off-diagonal) FCs are considered for the three substituted pyridine isomers. For
APh the number of FCs is reduced to 22 for in- plane modes (I 0 diagonal and 12 off-diagonal)
and 15 for out-of-plane modes (5 diagonal and 10 off-diagonal). The computations are
performed separately for the planar and non-planar modes.
The final set ofFCs determined in this study, their descriptions and numerical values are
given in table IIIA.1. The initial set of FCs is judiciously transferred from previous work on
benzene [16, 17], pyridine [18, 19], toluene [20], methylpyridine [1 0] and acetophenone [2].
Some off-diagonal force constants, which are thought to be important, are also introduced to
account for the interaction between the acetyl and phenyl or pyridyl ring. Cautiously varying the
initial set, we generated the final set of the force field.
As it is typical for calculations involving polyatornic molecules as large as these, the
problem is grossly underdetermined in that there are many more adjustable parameters (i.e. FCs)
than available experimental wavenumbers. In general, complication is remedied by the
acquisition of the spectra of isotopically labeled analogues. Initially we started our calculation
based on the vibrational data of three isomeric APys. Once a common moderately good set of
GVFF for these three isomers was determined, we included the vibrational data of APh. This
introduction helps in the augmentation of the vibrational wavenumbers without increasing the
number of FCs. Thus we considered APh and the isomeric APys at the same time with the
objective of obtaining a common valence force field. Another effort was made to limit the
number of independent FCs. This was accomplished by expressing certain off-diagonal elements
in terms of other off-diagonal elements rather than including them as independent force
constants. Regarding the present calculation, the 1-3 and 1-4 stretch-stretch interaction constant
are linked to the 1-2 interaction constant by incorporation of appropriate Z matrix modifications

69
[ 11-13, 21, 22]. This strategy also accomplishes another important goal: it helps to prevent the
evolution ofphysically unrealistic values ofFCs during the mathematical adjustment procedure,
wherein the calculated wavenumbers are fitted to the observed values. However, it is also true
that some flexibility is lost which prevents the highly precise reproduction of the observed
wavenumbers. Anyway, for a comparison, the initial set of the force field was transferred from
those derived previously for benzene [ 16, 17], pyridine [ 18, 19], toluene [20], methylpyridine
[1 0], acetophenone [2] and acetaldehyde [23] and are given in table IIIA.1 along with the fmal
set of the force field calculated in the present case.

illA.3 CHOICE OF FUNDAMENTALS

Planar modes :- For the 2-APy molecule, the fundamentals selected for the present NCA are
the same as assigned earlier [ 1] except in two cases. Under the i species, the assignments of the
fundamentals at 1421 and 1437 cm- 1 are interchanged for the reason of a better fit between the
observed and calculated wavenumbers. The wavenumbers 1421 and 1437 cm-1 are assigned as
the CH 3 asymmetric deformation mode and CC/CN stretching mode, respectively. The
1
wavenumber 1421 cm- is dropped from the observed fundamentals, as we are less interested in
the deformation of the methy 1 part of the acethyl group. The lowest i fundamental is calculated
to be 229 em -t. Medhi [ 1] assigned the wavenumber 215 cm-1 as the C-CH3 out-of plane bend
11
(wag) mode under a species. However, NCA with a similar type of molecule [2, 10, 20, 23]
shows that such an assignment (i.e. 215 cm-1 as the 0ex mode) corresponds to the lowest i
fundamentals.
For the 3-APy molecule, all the i fundamentals assigned earlier [1] are taken as such,
with the exception of some changes as discussed below. As for the 2-isomer, for the 3~isomer
1
also the lowest a fundamentals calculated to be 230 cm-1. The observed wavenumber of221 cm-
1 is correlated with the ~ex mode for the same reason as discussed earlier. Medhi [1] assigned
the wavenumber 1325 em -I as a combination band (623 + 704 = 1327), under l species.
However, we introduced it as a ~ex (a ) fundamental owing to its better fit.
1
Therefore, we
dropped one previously assigned ~eH mode at 1127 cm- 1 [which may be a combination band (958
+ 162 = 1120)], appearing just as a shoulder on the intense IR band at 1118 cm- 1 (already
assigned as another ~CH mode).

For the 4-APy molecule we agree with the earlier [1] assignments of the fundamentals
except for the lowest one of i species, which was previously (1] assigned at 358 cm-1• In the

70
 1
present calculation we put it near 219 cm- • Therefore, as discussed earlier, the calculated
wavenumber 229 cm- 1 is correlated with the 0cx (a!) fundamental.
The earlier assignments of the a! fundamentals of the APh molecule are in good
agreement with the result obtained here except in two cases only. Surprisingly, Gambi et al. [2]
did not assign any particular band corresponding to the Veacm stretching mode, but he considered
the wavenumber 955 cm- 1 as a mixed mode of aliphatic and aromatic C-C stretch. Moreover,
according to him the wavenumber 1021 cm-1 (shoulder) corresponds to the methyl rocking
p(CH3) mode. In the case oftoluene, La Lau and Snyder [20] have shown that the wavenumber
of the methyl rocking mode is 967 cm- 1• Therefore, in the present work, the wavenumber 955
1 1
cm- is correlated with the CH 3 deformation mode and the wavenumber 1021 cm- , which
appears just as a shoulder on the strong IR band at I 025 cm- 1 (assigned as C-H in plane angel
bending mode) is taken as a combination band [1430-413 =1017 (a1)]. Gambi et al. [2] obtained
1
the calculated wavenumber at 963 cm- , which was correlated with the observed wavenumber
1025 cm- 1. Previously, they neglected the weak but definite IR band at 1103 cm-1• However, we
have taken it in our calculation as a fundamental 0CH mode (also supported by Mross and Zundal
[5]). This modification also gives a better fit. Moreover, the assignment of the Vcaem mode (at
1
1078 cm- ) is consistent with the previous result for acetaldehyde [23]. For this molecule the
aliphatic C-C stretch mode is calculated at 1081 cm-1•
Non-planar modes :- Compared with assignments of the fundamentals reported earlier [1],
11
the a fundamentals in the present calculation differ only in one case each for the 2-,3- and 4-APy
molecules. As discussed earlier, the wavenumbers 215,221 and 219 cm-1 are assigned as the 0cx
1
mode of a species instead of the C-CH3 out-of-plane deformation mode [1]. The lowest
fundamental under a11 species is calculated to be 26 cm-1 for all three isomers. No observed
wavenumber could be associated with it. The PED corresponding to this vibration shows that it
may be assigned as a C-CH 3 torsion mode.
The present selection of the non-planar modes for the AP molecule is consistent with that
of Gambi et al. [2] and does not need any further modification.

71
Table- IIIA.2
Observed & Calculated fundamental wavenumbers ( v) for 2-APy

Symmetry Observed Calculated Potential Energy Distribution Present According

1
Species (vI cm- ) (vI cm-1) (PED) Assignment Gambi
(1) (2) (3) (4) (5) (6)

a' 3062 3063 3 (99) VcH 20b

3062 3062 3 (99) VCH 2
3062 3062 3 (99) VcH 20a
3062 3061 3 (99) VCH 7b
I697 I690 4 (73), 9 (I 0) Vco (subs.) Vco
1585 I589 I (15), 2 (64), 7 (11), 8 (22) VcC/CN 8a
1568 1568 1 (22), 2(54), 7 (1 0), 8 (20) VcCJCN 8b
1465 1471 1 (24), 2 (18), 8 (49) VcCJCN 19a
1437 1437 1 (07), 2 (28), 8 (59) VcCJCN 19b
1296 1302 1 (10), 2 (36), 5 (24), 6 (13), 8 (33) Voca (x-sens.) 14
1281 1275 1 (48), 2 (59), 5 (17), 6 (14), 8 (11) VcCJCN 3
1238 1224 1 (20), 6 (14), 8 (51) PCH VcaCm
1150 1183 2 (13), 8 (79) PCH 9a
110 I 1113 2 (25), 8 (49) PCH 15
1086 1084 6 (19), 7 (31), 8 (21) Vcacm (subs.) I3
1044 1056 2 (18), 7 (37), 8 (27) PCH 18a
996 1006 1 (18), 2 (52) VcCJCN 1
(ring breathing)
750 750 2 (11), 5 (25), 6 (11), 7 (32) accc 12
622 622 7 (62), 8 ( 1I ), 10 (1 0) accc 6b
590 593 7 (31 ), 11 (26) Pco (subs.) Pco
- 543 9 (27), 10 (23),11 (12) Pocaem (subs.) 6a (x- sens.)
362 359 5 (12), 7 (12), 11 (38) accxe (x-sens.) 18b
215 229 9 (48), I 0 (25), 11 (24) Pcx (x-sens.) Ycaem

