The authors have declared that no competing interests exist.
The FT-IR, FT-Raman and UV-Vis spectra of E-[1-(3'-methylthienyl)-5-Phenyl-2,4-Pentadiene-3-one (MPPO) were recorded. The optimized molecular bond parameters, harmonic frequencies were calculated using B3LYP method with 6-311++G (d,p) basis set.The various normal modes were precisely assigned with thehelp ofTED calculation. The theoretical spectrograms for FT-IR, FT-Raman and Ultra Violet visible. Spectra of the title molecule had been constructed. The ICT was calculated by means of Natural Bond Orbital analysis. The Non Linear Optical properties related to polarizability and hyperpolarizability based on the finite-field approach were calculated.The band gap energy was calculated using HOMO-LUMO analysis. Furthermore, the Molecular Electrostatic Potential, Mulliken atomic charges and thermodynamic properties of MPPO were also calculated.
Chalcones belong to the flavonoid families which are synthesized in factories to preserve the health of plants against infections and parasites. They have attractedincreasing attention due to numerous pharmacological applications
Chidan Kumar et al.,
In light of the above literature survey, it was clear that inspite of many important applications of MPPO not many works were carried out on this molecule; particularly the complete vibrational analysis supported by quantum computations was not carried out. Hence in this study, FTIR, FT-Raman and UV-Vis. spectral analysis of the compound MPPO was carried out. The NBO analysis, with emphasis on HOMO-LUMO, NLO, MEP, Mulliken’s charges, and various thermodynamic parameters were also calculated using quantum computations by DFT/B3LYP method.
Mono benzal acetone (1.46g, 0.01mol) was dissolved in 15 mL of ethanol with slight warning. To this hot solution methyl thiophen-2-carboxaldehyde (1.4 mL, 0.01mol) and few drops of solution hydroxide solution 10%) were added. The solution gradually turned red on warming and yellow crystals separated. The product was filtered off and recrystalised twice from ethanol. The yield and melting point of the crystal is 76% and 148 respectively.
The FT-IR spectrum on an IFS 66v spectrophotometer of MPPO was recorded in the spectral region between 400–4000 cm-1 using the KBr pellet technique. The spectrum was recorded at room temperature with a scanning speed of 10 cm-1 per minute and at the spectral resolution of 2.0 cm-1 in the Department of Chemistry, Jamal Mohamed College, Trichy, Tamilnadu, India. The FT-Raman spectrum of title compound was recorded using the 1064 nm line of an Nd: YAG laser as excitation wavelength in the region 50–3500 cm-1 on Bruker model IFS 66V spectrophotometer equipped with an FRA 106 FT-Raman module accessory and at spectral resolution of 4 cm-1. The FT-Raman spectral measurement was carried out from SAIF Laboratory, IIT Madras, Tamilnadu, India. The UV-Vis absorption spectrum of MPPO was recorded in the range of 200–500 nm using a Shimadzu – 2600 spectrometer in the Department of Chemistry, Jamal Mohamed College, Trichy-20. The UV pattern was taken from a 10-5 molar solution of MPPO dissolved in benzene.
For meeting the requirements of both accuracy and computing economy, theoretical methods and basis sets should be considered. DFT had proved to be extremely useful in treating electronic structure of molecules. The density functional theory parameter hybrid model DFT/B3LYP/6 basis set was adopted to calculate the properties of the title molecule in this work.
The optimized geometrical parameters for MPPO are calculated using B3LYP/6-311++G(d,p) level of calculation and are presented in