Average error= 6.19 cm- 1 (0.79°/o)

72
Table- IIIA.2 (cotinued)

(1) (2) (3) (4) (5) (6)

a" - 965 1 (86), 5 (48) YCH -

954 953 1 (92), 5(39), 6 (14) YcH 17a
903 912 1 (75), 5 (37) YcH 5
779 773 1 (76), 5 (22) YcH lOb
700 700 1 (51), 5 (23), 6 (07) <I> Ring 4
492 492 1 (23 ), 2 (60), 5 (3 7), 6 (05) <I> Ring 11
409 422 2 (27), 3 (113) Yeo (subs.) Yeo
409 395 1 (22), 2 (43), 5 (17), 6 (25) <I>Ring 16a
163 163 1 (12), 2 (44), 5 (36), 6(38) Ycx (x-sens.) 16b
- 26 4 (100) <perca (subs.) -

Average error= 6.80 cm· 1 (1.29 %)

OIA.4 ASSIGNMENT OF NORMAL MODES

The observed fundamentals [ 1, 2], the calculated wavenumbers, their corresponding

PEDs and the proposed vibrational assignments for 2-, 3- and 4-APy and APh are given in tables
IIIA.2, IIIA.3, IIIA.4 and IIA.5, respectively. It is clear from these tables that the calculated
wavenumbers agree fairly satisfactorily with the observed values. These tables also show that
the assignments for the several of the pyridyl and phenyl ring modes are obvious and require no
further discussion. Therefore, a brief discussion only for some controversial and important
modes is given below.
Planar modes :- The assignments of the fundamental modes in the present case are almost
same as in the earlier work [1] for all the isomers of acetylpyridine except only for the following
cases. For 2-APy the wavenumbers 1296,1281, 1238 and 1086 cm· 1 assigned earlier [1] to
modes 14, 3, v(C-CH3) and 13, respectively, are now assigned as shown in table IIIA.2 in the
light of the PED. For the same reason, the wavenumbers 1325,1247, 1243,1195 and 1091 cm· 1
for 3-APy and 1324,1267,1253 and 1084 cm· 1 for 4-APy have been reassigned as shown in tables
IIIA.3 and IIIA.4, respectively.

73
Table - IIIA.3
Observed & Calculated fundamental wavenumbers ( v) for 3-APy

Symmetry Observed ~alculated Potential Energy Distribution Present According

1 1 Gambi
Species (vI cm- ) (vI cm- ) (PED) Assignment
(I) (2) (3) (4) (5) (6)

a' 3059 3064 3 (99) VcH 20b

3059 3062 3 (99) VCH 2

3059 3061 3 (99) VCH 20a

3059 3060 3 (99) VCH 7b

1690 1690 4 (73), 9 (1 0) Vco (subs.) Vco

1586 1586 I (21), 2 (60), 7 (11), 8 (22) VcCJCN 8a

1574 1576 1 (23), 2 (52), 7 (I 0), 8 (22) VCCJCN 8b

1480 1483 I (15), 2 (25), 8 (51) VCC/CN 19a

1417 1404 1 (13),2(29),8(41) VcCJCN 19b

1325 1312 2 (49), 8 (70) PCH 623+704 =1327 (l)

1274 1279 1 (33), 2 (22), 5 (33), 6 (25) verca (x-sens.) 14

1243 1249 1 (30), 2 (32), 5 (12), 6 (14), 8 (28) VccJCN 3

1195 1178 2 (10), 8 (80) PCH Vcaem

1I I 8 I I02 I (12), 2 (18), 8 (48) PCH 15

1091 1084 2 (17), 6 (24), 7 (22), 8 (23) Verca (subs.) 13

1078 1057 2 (18), 7 (39), 8 (26) PCH 18a

1034 1001 1 (27), 2 (39) VCCJCN 1

(ring breathing)
749 748 1 (15), 5 (16), 6 (II), 7 (32) <Xccc 12

623 622 7 (70), 8 (12) <Xccc 6b

591 593 7 (25), 10 (14), 11 (27) Pco (subs.) 13co

- 546 2 (14), 9 (27), 10 (23), 11 (10) Percaem (subs.) 6a (x-sens.)

366 356 5 (12), 7 (12), I 1 (39) accc (x-sens.) 18b

221 230 9 (48), 10 (26), 11 (24) Pcx (x-sens.) Yeaem

Average error= 7.77 cm- 1 (0.88%)

74
Table- IIIA.3 (cotinued)

(1) (2) (3) (4) (5) (6)

a" - 988 1 (77), 5 (15), 6 (16) YCH -

958 958 1 (91), 5 (51) YcH 17a

928 928 1 (86), 5 (29), 6 (12) YCH 5

809 782 1 (92), 5 (14) YCH lOb
704 700 1 (19), 2 (15), 5 (40), 6 (07) <{>Ring 4
472 491 1 (24), 2 (37), 5 (29), 6 (05) <{>Ring 11

405 419 2 (39), 3 (120), 5 (1 0) Yeo (subs.) Yeo

405 387 1 (18), 5 (27), 6 (26) <j}Ring 16a
162 162 I (21 ), 2 (89), 5 (57) Ycx (x-sens.) 16b

- 26 4 (100) <paca (subs.) -

Average error= 10.14 cm- 1 (1.96 %)

As discussed earlier, previous knowledge [2, 5, 10] helped us to assigned the

1
wavenumbers 362 and 215 cm- (for 2-APy), 366 and 221 cm-1 (for 3-APy) and 358 and 219 cm-1
(for 4-APy) as substituent-sensitive modes. These assignments are also strongly supported by the
present calculation for all three isomeric molecules. Previously [1] both the ~co and ~creaem
1
modes were assigned at 590 cm- for all the isomers. However, the present calculation places the
Pco and ~creacm modes in the wavenumber regions 589-593 and 543-549 em-\ respectively, for
all the three isomers.
According to the PED, for the APh molecule the previous assignments of the three pairs
of wavenumbers 1312 and 1303 cm- 1, 1000 and 730 cm-1 and 547 and 368 cm-1 are just
interchanged between themselves. These rearrangements do not reveal any dramatic change to
the conclusions. The changes of assignments made in the previous section is consistent with the
PED and is shown in table IIIA.5.

75
Table- IIIA.4
Observed & Calculated fundamental wavenumbers ( v) for 4-APy

Symmetry Observed !Calculated Potential Energy Distribution Present According

Species (vI cm- 1) (vI cm- 1) (PED) Assignment Gambi
(J) (2) (3) (4) (5) (6)

a' 3066 3064 3 (99) VcH 20b

3066 3062 3 (99) VcH 2
3066 3062 3 (99) VcH 20a
3066 3060 3 (99) VCH 7b
1694 1691 4 (73), 9 (1 0), vco (subs.) Vco
1596 1596 1 (15), 2 (67), 7 (11), 8 (22) VcCJCN 8a
1557 1556 1 (31), 2 (44), 7 ( 10), 8 (I 5) VcctCN 8b
1494 1494 1 (20), 2 (21), 8 (56) VccJCN 19a
1410 1406 2 (39), 8 (48) Vcctc..'N 19b
1324 1303 2 (48), 8 (58) BCH 14
1267 1267 5 (3 7), 6 (34 ), 8(23) Verca (x-sens.) 3
1253 1259 1 (62), 2 (51), 8 (16) VcctCN Vcaem
1214 1 I 72 8 (80) BCH 9a
1115 1 122 2 (25), 8(54) BCH 15
1084 1084 2 (13), 6 (25), 7 (28), 8 (17) Veacm (subs.) 13
1063 1050 2 (19), 7 (41), 8 (26), Brn 18a
993 IOOI I (42), 2 (28) VcCJCN I
(ring breathing)
736 734 2 (14), 5 (28), 6 (12), 7 (33) accc 12
603 637 7 (65), 8 (15), accc 6b
589 589 7 (28), 10 (I 5), 11 (26) Bco (subs.) Bco
- 549 2 (13), 9 (27), 10 (22), 11 (13) Bcreacm (subs.) 6a (x-sens.)
358 357 5 (12), 7 (13), 11 (38) accc (x-sens.) 18b
219 229 9 (4 7), 10 (25), 11 (25) Pcx (x-sens.) Ycaem

Average error= 7.68 em·• (0.92 °/o)

76
Table- IIIA.4 (cotinued)

(1) (2) (3) (4) (5) (6)

a" - 987 1 (88), 5 (30) Ym -

963 975 I (90), 5 (37), 6 (17) YCH 17a
875 868 I (77), 5 (23), 6 (13) YCH 5
817 817 1 (92), 5 (17) YeH lOb
666 673 1 (13), 2 (23), 5 (46), 6 (12) {j>Ring 4
465 464 1 (25), 5 (47) {j>Ring 11
417 426 1 (30), 2 (56), 5 (8), 6 (14) {j>Ring 16a
4I7 412 2 (28), 3 (132), 5 (13) Yeo (subs). Yeo
158 155 I (15), 2 (101), 5 (78), 6 (11) Yex (sens). 16b
- 26 4 (100) <i>erea (subs). -

Average error= 5.60 cm-1 (1.10 %)

Non-Planar modes :- The out-of plane C-H wagging (yrn) modes have been assigned in the
three isomeric acetylpyridines in a different way with respect to the previous assignments [1].
For these molecules other corrections are made for the wavenumbers in the regions 465-495 and
1
I58-I65 cm- • We interchanged the mode assignments made previously by Medhi [1]. These
results are in good agreement with earlier studies [2, 5, 10, 24].
The Yeo mode is the only controversial mode for the APh molecule. According to the
1
PED the wavenumber 413 cm- is correlated with the Yeo mode and the wavenumber 467 cm-1
with the ring distortion mode. The assignment of the Yeo mode at 413 cm-1 is well supported by
Allkins and Lippincott (25], Handi et al. (26, 27] and others [1, 23, 28, 29].

77
Table - IIIA.5
Observed & Calculated fundamental wavenumbers ( v) for APh

Symmetry Observed !Calculated Potential Energy Distribution Present According

1 1
Species (vI cm- ) (vI cm- ) (PED) Assignment Gambi
(1) (2) (3) (4) (5) (6)

a' 3067 3064 3 (99) VCH -

3061 3062 3 (99) VCH -

3061 3061 3 (99) VCH -
3061 3061 3 (99) VCH -
3061 3058 3 (99) VCH -

1685 1687 4 (73), 9 (1 0) Vco (subs). Vco

1599 1596 2 (80), 7 (11 ), 8 (23) Vee 8a

1582 1580 2 (77), 8 (20) Vee 8b

1492 1487 2 (39), 8 (58) Vee 19a

1450 1460 2 (39), 8 (50) Vee 19b

1312 1336 8 (88) ~CH 14

1303 I307 2 ( 141 ), 8 ( 16) Vee 3

1265 I266 2 (11), 5 (43), 6 (39), 8 (I2) Verea (x-sens.) 13

1181 1186 2 (12), 8 (81) ~CH 9a

1160 1170 2 (11), 8 (80) ~CH 15

II 03 1093 2 (30), 8 (45) ~CH -

I078 1081 2 (13), 6 (23), 7 (34), 8 (18) Veaem (subs.) 18b

I025 1046 2 (31 ), 7 (26), 8 (31) ~CH 18a

1000 1002 2 (70) Vee 1

(rll1g breathll1g)
730 747 2 ( 18), 5 (26), 7 (31) accc 12 (x-sens.)

6I8 628 2 (12), 7 (66), 8 (16) accc 6b

590 590 7 (25), I 0 (13), 11 (27) ~oo (subs.) ~co

547 540 2 (13), 9 (27), 10 (24), 11 (12) ~creacm (subs.) 6a (x-sens.)

368 355 5 (11), 7 (12), 1 I (40) accc (x-sens.) ~CrCaCm

226 225 9 ( 48), 10 (25), I 1 (24) ~ex (x-sens.) 9b

Average error= 6.33 cm- 1 (0. 72 o/o}

78
Table- IIIA.S (cotinued)

(1) (2) (3) (4) (5) (6)

a" 980 969 1 (84), 5 (32) YCH 5

974 954 1 (91 ), 5 (54) YcH 17a
925 931 I (84), 5 (65) YCH I7b
848 861 1 (78), 5 (34) YCH lOa
761 777 1 (4I), 5 (35) <prung 11
691 720 1 (95), 5 (13) YeH 4
520 504 1 (25), 2 (41 ), 5 (3 7) <!'Ring 16b
467 490 1 (26), 5 (45) <prung Yeo
413 413 2 (47), 3 (126), 5 (13) Yeo (subs.) 16a
I60 160 1 (22), 2 (1 06), 5 (68) Yex (sens.) lOb
- 25 4 (I 00) <perea (subs.) <i'CrCa

Average error= 13.38 cm- 1 (1.96 o/o)

llJA.5 DECOMPOSITION OF NORMAL COORDINATE VlBRATIONAL

WA VENUMBERS

A decomposition scheme for partitioning the normal coordinate vibrational wavenumbers

into individual internal coordinate wavenumbers was put forward by Baatz and Gorden [3] and
Mallick et al. [4]. In this scheme, each internal coordinate is assigned to a wavenumber that is
representative of a vibration described solely by motion of that particular internal coordinate.
The total potential energy (V) for a given molecule may be expressed in terms of the
internal coordinates as,
s
2V = L: Fi,J RiR i (IIIA.l).
i<j
where F;J is the force constant connecting the pair of internal coordinates R; and R1 and S is the
total number of internal coordinates. The usual procedure is to use S [= 3N -6(5)] internal
coordinates [according to non-linear (or linear) molecules] which are complete. However, often
a redundancy problem arises in the normal coordinate calculation. In such a case, S>3N-6(5).

79
Here the set of symmetrically equivalent internal coordinates is so chosen that they are complete
in the sense that all vibrational degrees of freedom must be described [3].
The internal coordinates (R/s) are related to the normal coordinates (Qk's), as follows:
3N-6(5)
Ri = L 4kQk (IIIA.2)
k=l
where L;k is the component of the so-called L-matrix. Substitution of equation (IIIA.2) into
equation (I) yields,
s
2V = L Fij L LikQk L Ljk'Qk'
i,j k k'
(IIIA.3)

= L[t
k I,.J
FijLikL jk]Q:

According to the definition of the normal coordinates, equation (IIIA.3) becomes,

2V = LAkQJ (IIIA.4)
k

where Ak =(4n 2vf c 2 ) gives the potential energy per unit displacement of the normal

coordinate Qk and vk is the wavenumber of the k-th normal mode. Equations (IIIA.3) and

(IIIA.4) thus give,

s
I= L( FijLikLjk )I Ak
i,j (IIIA.5)
=L_Pj
i,j

The quantity (FiJ Lk LJIJ!Ak is known as the potential energy distribution (PED) of the k-th
normal mode of vibration corresponding to the force constant Fy and is a measure of the
fractional contribution to Ak arising from the various F-matrix elements. These PEDs are
available in the output of standard programs. Thus the diagonal elements (i.e. where i =j) of the
PED can be used to obtain the contribution of vibrational wavenumbers to the i-th internal
wavenumbers. Therefore, it is possible to generate 'pseudo-diatomic' simple harmonic motion
corresponding to the internal coordinate (say Ri) having a wavenumber associated with it:
Jn-6(5) k-
wi = L Pu v k (IIIA.6)
k=l
Generally, owing to symmetry properties we need not sum over all the 3N-6(5) normal modes of
vibration in equation (IIIA.6). Instead, only those normal modes belonging to certain symmetry
species are necessary for which the relevant force constant F;; and the PEDs (P/ 's) are effective.