Parameters | B3LYP/ 6-311++G(d,p) | XRD |
Bond Lengths (Å) | ||
C1-C2 | 1.401 | 1.375 |
C1-S5 | 1.762 | 1.728 |
C1-C12 | 1.436 | |
C2-C3 | 1.415 | 1.431 |
C2-C8 | 1.507 | |
C3-C4 | 1.372 | 1.37 |
C3-H6 | 1.083 | 1.081 |
C4-S5 | 1.717 | 1.717 |
C4-C7 | 1.081 | |
C8-H9 | 1.091 | |
C8-H10 | 1.094 | |
C8-H11 | 1.094 | |
C12-H13 | 1.087 | 0.950 (6) |
C12-C14 | 1.361 | |
C14-H15 | 1.085 | 0.951 (8) |
C14-C16 | 1.467 | |
C16-C18 | 1.479 | |
C16-O17 | 1.235 | 1.190 (3) |
C18-H19 | 1.086 | 0.951 (8) |
C18-C20 | 1.358 | |
C20-H21 | 1.089 | 0.950 (6) |
C20-C22 | 1.463 | |
C22-C23 | 1.412 | 1.366 (4) |
C22-C24 | 1.409 | |
C23-C25 | 1.389 | |
C23-H26 | 1.085 | 0.954 (2) |
C24-C27 | 1.391 | |
C24-H28 | 1.08 | 0.949 (2) |
C25-C29 | 1.395 | |
C25-H30 | 1.084 | 0.950 (3) |
C27-C29 | 1.395 | |
C27-H31 | 1.084 | 0.950 (2) |
C29-H32 | 1.085 | 0.950 (3) |
Bond Angles (°) | ||
C2-C1-S5 | 110.34 | 111.80 |
C2-C1-C12 | 122.15 | |
S5-C1-C12 | 127.51 | |
C1-C2-C3 | 112.64 | 112.20 |
C1-C2-C8 | 124.93 | |
C3-C2-C8 | 122.43 | |
C2-C3-C4 | 112.9 | 112.05 |
C2-C3-H6 | 123.42 | 123.3 |
C4-C3-H6 | 123.68 | |
C3-C4-S5 | 112.86 | 112.13 |
C3-C4-H7 | 127.42 | |
S5-C4-H7 | 119.72 | |
C1-S5-C4 | 91.27 | 92.00 |
C2-C8-H9 | 110.2 | |
C2-C8-H10 | 111.96 | |
C2-C8-H11 | 111.96 | |
H9-C8-H10 | 107.48 | |
H9-C8-H11 | 107.48 | |
H10-C8-H11 | 107.55 | |
C1-C12-H13 | 110.92 | |
C1-C12-C14 | 135.87 | |
H13-C12-C14 | 113.2 | 121.2 (6) |
C12-C14-H15 | 115.61 | 116.1 (7) |
C12-C14-C16 | 128.31 | 127.7 (6) |
H15-C14-C16 | 116.08 | 116.3 (6) |
C14-C16-O17 | 121.39 | 106.5 (3) |
C14-C16-C18 | 114.24 | 147.1 (4) |
O17-C16-C18 | 124.37 | 106.5 (3) |
C16-C18-H19 | 113.14 | 116.3 (6) |
C16-C18-C20 | 132.74 | 127.7 (6) |
H19-C18-C20 | 114.12 | 116.1 (7) |
C18-C20-H21 | 112.56 | 121.2 (6) |
C18-C20-C22 | 136.42 | 117.6 (5) |
H21-C20-C22 | 111.03 | 121.2 (4) |
C20-C22-C23 | 116.08 | 140.3 (3) |
C20-C22-C24 | 125.99 | 101.8 (3) |
C23-C22-C24 | 117.93 | 117.5 (2) |
C22-C23-C25 | 121.5 | 121.2 (3) |
C22-C23-H26 | 119.09 | 119.4 (3) |
C25-C23-H26 | 119.41 | 119.4 (3) |
C22-C24-C27 | 120.34 | 120.4 (2) |
C22-C24-H28 | 118.84 | 119.8 (2) |
C27-C24-H28 | 120.82 | 119.7 (2) |
C23-C25-C29 | 119.76 | 120.4 (3) |
C23-C25-H30 | 119.96 | 119.8 (3) |
C29-C25-H30 | 120.29 | 119.8 (3) |
C24-C27-C29 | 120.88 | 120.8 (2) |
C24-C27-H31 | 119.27 | 119.6 (3) |
C29-C27-H31 | 119.85 | 119.6 (3) |
C25-C29-C27 | 119.59 | 119.7 (3) |
C25-C29-H32 | 120.15 | 120.2 (3) |
C27-C29-H32 | 120.26 | 120.2 (3) |
Dihedral Angles (°) | ||
S5-C1-C2-C3 | 0 | |
S5-C1-C2-C8 | 180 | |
C12-C1-C2-C3 | 180 | |
C12-C1-C2-C8 | 0 | |
C2-C1-S5-C4 | 0 | |
C12-C1-S5-C4 | -180 | |
C2-C1-C12-H13 | 0 | |
C2-C1-C12-C14 | 179.99 | |
S5-C1-C12-H13 | 179.99 | |
S5-C1-C12-C14 | 0 | |
C1-C2-C3-C4 | 0 | |
C1-C2-C3-H6 | 180 | |
C8-C2-C3-C4 | -179.99 | |
C8-C2-C3-H6 | 0 | |
C1-C2-C8-H9 | -180 | |
C1-C2-C8-H10 | 60.43 | |
C1-C2-C8-H11 | -60.44 | |
C3-C2-C8-H9 | 0 | |
C3-C2-C8-H10 | -119.57 | |
C3-C2-C8-H11 | 119.56 | |
C2-C3-C4-S5 | 0 | |
C2-C3-C4-O7 | -180 | |
H6-C3-C4-S5 | -180 | |
H6-C3-C4-H7 | 0 | |
C3-C4-S5-C1 | 0 | |
H7-C4-S5-C1 | 180 | |
C1-C12-C14-H15 | 179.99 | |
C1-C12-C14-C16 | 0 | |
H13-C12-C14-H15 | 0 | |
H13-C12-C14-C16 | 179.99 | |
C12-C14-C16-O17 | 0 | |
C12-C14-C16-C18 | -180 | |
H15-C14-C16-O17 | 180 | |
H15-C14-C16-C18 | 0 | |
C14-C16-C18-H19 | 0 | |
C14-C16-C18-C20 | 180 | |
O17-C16-C18-H19 | 179.99 | |
O17-C16-C18-C20 | 0 | |
C16-C18-C20-H21 | 180 | |
C16-C18-C20-C22 | 0 | |
H19-C18-C20-H21 | 0 | |
H19-C18-C20-C22 | 179.99 | |
C18-C20-C22-C23 | -179.99 | |
C18-C20-C22-C24 | 0 | |
H21-C20-C22-C23 | 0 | |
H21-C20-C22-C24 | -179.99 | |
C20-C22-C23-C25 | 180 | |
C20-C22-C23-H26 | 0 | |