80
Table- IIIA.6
Pseudodiatomic Wavenumber (PDW) associated with different Internal
Coordinates

Internal Pseudodiatomic wavenumber (PDW) *

Co-ordinate 2-APy 3-APy 4-Apy APh
(1) (2) (3) (4) (5)

Planer modes

VCN 2624 (2) 2611 (2) 2621 (2) -

Vee 5370 (4) 5382 (4) 5372 (4) 8038 (6)

VCH 12164 (4) 12164 (4) 12164 (4) 15200 (5)

Ve=O 1530 1530 1530 1530

Verea 1154 1150 1150 1151

Veacm 1139 1139 1139 1139

UecC/eCN/CNe 2264 (6) 2269 (6) 2269 (6) 2211 (6)

~CH 5594 (4) 5593 (4) 5593 (4) 6979 (5)

~ex 929 927 930 915

8creacm 495 494 494 487

0 e=O 648 648 648 637

Non-~laner Modes

YCH 3554 (4) 3516 (4) 3524 (4) 4443 (5)

Ycx 784 691 729 737

Ye=o 523 523 529 529

terea 26 26 26 26

<Pee 1851 (4) 1682(4) 1723 (4) 2663 (6)

<j)CN 450 (2) 608 (2) 597 (2) -

The number of symmetry equivalent internal co-ordinates associated with PDW is indicated in the
parentheses.

81
 Let us now illustrate the result available from the calculation of 'pseudo-diatomic'
wavenumbers (PDWs), given by equation (6), determined for different internal coordinates for
the above molecules. In our normal coordinate calculation, redundancies appeared owing to the
inclusion of different symmetry-equivalent internal coordinates and that chosen set of internal
coordinates is complete following the sense mentioned by Boatz and Gorden [3]. In table IIIA.6
are given the total PDWs associated with different types of symmetry-equivalent internal
coordinates and the numbers in parentheses indicate the total number of internal coordinates in
the corresponding symmetry-equivalent internal coordinate.
The result is consistent and in agreement with those ofBoatz and Gorden [3] and Mallick
et al. [4]. The total PDWs associated with the six ring C-C stretching in APh is more or less
equal to the sum of those for the two C-N stretching and four C-C stretching wavenumbers in the
three isomers of acetyl pyridine. The average (pseudo-diatomic) ring C-C stretching
wavenumbers are thus approximately 1340 cm- 1 for APh and 1343, 1346 and 1343 cm- 1 for 2-,3-
and 4-APy, respectively (as can be seen from data given in table IIIA.6). In a similar fashion, the
1
PDWs per C-N stretching are seen to be approximately 1312,1305 and 1312 cm- in the
respective isomers of acetylpyridines. The relative magnitudes of these two average PDWs are
in accordance with our expectation. Further, these wavenumbers are consistent with those values
of vcctCN with the corresponding bond orders lying between one and two [3, 4]. There are two
types of substitutent C-C bonds: one is CRCA and the other is CACM. From Table 4, we see that
the PDW associated with the former internal coordinate is slightly greater than that of the latter in
all four molecules. This is according to our expectation because, both the carbon atoms, CR and
2
CA, exhibit sp hybridization, whereas the CM atom of the methyl group exhibits sp 3
hybridization. Moreover, all the other PDWs, associated with different types of internal
coordinates (for both planar and non-planar motions), as shown in Table 4, are up to the
expectation (3], which is a check of the consistency of the present normal coordinate calculation.

82
IIIA.6 REFERENCES

[1] K. C. Medhi, Indian}. Phys., SlA, 99, (1977).

[2] A. Gambi, S. Giorgianni, A. Passerini, R. Visinoni and S. Ghersetti, Spectrochim Acta.,
36A, 871, ( 1980).
[3] J. A. Boatz and M.S. Gorden, .f. Chern. Phys., 93, 1819, (1989).
[4] P. K. Mallick, D. P.Strommenand J. R. Kincaid,}. Am. Chern. Soc., 112,1686, (1990).
[5] W. D. Mross and G. Zundal, Spectrochim Acta., 26A, 1097, (1970).
[6] B. Bak, L. Hansen and N. R. Andersen, J. Chern. Phys., 22,2013, (1954).
[7] G. 0. Sorensen, L. Mahler and N. R. Andersen, J. Mol. Struct., 20, 119, (1974).
[8] 1. E. Del Bene, J. Am. Chern Soc., 101, 6184, (1979).
[9] R. C. Weast (Ed.), Handbook of Chemistry and Physics (65-th Edn.), CRC Press: Boca
Raton, FL, (1984-85).
[10] J. A Draeger, Spectrochim Acta., 39A, 809, (1983).
[11] E. B. Wilson Jr., J. C Decius and P. C. Cross, Molecular Vibrations, McGraw-Hill: New
York, ( 1955).
[12] E. B. Wilson, J. Phys. Rev., 45, 706, (1934).
[13] J. H. Schachtschneider, Technical Reports Nos 231-64and 57-65, Shell Development,
Emoryville, CA, ( 1964).
[14] N. Neto, M. Scrocco and S. Califano, Spectrochim Acta., 22A, 1981, (1966).
[15] J. R. Scherer, Spectrochim Acta., 20, 345, (1964).
[16] P. C. Painter and J. L. Koening, SpectrochimActa., 33A, 1019, (1977).
[17] P. C. Painter and R. W. Snyder, Spectrochim Acta., 36A, 337, (1980).
[18] D. A. Long, F. S. Murfin and E. L. Thomas, Trans. Faradey Soc., 12, 59, (1963).
[19] J. W. Emsley, J. C. Lindon and J. Tabony, J. Chern Soc. Faraday Trans.-2, 71,511,
(1975).
[20] C. La Lau and R. G. Snyder, Spectrochim Acta., 27A, 2073, (1971).
[21] P. K. Mallick, G. D. Denzer, D. P Strommen and J. R. Kincaid, J. Phys. Chern., 92, 5628,
(1988).
[22] D. P Strommen, P. K. Mallick, G. D. Denzer, R. S. Lumpkin and J. R. Kincaid, J. Phys.
Chern., 94, 1357, (1990).
[23] P. Cossee and J. H. Schachtschneider, J. Chern. Phys., 44, 2073, (1971).
[24] G. Varsanyi, Vibrational Spectra of Benzene Derivatives, Academic Press: New York,
(1969).

83
[25] J. R. Allkins and E. R. Lippincott, Spectrochim Acta., 25A, 761, (1969).
[26] A. Handi, Ann. Phys., 10, 874, ( 1955).
[27] A. Handi, J. Deschamps and M. L. Josien, C. R. Acad Sci., 242, 1014, (1956).
[28] J. Lecomte, M. L. Josien and J. Lascombe, Bull. Soc. Chim. Fr., 163, (1956).
[291 J. Lecomte, Handhuch der Physik., Band XXVI: Springer, Berlin, ( 1958).

84
 CHAPTER IIIB

RAMAN EXCITATION PROFILES OF

THREE ISOMERIC ACETYLPYRIDINES
AND ACETOPHENONE
IIIB.l INTRODUCTION

A better understanding of the photophysical and photochemical behavior requires

elucidation of the electronic and geometrical structures of molecules in the ground and excited
electronic states [1-11 ]. Importance of Raman spectra in determining the structure of molecule
in the ground electronic state is very well known. Resonance Raman spectroscopy was shown
to be a very useful technique in probing the excited states of molecules [12-14]. Actually,
resonance Raman spectroscopy bridges the gap between electronic spectroscopy (absorption and
emission) on one hand and ordinary Raman spectroscopy on the other hand. Thus resonance
Raman effect has proved to be a rich source of information on the nature of the excited
electronic states and on the intricate mechanism often involved in their coupling. Raman
excitation profiles give us better knowledge to understand the change of molecular excited state
geometry (with respect to ground state) and may also conftrm whether the same symmetry in
different electronic states exists or not. For resonance excitation, Raman intensity is mainly
dominated by the contributions from the resonating and its nearby states and this Raman
excitation profile (REP) is, generally, explained in terms of several parametric values of those
states [15-29]. For excitation in a region not very close to an excited electronic state,
contributions from several electronic states might be important [11, 15, 30-41 ]. In this region of
excitation, extensive investigation of REPs is found to be very helpful in getting structural
insights and studying many other interesting properties of the molecule in different excited
electronic states. In the present work, we thoroughly examined the REPs of several normal
modes of vibration of 2-, 3-, and 4-acetylpyridines (henceforth named as 2-Apy, 3-Apy, and
4Apy,respectively) and acetophenone (henceforth denoted as APh) for excitation in the region,
where the contributions of several electronic states are not unlikely, and thus tried to make a
comparative study and to investigate many other interesting properties of the molecules in the
ground and excited electronic states, which, in turn, might be helpful in determining the
dependence of the photophysical/photochemical behavior on the position of the acetyl group
with respect to theN atom of the pyridyl ring.

DIB.2 DISCUSSION

To get a prior knowledge about the nature of different normal modes of vibration, along
with the investigation of REPs, critical analyses of the IR and polarized Raman spectra of the
four compounds are necessary. Detailed normal coordinate analyses of the said molecules have
been performed and presented in the previous chapter and in reference [42]. Assignments to the
86
different normal modes of vibration has been done on the basis of the potential energy
distribution [PED] obtained from the calculation and compared with those done in previous
work [43-45].

111B.2A Electronic Spectra

1.2 .......------

'
I \
·' I' I
-APh
q ·.I I ~ .• \
..... 2.-/<P'j
l\ :~·:. ·.. '·'
I' ··· .. ;i.AI~
<1-Ar'y
'•
I I / •••• 0

' 1." 'i'

l>
'I

I· I i:
r,;.; \
.- I .·~~ .. \
.. ,.. .J·.· . /
I I'
·~
\
\ ~
·,
( 1: ' I ' ··./ '1 \ ' \
..: \ I .I I ·, I! I / .,
'.
I
II ~( r I·
'.
'\
l \ /:· i':"\/ \
I
'·.
'
I~ 1
1 / \J~ ...... I
~

. I ' \ 0

I
. . •

\_// .\ ' .. \

. '
\ ' . ' .
\... ... \' '

tl.U
. . _---·---~=---.·-.:-·-"'""-.--r-;
. . :'.:..- ·~· :-:. ··--·· .......
.. ~·~·r..,..;.·

200 550

Wavelength I nm

Figure IIIB.l Absorption spectra of2-Apy, 3-Apy, 4-Apy and Aph in EtOH solution.

The electronic absorption spectra of the title compounds (i.e.,2-APy,3-APy, 4-APy, and
APh) are shown in figure IIIB. 1. For 2-APy, there are three bands at 268, 230, and 204nm,
1
which are assigned as Lb, 'La, and 1Bb bands [46], respectively. In 3- and 4-Apy, the
corresponding bands appear at 268,229, and 205nm and 276,218, and 204nm, respectively. As
1
expected, the Lh band in each of the three isomers of acetylpyridine is weaker than the
respective 1La band. For the remaining molecule APh, the 1Bb band appears more or less at the
same position (204nm). On the longer wavelength region of the absorption spectra, the intensity
1
of the La band at 240 nm is slightly less than those of the three APys, but compared to other
three isomeric molecules of APy, 1Lb band (appeared around 280nm) of APh is found to be
rather weak, broad and diffuse. From a comparative study of the spectra, it is also found that
both 1Lh and 1La bands of the aforementioned isomers of APys are definitely blue shifted with
respect to the corresponding bands of APh. The shift of 1La band is largest in the 4-isomer,

87
 1
whereas greater shift of the Lh band is observed in 2-and 3-APys. The shifts in the
wavenumbers of the 1Lh and 1La band systems may be attributed to the significant variation of
the charge-transfer character involved in these transitions in order of increasing distance of the
acetyl group from N-hetero atom of the pyridyl ring in the isomers from 2-Apy to 4-Apy. These
excited states in all the four molecules are designated as S~, Sz, and S3 in order of increasing
energies such that the electronic transitions G~S~, G~Sz, and G~S3 correspond to L~>, La,
1 1

1
and Ba bands, respectively. Further elaboration of the electronic absorption spectra is made
below during our discussion on REPs.

1118.28 Raman Excitation Profile

Both observed and calculated REPs of several normal modes of vibration of the four
molecules are presented in figures IIIB.2, 1118.3, 1118.4 & 1118.5. The observed profiles in
chloroform and carbon tetrachloride solutions at room temperature (around 30°C) are presented
by symbols. The theoretically determined REPs, i.e.,the diagonal (A-term) and off-diagonal (B-
term) contributions from different excited electronic states and also the classical contribution
p.e.,(vo-Va )~ dependence l, are represented by different curves accordingly marked to indicate
the contributors. The effect of the linewidth on REPs was checked as was done by
Chattopadhyay et al. [9] and Sett et al. [ 10, II], but no significant effect was found. An attempt
1
was made to measure the REPs in the polar-solvent methanol, but the solvent band at 1032 cm-
(generally used as internal standard) overlap with the solute bands in this region so profoundly
that the idea of measuring REPs in this solvent was left undone. To test the consistency of the
present experimental observations, REPs in chloroform and carbon tetrachloride solutions using
proper internal standards, mentioned in the experimental section of chapter II, were measured.
The accuracy of the measurements of intensities of different Raman bands varies, but REP
values are confined within the error ±0.05.
As mentioned in the earlier work, the strong and highly polarized Raman band at I 000
1
cm- corresponds to ring breathing mode of the phenyl ring in APh. The corresponding pyridyl
ring modes in 2-, 3-, and 4-Apy are of wavenumbers 995,1035, and 993 em-\ respectively.
From figures 1118.2, IIIB.3, 1118.4 & IIIB.5 we can see that none ofthe above three electronic
states S~, Sz or S3 contributes chiefly to this mode through A or B term. In 2-APy, this ring-
breathing mode follows more or less the classical excitation wavenumber dependence [i.e., a
3
(vo-va) dependence]. This means that the mode gets an intensity contribution :from the
electronic states lying very high on the energy scale. But in the case of other three molecules

88
(i.e. 3-APy, 4-APy and APh), certain interesting observations were made. If one AIG is chosen
around 170nm, intensity contributions to various Raman fundamentals from the corresponding
excited state become very fascinating. Let the corresponding electronic state be named as S4.
From figures IIIB.3, IIIB.4 & IIIB.5 it is seen that the contribution from this state to this mode is
a favourable one through A-term. The dominating A-term contribution indicates that distortion
in all the molecules (except 2-APy) along this mode is significant in the electronic state S4,
which means that the corresponding pyridyl or phenyl ring dimension changes significantly in
this electronic state. This is because, as stated earlier, the intensity contributions to the a-th