C24-C22-C23-C25 | 0 | |
C24-C22-C23-H26 | 180 | |
C20-C22-C24-C27 | -180 | |
C20-C22-C24-H28 | 0 | |
C23-C22-C24-C27 | 0 | |
C23-C22-C24-H28 | -180 | |
C22-C23-C25-C29 | 0 | |
C22-C23-C25-H30 | -180 | |
H26-C23-C25-C29 | 180 | |
H26-C23-C25-H30 | 0 | |
C22-C24-C27-C29 | 0 | |
C22-C24-C27-H31 | 180 | |
H28-C24-C27-C29 | 180 | |
H28-C24-C27-H31 | 0 | |
C23-C25-C29-C27 | 0 | |
C23-C25-C29-H32 | -180 | |
H30-C25-C29-C27 | 180 | |
H30-C25-C29-H32 | 0 | |
C24-C27-C29-C25 | 0 | |
C24-C27-C29-H32 | 180 | |
H31-C27-C29-C25 | 180 | |
H31-C27-C29-H32 | 0 |
O. Brathen, K. Kveseth, K.J. Nielsen, K. Hagen, J. Mol. Struct. 145 (1986) 45
O.K. Geiger, H.C. Geiger, L. Williams, B.C. Noll, ActaCryst E68 (2012) o420
Vanchinathan et al., Physica B, 406 (2011) 4195
Karol Pasterny et al., J. Mol. Struct, 614 (2002) 297-304
The molecule MPPO belongs to C1 point group symmetry. This molecule has 32 atoms and hence90 normal modes of fundamental vibrations are possible, which span the irreduciable representation:61A'+29A''. All the 90 fundamental modes are active in both IR and Raman. The vibrational analysis of MPPO is performed on the basis of the characteristic vibrations of carbonyl, methyl, thiophene, pentadiene and phenyl ring modes. In this study, the harmonic vibrational frequencies are calculated at B3LYP level using 6-311++G(d,p)basis set have been collected in
Mode No | Calculated | Observed Frequencies (cm-1) | IR Intensity | Raman Intensity | Reduced Masses | Force Consts | Vibrational Assignments≥10% (TED)d | ||
Frequencies (cm-1) | |||||||||
Un Scaled | Scaleda | FT-IR | FT-Raman | Rel.b | Rel.c | ||||
1 | 3231 | 3104 | 0.03 | 0.61 | 1.1 | 6.75 | νC24H28(95) | ||
2 | 3225 | 3098 | 12.04 | 0.37 | 1.09 | 6.7 | νC14H15(98) | ||
3 | 3193 | 3068 | 2.69 | 0.6 | 1.09 | 6.55 | νC8H11(94) | ||
4 | 3188 | 3063 | 3064 vw | 3059 vw | 4.7 | 1.04 | 1.1 | 6.57 | νC8H9(83) |
5 | 3177 | 3052 | 4.94 | 0.33 | 1.09 | 6.5 | νC8H10(85) | ||
6 | 3172 | 3047 | 4.12 | 0.59 | 1.09 | 6.46 | νC18H19(87) | ||
7 | 3165 | 3041 | 0.42 | 0.38 | 1.09 | 6.42 | νC23H26(84) | ||
8 | 3158 | 3034 | 0.99 | 0.13 | 1.09 | 6.38 | νC12H13(72) | ||
9 | 3151 | 3027 | 3021 vw | 0.77 | 0.08 | 1.09 | 6.37 | νC3H6(75) | |
10 | 3139 | 3016 | 0.87 | 0.15 | 1.08 | 6.29 | νC20H21(83) | ||
11 | 3111 | 2989 | 1.45 | 0.17 | 1.08 | 6.19 | νC4H7(85) | ||
12 | 3106 | 2984 | 3.59 | 0.28 | 1.1 | 6.25 | νC25H30(92) | ||
13 | 3073 | 2953 | 2919 w | 2921 vw | 2.57 | 0.27 | 1.1 | 6.13 | νC27H31(100) |
14 | 3025 | 2907 | 2843 vw | 6.13 | 1.12 | 1.04 | 5.6 | νC29H32(92) | |
15 | 1696 | 1629 | 1647 s | 1647 vw | 12.94 | 3.2 | 7.03 | 11.91 | νC16O17(85) |
16 | 1642 | 1578 | 1617 m | 1616 w | 17.67 | 1.55 | 5.53 | 8.78 | νC24C27(18)+νC23C25(25)+νC25C29(14)+βH26C23C25(15) |
17 | 1624 | 1560 | 1586 vs | 1584 vs | 100 | 21.83 | 5.42 | 8.43 | νC4C3(32)+νC24C27(12) |
18 | 1604 | 1541 | 1550 m | 1551 vw | 98.37 | 3.24 | 5.33 | 8.08 | νC18C20(46)+βH32C29C27(20) |
19 | 1583 | 1521 | 4.3 | 100 | 7.4 | 10.93 | νC16O17(66) | ||
20 | 1534 | 1474 | 1492 m | 1494 vw | 5.18 | 0.67 | 3.93 | 5.44 | νC16C18(45) |
21 | 1524 | 1464 | 1.92 | 3.21 | 2.16 | 2.95 | νC12C14(12)+βH15C14C16(50) | ||
22 | 1504 | 1445 | 1447 w | 2.05 | 1.15 | 1.19 | 1.58 | βH10C8H11(60)+βH13C12C14(10) | |
23 | 1495 | 1437 | 5.7 | 7.89 | 2.04 | 2.69 | βH13C12C14(42) | ||
24 | 1490 | 1432 | 1.67 | 0.22 | 1.04 | 1.36 | βH9C8H10(78)+τH9C8C2C3(10)+τH10C8C2C3(10) | ||
25 | 1486 | 1428 | 2.28 | 3.84 | 1.72 | 2.24 | βH21C20C22(60) | ||
26 | 1467 | 1409 | 1404 m | 1406 vw | 2.2 | 0.77 | 1.82 | 2.31 | βH19C18C20(58) |
27 | 1426 | 1370 | 8.06 | 2.12 | 2.81 | 3.36 | νC2C3(24)+νC1C2(14)+βH6C3C4(25) | ||