Raman mode coming from an excited state II> through A term is found to be proportional to the

square of the displacement of the potential minimum of that state with respect to that of the
ground state, i.e., !'J\. The depletion of the observed REPs in the 3-isomers of Apy

corresponding to Ao = 457.9 nm indicates that some destructive interference between the A term
(diagonal contribution from the state S4) and B term (off-diagonal contribution from the pair of
the states S1 and S4) might take place in this region of excitation. Such a possibility was pointed
out previously in earlier works [9, 15]. There is also a second possibility in which case some
electronic state (s), lying above S4, may be better contributor(s) and in that case the above
interference becomes less important. Besides, the absence of off diagonal B-term contribution
from different pairs of the excited electronic states indicates that the vibronic interactions
between these electronic states through this mode are weak. It is noteworthy to mention that the
vibronic coupling of the state S4 withStand Sz were excluded from our consideration because of
a large energy gap between them. Moreover, as the excited electronic states (St to S3) do not
contribute to this mode through A term, the corresponding ring geometry is not expected to
change very much in these electronic states.
One point, worth mentioning here, IS that we observed absorption spectra at
concentration 10 4 M, whereas the REPs measured at higherconcentratiori (ofthe order of IM).
So one might expect the occurrence of some kind of dimerization or other aggregation
phenomena since aromatic molecules can easily form dimers and/or oligmers in high
concentration. To understand critically what is actually happening at higher concentrations, we
took absorption spectra at various concentrations in the range 104 to I M in 4-acetylpyridine.
Only the band intensities are found to increase with the increase of solute concentration and the
spectra become very broad at concentration on and above 10-1 M. Besides, the 1Bb band around
200nm exhibits a red shift of about 1Onm at higher concentration. The same type of effect was
also observed in acetophenone and in other two isomers of acetylpyridine, so one might expect

89
 1
that either the Bh band is red shifted on aggregation or split into exciton bands of which one
component is shifted toward red by about 1Ocm- 1 and the other is shifted toward vacuum
ultraviolet region. So the S4 state, corresponding to the band around l70nm, is either a
molecular state, probably 1Ba or the other split component of the above mentioned exciton bands
1
(14). In all four molecules, the peak positions of 1La and Lh bands do not practically undergo
1
any change even at higher concentrations; only a weak band around 325cm- appears in all the
molecules (except 4-acetylpyridines). So this band is assigned as an aggregation band, which
·. .
was not found to be important for contribution to Raman intensities.
1
The wavenumber 750cm- is assigned [43-45] as the triangular mode (number 12
according to Wilson notation) in 2-APy. REP of this mode (figure IIIB.2) shows that none of
the above states (St to S4) contributes to this mode. Instead this mode follows the classical
excitation wavenumber dependence. For the 3-isomers the chief contribution to this mode
1
(751cm- ) comes from the electronic state S4 through A term (as shown in figure IIIB.3). This
means that the molecule in the state S4 is undergoing appreciable distortion along this mode.
The B term contribution from the pair of electronic states S3 and S4 is also not unlikely. This
means that this mode may be an effective one in mixing the two electronic states S3 and S4,
affirming the ring symmetries to remain the same in these states. Figure IIIB.4 shows that REP
1
of this mode (at wavenumber 739cm- of 4-APy) lies between the curves corresponding to
classical contribution and that of diagonal contribution from the electronic states S4, which
means that some state( s) lying above S4 may be important contributor( s) to this mode. In APh
this mode (731cm- 1) follows classical wavenumber dependence. A similar kind of observation
(as that witnessed for the triangular mode in the respective molecules) was made with the in-
plane ring-distortion mode accc (622 and 624 for 2- and 3- APys, respectively), but REP of this
1
mode (617cm- ) in APh is different and to some extend interesting. Apparently it seems that a
good contribution to this mode comes from the electronic state S4, but the depletion of the
observed data corresponding to the excitation wavelength Ao = 457.9 nm indicates that some
destructive interference between the A term (contribution from the state S4) and B term
(contribution from the pair of the states S3 and S4) might takes place in this region of excitation.
Alternatively, some higher state(s) lying above S4 might be better contributor(s). The same kind
of observation was made for the ring-breathing mode in 3-APy.

90
 2.4 1 1
163 cm·1 2.4 1,1 ~

. ~:=...., \
2.2 1,2 \
2-2
.
Ycx mode· 1,3,\ .
2.0 2. 2 2.0 2.2
2,3
~·~
1.S 3:4
4,4
1.8 !:!
t4,4
1.6 1.6
'
,;
1.4 1.4

1.2

2.4 1. 1 2.4 1,1 ~

750 cm·1 995 cm"1
2.2 1,2\ 2.2 1,2 \ .
1. 3 \ Clccc mode 1,3 \\ vCCICN mode
2.0 2,2
~II)
2.0 2,2
2,3 2,3
c 3,3 3.3
1.8 3,4 1.8 3, ..
....Q)c t4,4
-Q) 'Hi
4,4
1.6
>
;::: v
l

.!! 1. 4 1.4
Q)
0: 1.2 1.2

2.4 1,1 ~
1044 cm·1 1086 cm"1
2.2 1,2 \ . .
~cH mode 1,3\\ v~c (subs.)
2.0 2.0 2,2
2.3
3,3
1.8 1.8 3,4
-4,-4
1.6 1.6
i
1.4 1.4

1.2 1.2

Excitation Wavelength /Ao

Figure DIB.2 Measured and calculated REPs for 2-APy.

91
 2.4 1' 1
1101 cm·1 1238 cm·1
~CH mode ~cH mode

1.4

1.2 1.2

1.0
~~~~~~T-~~~~

4500 4600 4700 4800 4900 5000 5100

2.4 1
2.4 1, i
1282 cm· 1296 cm·1
2.2
VCCICN mode Vex mode

1.4

1.2
121
10
· l I I ' I I

4500 4600 4700 4800 4900 5000 5100

2.4 1,1 \
1569 cm·1
VCC/CN mode 2.2 11 • 23 ~\· VCC/CN mode

2.0 ~:~ ~~~~

1.8 !:1 ~~~\\.~\
1.6 ~~·,
v3 . ~·''·
1.4 ~ ·~~"
":::::
1.2

10
4500 4600 4700 4800 4900 5000 5100

Excitation Wavelength I Ao
Figure JIIB.2 (continued)

92
 2.4 1, 1
1585 cm' 1
1697 cm·1
2.2
vcCJCN mode vco (subs.)
2.0

1.8

1.6
i
1.4

4500 4600 4700 4800 4900 5000 5100

0
Excitation Wavelength I A
Fi
gure IIIB.2 (continued) Measured and calculated REPs for 2-APy. For each normal mode,
intensities of the different wavenumbers are normalized relative to that at 514.5 nm. The
3
symbols '+' & 'o' denotes the measured profiles in CHCh and CC14 solutions respectively. ·v
3
denotes classical calculated profiles considering (va- Vo ) dependence only. (i, j) denotes
calculated profile considering contribution from Si & Sj electronic states. [(i =j) denotes A-term
contribution and (i:;t: j) denotes B-term contribution and interference between two A-terms]. The
B-term contribution and interference between the two ~-terms superpose with each other. The
bold letters indicate the p1ost favourable contributors.

The wavenumber of the C=O stretching modes of the said molecules lie in the region
between 1680 and 1700 cm-1 [43-45]. Critical examination of REPs of this mode indicates that
the favourable contributors are B terms (especially in 2- and 3-APys), which mix the states (St
and S2) and (S 1 and S3). Apru:t from these contributors, this mode in 4-APy and APh also gets
possible A-term contribution from the states St and S2, respectively, some solvent effect being
1
observed in the former case. In this context it should be .noted that as the Lb band
(corresponding to G---;St transition) is weak in APh and the diagonal contribution comes from S2
ctLa) state. But in 4-APy diagonal contribution comes from St state where 1Lb band is not so
weak. The REPs of the other stretching modes [i.e., vcctCN, vex (x-sensitive mode), and Vee
(substitute- sensitive mode)] are shown in the figures. The Vex mode of 4-APy shows a certain
solvent effect. In CCJ.4 a major contribution comes from the pairs of states S1 and S3 through B-
term, whereas in CHCh solution major contribution comes from the diagonal A-term of the
electronic states S4. Of the three molecules, REP of the ~co could only be measured in 3-APy.
This mode (591cm- 1) chiefly gets classical contribution.

93
2.4 1., \
164 cm·1
2.4 1,1 \
591 cm·1 I
\ 2.2
2.2 1.2\ \
u\\ \
Ycx mode Pea (subs.)
2.0 2. 2 ~··\ \ 2.0
2, 3 " \.\ \
1.8 3. 3 '<>,'-<'\' \ 1.8
3. 4 '<'<;.~-;\.\
4.4 '-,,',.>,·'~\\'',

v'~~
1.6

:: 1.4 vl
'~~ 1.2
1.2

2.4 1.1 \
...........
7~1 ~'""·1
2.2
<lccc mode

1.2
J
1.0
~~~~~~~~~~~
4500 4600 4700 4800 4900 5000 5100 4500 4600 4i00 4800 4900 5000 5100