28 | 1412 | 1357 | 0.31 | 0.87 | 1.28 | 1.51 | βH9C8H10(88) | ||
29 | 1384 | 1330 | 1334 m | 13.7 | 9.15 | 2.76 | 3.12 | νC14C16(50) | |
30 | 1381 | 1327 | 5.07 | 8 | 1.45 | 1.63 | βH21C20C22(65) | ||
31 | 1360 | 1307 | 1314 w | 0.1 | 4.73 | 2.13 | 2.32 | νC18C20(14)+νC23C25(18)+βH26C23C25(40) | |
32 | 1342 | 1289 | 20.27 | 7.27 | 1.38 | 1.46 | βH13C12C14(58) | ||
33 | 1299 | 1248 | 1258 w | 0.51 | 0.51 | 1.83 | 1.82 | νC22C24(34)+βH28C24C27(20) | |
34 | 1261 | 1212 | 1193 m | 0.44 | 0.02 | 1.76 | 1.65 | νC2C8(15)+βH6C3C4(52) | |
35 | 1216 | 1168 | 1183 m | 1185 w | 3.88 | 0.24 | 1.25 | 1.09 | βH26C23C25(55) |
36 | 1205 | 1158 | 0.63 | 4.87 | 2.34 | 2 | νC20C22(25) | ||
37 | 1195 | 1148 | 4.24 | 0.45 | 2.1 | 1.77 | νC1C2(14)+νC2C3(10)+βH13C12C14(12) | ||
38 | 1184 | 1137 | 0.01 | 0.16 | 1.11 | 0.92 | βH32C29C27(60) | ||
39 | 1119 | 1075 | 1090 w | 1090 m | 36.76 | 1.15 | 1.92 | 1.42 | νC18C20(12)+νC16C18(24)+βH19C18C20(12)+βH7C4S5(16) |
40 | 1110 | 1066 | 0.16 | 0.21 | 1.35 | 0.98 | νC2C3(10)+βH7C4S5(50) | ||
41 | 1097 | 1054 | 50.3 | 0.07 | 2.95 | 2.09 | νC16C18(26) | ||
42 | 1052 | 1011 | 1012 m | 0.45 | 1.12 | 2.32 | 1.51 | νC25C29(48)+βH26C23C25(18)+βC23C25C29(12) | |
43 | 1051 | 1010 | 0.17 | 0.03 | 1.5 | 0.98 | βH9C8H11(22)+τH9C8C2C3(34)+τH10C8C2C3(34) | ||
44 | 1039 | 998 | 1000 w | 1.25 | 0.56 | 1.78 | 1.13 | νC2C8(10)+βH9C8H10(14)+τH9C8C2C3(20)+τH10C8C2C3(20) | |
45 | 1032 | 991 | 985 vw | 0.27 | 0.01 | 1.31 | 0.82 | τH28C24C27C29(72) | |
46 | 1019 | 979 | 0 | 0.16 | 1.28 | 0.79 | τH19C18C20C22(78) | ||
47 | 1015 | 976 | 0.42 | 5.13 | 6.19 | 3.76 | νC27C29(22)+βC24C27C29(50) | ||
48 | 997 | 958 | 0.01 | 0.24 | 1.29 | 0.75 | τH13C12C14C16(80) | ||
49 | 994 | 955 | 0.09 | 0.02 | 1.32 | 0.77 | τH32C29C27C24(70) | ||
50 | 973 | 935 | 2.46 | 0.51 | 2.83 | 1.58 | νC12C14(20) | ||
51 | 953 | 916 | 1.09 | 0.01 | 1.4 | 0.75 | τH26C23C25C29(78) | ||
52 | 930 | 894 | 1.52 | 0.64 | 3.7 | 1.89 | νC12C14(15)+βC14C16C18(22) | ||
53 | 897 | 862 | 0.44 | 0.02 | 1.28 | 0.61 | τH6C3C4S5(76) | ||
54 | 865 | 831 | 834 vw | 1.65 | 0 | 1.37 | 0.6 | τH19C18C20C22(78) | |
55 | 859 | 825 | 8.59 | 0.02 | 2.06 | 0.89 | τH19C18C20C22(22)+τC1C12C14C16(18)+τH13C12C14C16(20)+τH30C25C29C27(14) | ||
56 | 844 | 811 | 812 m | 8.45 | 0.33 | 4.61 | 1.93 | νC4S5(42)+βC1C2C3(15) | |
57 | 830 | 797 | 2.64 | 0.21 | 5.16 | 2.09 | νC4S5(28)+βC1C2C3(18) | ||
58 | 809 | 777 | 760 vw | 2.51 | 0.04 | 1.97 | 0.76 | τH13C12C14C16(12)+τH30C25C29C27(40)+τC22C24C27C29(12) | |
59 | 767 | 737 | 0 | 0.07 | 1.65 | 0.57 | τC1C12C14C16(26)+τH13C12C14C16(38) | ||
60 | 763 | 733 | 724 vw | 0.55 | 2.08 | 5.71 | 1.96 | νC20C22(18)+βC18C16O17(36) | |
61 | 734 | 705 | 13.14 | 0.03 | 1.23 | 0.39 | τH6C3C4S5(75) | ||
62 | 718 | 689 | 697 w | 691 vvw | 2.72 | 0.02 | 1.34 | 0.41 | τH19C18C20C22(44)+τC1C12C14C16(14)+τH30C25C29C27(26) |
63 | 715 | 687 | 0.12 | 7.15 | 6.89 | 2.07 | νC4S5(32)+βC1C2C3(22)+βC2C3C4(12) | ||
64 | 697 | 670 | 3.56 | 0.03 | 2.52 | 0.72 | τH28C24C27C29(12)+τC22C24C27C29(48) | ||
65 | 663 | 637 | 634 vvw | 0.04 | 0.55 | 6.25 | 1.62 | νC12C14(22)+βC23C25C29(12)+βC1C2C3(14)+βC2C3C4(10) | |
66 | 632 | 607 | 0.21 | 0.43 | 6.31 | 1.48 | βC18C20C22(62) | ||
67 | 625 | 601 | 0.14 | 0.11 | 2.93 | 0.68 | τH13C12C14C16(12)+ГC8C1C3C2(58) | ||
68 | 603 | 579 | 0.6 | 0.83 | 5.49 | 1.18 | νC1C2(35)+βC2C1C12(20) | ||
69 | 549 | 528 | 531 vw | 0.28 | 0.31 | 7.08 | 1.26 | βC1C2C3(10)+βC1C12C14(24) | |
70 | 529 | 508 | 0.23 | 1.58 | 6.2 | 1.02 | νC2C8(15)+βC1C2C3(50) | ||
71 | 526 | 505 | 0.08 | 0.42 | 3.06 | 0.5 | ГC20C23C24C22(65) | ||
72 | 490 | 470 | 455 m | 2.31 | 0.02 | 3.2 | 0.45 | ГC20C23C24C22(60) | |
73 | 463 | 445 | 424 w | 6.62 | 0.49 | 6.05 | 0.76 | βC22C24C27(10)+βC1C12C14(30) | |
74 | 423 | 407 | 402 vw | 0.3 | 0.24 | 3.28 | 0.35 | τC1C2C3C4(44)+τC23C25C29C27(22) | |
75 | 412 | 395 | 0.14 | 0.15 | 3.14 | 0.31 | τC1C2C3C4(20)+τC23C25C29C27(42) | ||
76 | 358 | 344 | 0.12 | 0.53 | 3.61 | 0.27 | βC3C2C8(60) | ||
77 | 350 | 336 | 0.34 | 0.13 | 3.4 | 0.25 | τC16C18C20C22(55) | ||
78 | 268 | 258 | 1.22 | 0.28 | 8.91 | 0.38 | βC14C16C18(60) | ||
79 | 237 | 228 | 0.5 | 0.07 | 3.64 | 0.12 | ГC8C1C3C2(62)+ГC20C23C24C22(15) | ||
80 | 226 | 217 | 0.31 | 5.93 | 7.6 | 0.23 | βC18C20C22(55) | ||
81 | 194 | 187 | 0.25 | 0.45 | 4.55 | 0.1 | νC3C4(12)+βC2C1C12(40) | ||
82 | 180 | 173 | 164 vw | 0.19 | 0.43 | 3.83 | 0.07 | τC24C27C29C25(55)+ГC20C23C24C22(12) | |
83 | 153 | 147 | 0.21 | 0.14 | 4.72 | 0.07 | ГC8C1C3C2(14)+ГC20C23C24C22(60) | ||
84 | 145 | 139 | 0.27 | 0.42 | 5.54 | 0.07 | βC22C24C27(10)+βC24C27C29 (65) | ||
85 | 110 | 106 | 0.02 | 0.27 | 1.03 | 0.01 | τH9C8C2C3(95) | ||
86 | 78 | 75 | 69 w | 0.71 | 0.1 | 7.08 | 0.03 | ГC20C23C24C22(75) | |
87 | 52 | 50 | 0.03 | 5.81 | 6.66 | 0.01 | βC12C14C16(78) | ||
88 | 47 | 45 | 0.02 | 3.67 | 4.51 | 0.01 | τC2C1C12C14(72) | ||
89 | 28 | 27 | 0.01 | 1.93 | 4.08 | 0 | τC3C2C1C12(62) | ||
90 | 14 | 13 | 0.22 | 0.06 | 5.21 | 0 | τC1C12C14C16(80) |
n: Stretching, β: in-plane-bending, Γ: out-of-plane bending, τ- Torsion, vw: very week, w: week, m: medium, s: strong, vs: very strong,
Scaling factor: 0.9608,
Relative IR absorption intensities normalized with highest peak absorption equal to 100,
Relative Raman intensities calculated by Equation (1) and normalized to 100.
Total energy distribution calculated at B3LYP/6-311++G(d,p) level.
The carbonyl stretching frequency has been most extensively studied by IR spectroscopy
The C-S stretching vibration is well known to mix with neighboring modes
Methyl groups are generally referred to as electron donating substituents in the aliphatic and aromatic ring system
The CH3 rocking modes usually appeared
The ring C=C and C-C stretching vibrationsknown as semicircle stretching usually occur in the region 1450–1625 cm-1
The βCCC and ΓCCCmodes are associated with smaller force constant than the stretching one and hence assigned to lower frequencies. The βCCC modes of benzene ring are expected to appear with considerable intensity under the reduced symmetry.The C-C-C in-plane bending vibrations can be observed in the FTIR spectrum at 1012cm-1 and in FT-Raman spectrum at 634 cm-1.Similarly the C-C-C out-of-plane bending modes can be observed as a medium band in FTIR spectrum at 455cm-1. These results are supported by computed wavenumbers 1011, 976, 637 and 670, 505, 470 cm-1 (mode nos:42, 47, 65 and 64, 71,72), respectively in addition to literature values
Literature survey reveals that the C-C stretching vibrations in substituted thiophen rings were reported in ranges of 1329-1431,1420-1501 and 1419-1519cm-1
The harmonic frequencies established at 1541,1474,1330,1075 cm-1(mode nos: 18,20,29,39) and 1158cm-1, (mode no:36) are attributed to νCC modes of pentadiene moietyand νC20-C22,νC1-C12 modes, respectively. These assignments are having considerable TED values (>25%) and also find support from the observed bands:1550,1492, 1334,1090 cm-1(FTIR)/1551,1494,1090 cm-1 FT-Raman. The mode no:34 (1212/1193cm-1:FTIR) is attributed νC2-C8 mode. The harmonic wavenumbers:894,607,528, 445 cm-1(mode nos:52,66,69,73) and 689,737,336cm-1(mode nos:62,59,77) are respectively assigned to βCCC and τCCC modes of pentadiene, in which mode nos:69,73 and 62 are agreeable with observed bands: (FT-Raman/FTIR)531/424cm-1 and 691/697cm-1. These assignment are also having considerable TED values.