2.4 1. 1 \

2.2 1,2, \

i~~
VCCICN mode ~cH mode
20
1.a.i;l~~\~·
4,4~ . \
161 . ·~~
1.4] vl .;; \

1.2

1.0
~~~~~~~--~~~
4500 4600.4700 4800 4900 5000 5100

Excitation Wavelength l A-:

Figure DIB.3 Measured and calculated REPs for 3-APy.

94
 2.4 2.4
1272 cm·1 1586 cm·1
2.2 2.2
vex mode VCCICN mode
2.0 2.0
1.8 1.8

1.6
v3
1.4

u.

2.4 , • 1
1686 cm·1
2.2 1,2~
1,3 vco (subs.)
2.2 .
2.0 2.3
3, 3
1.8 3,4
4,4
1.6
v3
14

Excitation Wavelength I A0

Figure IDB.3 (continued) Measured and calculated REPs for 3-APy. For each normal mode,
intensities of the different wavenumbers are normalized relative to that at 514.5 nm. The
3
symbols '+' & 'o' denotes the measured profiles in CHCh and CCl4 solutions respectively. v
denotes classical calculated profiles considering (va - Vo i dependence only. (i, j) denotes
calculated profile considering contribution from Si & Sj electronic states. [(i = j) denotes A-term
contribution and (i:t: j) denotes 8-term contribution and interference between two A-terms]. The
8-term contribution and interference between the two A-terms superpose with each other. The
bold letters indicate the most favourable contributors.

95
 2.6 r--------.----..,_ 2.6
1, 1
2.4
1' 1 1ao cm·1 2.4 666 cm·1
2.2 1, 2 'Ycx mode 2.2 1, 2 ~CCICN mode
1, 3 1, ~
2.0 2, 2 2.0 2.2
2, 3 2,3.
1.8 3, 3
3, 4 1.8 3.3
3,4
4.4 4,4
1.6 1.6

1.4 1.4

1.2 1.2

2.6 2.6 -r-------r:=:==:;;=.--._

1' 1
1, 1
1
2.4 739 cm" 2.4 993 cm"1
2.2 u accc mode 2.2 VCCICN mode
~ 1. 3
Ul 2.0 2.0
c:
! 1.8 1.8
.5
Q)
> 1.6 1.6
::
CG l
-; 1.4 v 1.4
0:::
1.2 1.2

1.0
4500 4600 4700.4800 4900 5000 5100

2.6
1.1 \
2.4 \
1064 cm·1 .1084 cm" 1
2.2

2.0 2,2''\
1,3'' \

5·
'33
1.8 3.4"
\
\
\
~cH mode

1.8
vee (subs.)

4,
1.6 1.6
J
v
1.4 1.4

1.2 1.2
1.0 1.0
~-r--~~--~~--~~
4500 4600 4700 4800 4900 5000 5100 4500 4600 4700 4800 4900 5000 5100

Excitation Wavelength I A0
Figure DIB.4 Measured and calculated REPs for 4-APy.

96
 2.6,--:---------;====~
1,1 \
2.6 r.-:--------;:====.,
1,1\
2.4 1214 cm· 1
2.4 1267 cm·1
1, 2 1,2
2.2 1, 3 ~cH mode 2.2 1 3 vex mode
'o
2.2
2.0 2, 2 . 2.0 2 3
. '2, 3
3, 3 3:3
1.8 3, 4 1.8 3, 4
4,4 4,4
1.6 1.6
v'
1.4

1.2 1.2
1.0
~~~-r~~--~~~~~
4500 4600 4700 4800 4900 5000 5100

2.6 2.6
1' 1 1, 1
2.4 1596 cm·1 2.4 1694 cm·1
2.2 VCCJCN mode 2.2 Yeo (subs.)

2.0 2.0

1.8 1.8

1.6 1.6
v3
1.4 1.4
1.2

1.0
~~--~--~~~~~~~
4500 4600 4700 4800 4900 5000 5100

Excitation Wavelength I Ao

Figure IDB.4 (continued) Measured and calculated REPs for 4-APy. For each nonnal mode,
intensities of the different wavenumbers are nonnalized relative to that at 514.5 nm. The
symbols '+' & 'o' denotes the measured profiles in CHCh and CCl4 solutions respectively. v3
3
denotes classical calculated profiles considering (va - Yo ) dependence only. (i, j) denotes
calculated profile considering contribution from Si & Sj electronic states. [(i = j) denotes A-term
contribution and (i :f. j) denotes B-term contribution and interference between two A-terms]. The
B-term contribution and interference between the two A-terms superpose with each other. The
bold letters indicate the most favourable contributors.

97
2.6 .,-------;:::::==::::l.,. 2.6

2.4 1,1~ 617 cm· 1

Ycx mode 2.2
1.2\
1, 3 ' a.ccc mode
2,2~\
23~~
2.0
1.8 3.3 ~" ~
3.4 ~<"' '\
···~ '~
,'~'
1.6
1.4

1.2
1.0
4500 4600 4700 4800 4900 5000 5100 4500 4600 4i00 4800 4900 5000 5100

2.6 ~~-----;::::=====~ 2.6..,-------------.

111. 1 \ 1.1 \
2.4 \
1.2\ \
1000 cm·1
a.ccc mode 2.2 1, 3 \.\ \ vt:r: mode
2.0
1.8

1.6 3 ~
1.4 v . ~
0 ~

1.2 ~

4500 4600 4700 4800 4900 5000 5100

1074 cm·1
vr:r: {subs.)

.
10~
~~--~--~--~~--~~
4500 460C 4700 4800 4900.5000 5100 4500 4600 4i00 4800 4900 5000 5100

Excitation Wavelength /A 0

Figure IIIB.S Measured and calculated REPs for APh.

98
 2.6 -r.-:-:------r====_,.
1,
1 \
2.6
1, 1
2.4 1, 2 1264 cm' 1
2.4 · 1599 cm-1
vex mode 2.2 vee mode
2.0
1.8

1.6 1.6

1.4 v'

1.2 1.2
1.0
~~---r--~--~~~~~
4500 4600 4700 4800 4900 &000 5100

1680·cm·1
v00 (subs.)

3,3
'1.6 3,4
4,4
1.6

t2
1.0
~~--~--T-~~-r--~~
4500 4600 4700 4800 4900 5000 5'100

Excitation Wavelength I A o

Figure IIIB.5 (continued) Measured and calculated REPs for APh. For each normal mode,
intensities of the different wavenumbers are normalized relative to that at 514.5 nm. The
symbols '+' & 'o' denotes the measured profiles in CHCh and CC4 solutions respectively. v 3
3
denotes classical calculated profiles considering (va - V0 ) dependence only. (i, j) denotes
calculated profile considering contribution from Si & Sj electronic states. [(i = j) denotes A-term
contribution and (i -:t. j) denotes B-term contribution and interference between two A-terms]. The
B-term contribution and interference between the two A-terms superpose with each other. The
bold letters indicate the most favourable contributors.