The νC-H modes of hetero aromatic structure are expected to occur in the range of 3000-3100cm-1 with some weak bands. The vibrational band in this region are not affected appreciably by the nature of the substituent’s
In aromatic compounds the C-H in-plane /out-of-plane bending frequencies appear in the ranges of 1000-1300/750-1000cm-1, respectively
The C-H stretching modes are expected to appear with multiple weak bands in the frequency range 3000-3100cm-1. These bands are not affected appreciably by the nature of the substituent’s
In this work, it has been established well and the calculated wavenumbers in the range 3098-3016cm-1 (mode nos:2,6,8,10) are designated as νC-H modes of pentadiene moiety
The total dipole moment and first-order hyperpolarizability (β0) of MPPO is calculated by using B3LYP/6-311++G(d,p) basis set and are listed in
Parameters | B3LYP/6-311++G(d,p) |
Dipole moment ( μ ) Debye | |
μx | -0.4885 |
μy | 0.5112 |
μz | 0.0001 |
Μ | 0.7071 Debye |
Polarizability ( α0) x10-30esu | |
αxx | 418.01 |
αxy | 4.69 |
αyy | 237.33 |
αxz | -0.01 |
αyz | 0 |
αzz | 113.8 |
α0 | 0.69x10-30esu |
Hyperpolarizability ( β0 ) x10-30esu | |
βxxx | 284.46 |
βxxy | 804.11 |
βxyy | 107.07 |
βyyy | 306.1 |
βxxz | 0.02 |
βxyz | -0.01 |
βyyz | 0.06 |
βxzz | 22.34 |
βyzz | -0.42 |
βzzz | 0.0044 |
β0 | 10.23x10-30esu |
Standard value for urea (μ=1.3732 Debye, β0=0.3728x10-30esu): esu-electrostatic unit
The NBO analysis is performed on MPPO using B3LYP/6-311++G(d,p) basis set. The E(2) energies and types of interactions are listed in
Type | Donor NBO (i) | ED/e | Acceptor NBO (j) | ED/e | E(2) KJ/mol | E(j)-E(i) a.u. | F(i,j) a.u. | ||||||||
σ-σ* | BD ( 1) C 1 - C 2 | 1.97397 | BD*( 1) C 1 - C 12 | 0.0274 | 3.73 | 1.22 | 0.06 | ||||||||
BD*( 1) C 12 - C 14 | 0.01462 | 1.94 | 1.96 | 0.055 | |||||||||||
π-π* | BD ( 2) C 1 - C 2 | 1.73778 | BD*( 2) C 3 - C 4 | 0.32831 | 16.62 | 0.27 | 0.06 | ||||||||
BD*( 1) C 8 - H 10 | 0.00953 | 1.87 | 0.66 | 0.034 | |||||||||||
BD*( 1) C 8 - H 11 | 0.00953 | 1.87 | 0.66 | 0.034 | |||||||||||
BD*( 2) C 12 - C 14 | 0.17953 | 20.25 | 0.33 | 0.074 | |||||||||||
σ-σ* | BD ( 1) C 1 - S 5 | 1.97486 | BD*( 1) C 4 - H 7 | 0.01311 | 2.76 | 1.22 | 0.052 | ||||||||
BD*( 1) C 12 - H 13 | 0.01378 | 1.76 | 1.08 | 0.039 | |||||||||||
σ-σ* | BD ( 1) C 1 - C 12 | 1.97917 | BD*( 1) C 12 - C 14 | 0.01462 | 1.53 | 1.96 | 0.049 | ||||||||
BD*( 1) C 14 - H 15 | 0.01324 | 1.42 | 1.16 | 0.036 | |||||||||||
BD*( 1) C 16 - C 18 | 0.05908 | 34.4 | 0.24 | 0.082 | |||||||||||
BD*( 1) C 18 - H 19 | 0.01254 | 120.55 | 0.08 | 0.09 | |||||||||||
BD*( 1) C 22 - C 24 | 0.02627 | 27.23 | 0.32 | 0.083 | |||||||||||
BD*( 2) C 22 - C 24 | 0.36662 | 36.29 | 0.13 | 0.067 | |||||||||||
σ-σ* | BD ( 1) C 2 - C 3 | 1.97199 | BD*( 1) C 1 - C 12 | 0.0274 | 4.38 | 1.19 | 0.065 | ||||||||
BD*( 1) C 3 - C 4 | 0.01512 | 2.83 | 1.36 | 0.056 | |||||||||||
BD*( 1) C 4 - H 7 | 0.01311 | 3.02 | 1.25 | 0.055 | |||||||||||
σ-σ* | BD ( 1) C 2 - C 8 | 1.97883 | BD*( 1) C 3 - C 4 | 0.01512 | 1.28 | 1.32 | 0.037 | ||||||||
σ-σ* | BD ( 1) C 3 - C 4 | 1.98319 | BD*( 1) C 4 - H 7 | 0.01311 | 1.34 | 1.3 | 0.037 | ||||||||
π-π* | BD ( 2) C 3 - C 4 | 1.8072 | BD*( 2) C 3 - C 4 | 0.32831 | 0.65 | 0.28 | 0.012 | ||||||||
σ-σ* | BD ( 1) C 3 - H 6 | 1.97779 | BD*( 1) C 3 - C 4 | 0.01512 | 1.33 | 1.21 | 0.036 | ||||||||
σ-σ* | BD ( 1) C 4 - S 5 | 1.97845 | BD*( 1) C 1 - C 12 | 0.0274 | 4.22 | 1.18 | 0.063 | ||||||||
σ-σ* | BD ( 1) C 4 - H 7 | 1.98573 | BD*( 1) C 3 - C 4 | 0.01512 | 1.3 | 1.23 | 0.036 | ||||||||
BD*( 1) C 16 - C 18 | 0.05908 | 13.02 | 0.08 | 0.03 | |||||||||||
BD*( 1) C 22 - C 24 | 0.02627 | 7.54 | 0.16 | 0.031 | |||||||||||
σ-σ* | BD ( 1) C 8 - H 9 | 1.98812 | BD*( 1) C 12 - C 14 | 0.01462 | 3.95 | 1.87 | 0.077 | ||||||||
BD*( 1) C 16 - O 17 | 0.01724 | 4.38 | 1.27 | 0.067 | |||||||||||
BD*( 1) C 24 - H 28 | 0.02271 | 2.98 | 1.1 | 0.051 | |||||||||||
BD*( 2) C 27 - C 29 | 0.33144 | 2.97 | 3.85 | 0.104 | |||||||||||
BD*( 1) C 27 - H 31 | 0.01409 | 2.52 | 4.81 | 0.098 | |||||||||||
σ-σ* | BD ( 1) C 8 - H 10 | 1.9793 | BD*( 1) C 22 - C 24 | 0.02627 | 74.35 | 0.12 | 0.086 | ||||||||
σ-σ* | BD ( 1) C 12 - H 13 | 1.96197 | BD*( 1) C 14 - H 15 | 0.01324 | 1.05 | 0.96 | 0.029 | ||||||||
BD*( 1) C 14 - C 16 | 0.05431 | 5.72 | 1.06 | 0.07 | |||||||||||
σ-σ* | BD ( 1) C 12 - C 14 | 1.98129 | BD*( 1) C 1 - C 12 | 0.0274 | 4.63 | 1.25 | 0.068 | ||||||||
BD*( 1) C 14 - C 16 | 0.05431 | 2.42 | 1.28 | 0.05 | |||||||||||
BD*( 1) C 16 - C 18 | 0.05908 | 8.93 | 0.27 | 0.044 | |||||||||||
π-π* | BD ( 2) C 12 - C 14 | 1.81895 | BD*( 2) C 16 - O 17 | 0.27328 | 21.41 | 0.29 | 0.072 | ||||||||
σ-σ* | BD ( 1) C 14 - H 15 | 1.97581 | BD*( 1) C 1 - C 12 | 0.0274 | 7.09 | 1.02 | 0.076 | ||||||||
BD*( 1) C 16 - O 17 | 0.01724 | 3.76 | 1.16 | 0.059 | |||||||||||
σ-σ* | BD ( 1) C 14 - C 16 | 1.9799 | BD*( 1) C 12 - H 13 | 0.01378 | 1.96 | 1.09 | 0.041 | ||||||||
BD*( 1) C 12 - C 14 | 0.01462 | 2.04 | 1.91 | 0.056 | |||||||||||
BD*( 1) C 16 - C 18 | 0.05908 | 5.72 | 0.19 | 0.03 | |||||||||||
BD*( 1) C 18 - H 19 | 0.01254 | 4.58 | 0.03 | 0.011 | |||||||||||
σ-σ* | BD ( 1) C 16 - O 17 | 1.99368 | BD*( 1) C 16 - C 18 | 0.05908 | 2.76 | 0.57 | 0.036 | ||||||||
π-π* | BD ( 2) C 16 - O 17 | 1.96036 | BD*( 2) C 12 - C 14 | 0.17953 | 4.25 | 0.43 | 0.039 | ||||||||
BD*( 2) C 18 - C 20 | 0.13135 | 4.57 | 0.4 | 0.039 | |||||||||||
σ-σ* | BD ( 1) C 16 - C 18 | 1.98102 | BD*( 1) C 12 - C 14 | 0.01462 | 1.59 | 1.91 | 0.049 | ||||||||
BD*( 1) C 18 - H 19 | 0.01254 | 6.35 | 0.03 | 0.012 | |||||||||||
BD*( 1) C 20 - H 21 | 0.01242 | 1.68 | 1.09 | 0.038 | |||||||||||
σ-σ* | BD ( 1) C 18 - H 19 | 1.97184 | BD*( 1) C 16 - O 17 | 0.01724 | 4.69 | 1.15 | 0.066 | ||||||||
BD*( 1) C 20 - H 21 | 0.01242 | 1.26 | 0.94 | 0.031 | |||||||||||
BD*( 1) C 20 - C 22 | 0.02819 | 7.7 | 1 | 0.078 | |||||||||||
σ-σ* | BD ( 1) C 18 - C 20 | 1.98216 | BD*( 1) C 16 - C 18 | 0.05908 | 14.3 | 0.27 | 0.056 | ||||||||
BD*( 1) C 18 - H 19 | 0.01254 | 8.42 | 0.11 | 0.028 | |||||||||||
BD*( 1) C 20 - C 22 | 0.02819 | 3.69 | 1.23 | 0.06 | |||||||||||
π-π* | BD ( 2) C 18 - C 20 | 1.84033 | BD*( 2) C 16 - O 17 | 0.27328 | 20.32 | 0.29 | 0.07 | ||||||||