99
 The REPs of some PcH modes were also measured for some of the comparatively intense
bands. Three strong and polarized Raman bands, belonging to this mode, appeared at 1044,
II 01, and 1238 cm- 1 in 2-APy. The former band gets classical contribution, whereas, the latter
bands gets favourable off-diagonal (B-term) contributions from the states S3 and S4, indicating
that corresponding states are effectively vibronically coupled through this mode. Moreover,
diagonal (A-term) contribution from S3 and S4 states, respectively, may also be effective for
1
these two latter wavenumbers. One such band in 3-APy is 1195 cm- • It gets A-term
contribution from the state S4 and B-term contributions from the pair of states S3 and S4. Two
PcH modes (at 1064 and 1214 cm-1) could be measured in 4-APy. They get favourable A-term
contributions from the states S4 and (S 2 and S3), respectively. The second mode also gets off-
diagonal contributions from the pair of states (S2 and S3) and (S3 and S4). REP of only one PcH
mode (at 1025 cm- 1) of APh could be measured. This observed profile lies between the
theoretically calculated REPs corresponding to diagonal contribution from the S4 state and
classical contribution, indicating intensity contribution(s) coming from state(s) lying above S4.
We could measure the REPs of two out-of-plane modes: the first one is Ycx mode,
around the wavenumber 160 cm- 1 for all four molecules, and the other mode is r cctCN at 666 em·
1
(only for 4-APy). All of them show classical dependence.

1Iffi.3 CONCLUSION

From the above discussion it is found that the excited electronic states S2 and S3 are
mainly involved with the ring stretching modes (vcCtCN), whereas the lowest excited state S 1 is
involved only with the Vco vibration in 4-APy in the Raman scattering phenomenon. It is also
noteworthy that although the diagonal contribution is not significant for the S1 state
1
(corresponding to the weak Lb band) but becomes important from the s2 state. (corresponding to
1
the more intense La band) in APh. An excited singlet state (S4), about 170 run above the ground
state, is found to play a very significant role in the scattering phenomenon in all the four
molecules. This S4 state is either a molecular state (probably 1Ba) or one appearing from the
aggregation effect in the solution at high concentration. Even for some cases the state(s), lying
above S4 in the vacuum UV region, is (are) found to be better contributor(s). The change of
molecular geometry (with respect to ground state) is appreciable specially in each of the three
upper electronic states. Further, effective vibronic coupling through different totally symmetric
modes between different pairs of electronic states indicates th~t the molecular symmetries in all
these states remain the same.

100
IDB.4 REFERENCES

[1] P. Jana, T. Ganguly, S. K. Sarkar, A. Mitra and P. K. Mallick, J Photochem. Photobiol.,

94A, 113, ( 1996).
[2] S. K. Sarkar and T. Ganguly, Bull. Chem. Soc . .Jpn., 63,2372, (1990).
[~] S. Chakrovorty, S. K. Sarkar and P. K. Mallick, Chem. Phys. Lett., 187, 93, (1991 ).
[4] S. K. Sarkar and G. S. Kastha, Spectrochim Acta., 48A, 1611, (1992).
[5] T. K. Pal, G. S. Mallick, S. Laha, K. Chatterjee, T. Ganguly and S. B. Banerjee,
Spectrochim Acta, 43A, 853, (1987).
[6] P. Jana and T. Ganguly, Spectrochim Acta., 49A, 1515, (1993).
[7] S.C. Shim, D. W. Kim and M.S. Keins, J Photochem. Photobiol., 56A, 227, (1991).
[8] C. Dubroca and P. Lazaro, Chem. Phys. Lett., 24, 49, (1974).
(9] S. Chattopadhyay, P. Jana, A. Mitra, S. K. Sarkar, T. Ganguly and P. K. Mallick, .!.
Raman Spectrosc:, 28, 559, (1997).
(10] P. Sett, N. Paul, S. Chattopadhyay and P. K. Mallick,.!. Raman Spectrosc., 30,277,
(1999).
(11] P. Sett, S. Chattopadhyay and P. K. Mallick, SpectrochimActa., 56A, 855, (2000).
(12] G. Marconi, J Raman Spectrosc., 22, 361, (1991).
(13] G. Marconi and M. Z. Zgierski,.!. Mol. Struc. Theochem., 105,259, (1983).
[14] F. Zerbetta and M. Z. Zgierski, Chern. Phys., 110,421, (1986).
[ 15] A. Mitra and P. K. Mallick, Ind. .J. Phys., 688, 47, (1994).
(16] H. Okamoto, H. Hamaguchi and M. Tasumi,.!. Raman Spectrosc., 20,751, (1989).
(17] E. J. Heller, Ace. Chem. Res., 14, 368, (1981).
(18] E. J. Heller, R.N. Sundberg and D. Tannor, J Phys. Chern., 86, 1822, (1982).
[19] A. Biancalana, E. Campani, D. D. Domenico, G. Gorini and G. Masett~ J Raman
Spectrosc., 24, 43, (1993).
(20] J. B. Page and D. L. Tonks,.!. Chern. Phys., 75,5694, (1984):
[21] D. L. Tonks and J. B. Page,.!. Chern. Phys.Lett., 79,247, (1981).
[22] D. L. Tonks and J. B. Page, .J. Chern. Phys.Lett., 66,449, (1979).
[23) L. F. C. Oliveria, P. S. Santos and M. C. C. Rebeiro,.!. Raman Spectrosc., 28, 53, (1997).
[24] M. C. C. Rebeiro, W. J. Baretto and P. S. Santos, .J. Raman Spectrosc., 25, 923, (1994).
(25] M. C. C. Rebeiro, W. J. Baretto and P. S. Santos, J Raman Spectrosc., 24,434, (1993).
(26] L. S. Hoskin, A. X. Pham and G. C. Rutt,.!. Raman Spectrosc., 21,543, (1990).
(27] V. Hizhnyakov and I. Tehver,.!. Raman Spectrosc., 24, 653, (1993).

101
(28) R. Islampour, M. Hayashi and S. H. Lin, .f. Raman Spectrosc., 28, 331, (1997).
(29) R. Islampour, M. Hayashi and S. H. Lin, Chern. Phys. Lett., 234, 7, (1995).
[30) A. P. Shreve and R. A. Mathies, .f. Phys. Chern., 99,7285, (1995).
[3 1] A. C. Albrecht, R. J. H. Clark, D. Oprescu, S. J. R. Owens and C. Srendren, J. Chern.
Phys., 101, 1890, (1994).
l32) C. Sourisseasu and P. Maraval, .f. Raman Spectrosc., 25,477, (1994).
[33) K. S. K. Shin and J. I. Zink, .f. Amer. Chern. Soc., 112,7148, (1990).
[34} A. Aminzadeh, V. Fawcatt and D. A. Long, .f. Raman Spectrosc., 9, 214, (1980).
[35) A. Aminzadeh, V. Fawcatt and D. A. Long, .f. Raman Spectrosc., 9, 219, (1980) ..
[36] A. C. Albrecht and M. C. Hutley, .f. Chern. Phys., 55, 4438, (1971 ).
[37] J. Tang and A. C. Albrecht, in Raman Spectroscopy: Theory and Practice, H. A.
Szymanski (Eds.), Vol. 2, Chapt. 2, Plenum Press, New York, (1970).
(38] A. C. Albrecht,J. Chern. Phys., 34,1476, (1961).

[39] R. J. H. Clark and T. J. Dines, Mol. Phys., 42, 193, (1981).

[40] R. J. H. Clark and T. J. Dines, Chern. Phys. Lett., 79, 321, (1981).
[41] I. W. Sztainbuch and G. E. Leroi,.! Chern. Phys., 93, 4642, (1990).
[42] P. Sett, S. Chattopadhyay and P. K. Mallick, J. Raman Spectrosc., 31, 177, (2000).
[43] K. C. Medhi, lndianJ. Phys., 51A, 99, (1977).
[44] A. Gambi, S. Giorgianni, A. Passerini, R. Visinoni and S. Ghersetti, Spectrochim Acta.,
36A, 871, (1980).
[45] W. D. Mross and G. Zundal, Spectrochim Acta., 26A, 1097, (1970).
(46] S. K. Sarkar, S. K. Ghosal and G. S. Kastha, Proc. Indian Acad (Chern.). Sci., 92, 47,
(1983).

102