σ-σ* | BD ( 1) C 20 - H 21 | 1.97149 | BD*( 1) C 16 - C 18 | 0.05908 | 73.62 | 0.05 | 0.056 | ||||||||
BD*( 1) C 22 - C 24 | 0.02627 | 40.86 | 0.13 | 0.065 | |||||||||||
σ-σ* | BD ( 1) C 20 - C 22 | 1.97691 | BD*( 1) C 16 - C 18 | 0.05908 | 9.02 | 0.2 | 0.038 | ||||||||
BD*( 1) C 22 - C 23 | 0.02207 | 2.06 | 1.22 | 0.045 | |||||||||||
BD*( 1) C 22 - C 24 | 0.02627 | 32.81 | 0.27 | 0.085 | |||||||||||
BD*( 2) C 22 - C 24 | 0.36662 | 7.71 | 0.08 | 0.025 | |||||||||||
σ-σ* | BD ( 1) C 22 - C 23 | 1.97392 | BD*( 1) C 20 - C 22 | 0.02819 | 2.17 | 1.17 | 0.045 | ||||||||
BD*( 2) C 22 - C 24 | 0.36662 | 120.04 | 0.1 | 0.106 | |||||||||||
σ-σ* | BD ( 1) C 22 - C 24 | 1.9728 | BD*( 1) C 23 - H 26 | 0.0143 | 3.64 | 1.12 | 0.057 | ||||||||
BD*( 1) C 24 - C 27 | 0.01547 | 2.59 | 1.27 | 0.051 | |||||||||||
π-π* | BD ( 2) C 22 - C 24 | 1.5862 | BD*( 2) C 18 - C 20 | 0.13135 | 13.05 | 0.29 | 0.059 | ||||||||
BD*( 2) C 23 - C 25 | 0.31148 | 20.9 | 0.29 | 0.071 | |||||||||||
BD*( 2) C 27 - C 29 | 0.33144 | 2.84 | 3.47 | 0.09 | |||||||||||
σ-σ* | BD ( 1) C 23 - C 25 | 1.97917 | BD*( 1) C 4 - H 7 | 0.01311 | 3.66 | 1.28 | 0.061 | ||||||||
BD*( 1) C 20 - C 22 | 0.02819 | 3.26 | 1.21 | 0.056 | |||||||||||
BD*( 1) C 22 - C 23 | 0.02207 | 4.39 | 1.27 | 0.067 | |||||||||||
σ-σ* | BD ( 1) C 23 - H 26 | 1.98069 | BD*( 1) C 22 - C 23 | 0.02207 | 0.69 | 1.07 | 0.024 | ||||||||
σ-π* | BD ( 1) C 24 - C 27 | 1.97888 | BD*( 2) C 3 - C 4 | 0.32831 | 3.77 | 0.9 | 0.056 | ||||||||
BD*( 1) C 4 - H 7 | 0.01311 | 6.05 | 1.47 | 0.084 | |||||||||||
BD*( 1) C 16 - O 17 | 0.01724 | 4.9 | 1.55 | 0.078 | |||||||||||
BD*( 1) C 20 - C 22 | 0.02819 | 4.41 | 1.39 | 0.07 | |||||||||||
σ-σ* | BD ( 1) C 24 - H 28 | 1.97705 | BD*( 1) C 16 - C 18 | 0.05908 | 27.9 | 0.02 | 0.023 | ||||||||
BD*( 1) C 22 - C 23 | 0.02207 | 4.86 | 1.05 | 0.064 | |||||||||||
BD*( 1) C 22 - C 24 | 0.02627 | 27.94 | 0.1 | 0.048 | |||||||||||
σ-π* | BD ( 1) C 25 - C 29 | 1.97941 | BD*( 2) C 3 - C 4 | 0.32831 | 4.09 | 0.69 | 0.052 | ||||||||
BD*( 1) C 12 - C 14 | 0.01462 | 10.22 | 1.94 | 0.126 | |||||||||||
BD*( 1) C 16 - O 17 | 0.01724 | 9.45 | 1.34 | 0.101 | |||||||||||
BD*( 1) C 23 - H 26 | 0.0143 | 6.31 | 1.13 | 0.075 | |||||||||||
BD*( 1) C 24 - H 28 | 0.02271 | 8.21 | 1.17 | 0.087 | |||||||||||
σ-σ* | BD ( 1) C 25 - H 30 | 1.98016 | BD*( 1) C 4 - H 7 | 0.01311 | 3.33 | 1.1 | 0.054 | ||||||||
BD*( 1) C 22 - C 23 | 0.02207 | 5.6 | 1.08 | 0.069 | |||||||||||
BD*( 1) C 24 - H 28 | 0.02271 | 3.22 | 1 | 0.051 | |||||||||||
BD*( 1) C 29 - H 32 | 0.01371 | 2.72 | 2.61 | 0.075 | |||||||||||
σ-π* | BD ( 1) C 27 - C 29 | 1.98062 | BD*( 2) C 3 - C 4 | 0.32831 | 4.13 | 0.69 | 0.052 | ||||||||
BD*( 1) C 12 - C 14 | 0.01462 | 9.11 | 1.94 | 0.119 | |||||||||||
BD*( 1) C 16 - O 17 | 0.01724 | 9.4 | 1.34 | 0.1 | |||||||||||
BD*( 2) C 27 - C 29 | 0.33144 | 16.2 | 3.92 | 0.245 | |||||||||||
π-π* | BD ( 2) C 27 - C 29 | 1.64275 | BD*(2) C 23 - C 25 | 0.31148 | 18.55 | 0.29 | 0.066 | ||||||||
σ-σ* | BD ( 1) C 27 - H 31 | 1.98023 | BD*(1) C 4 - H 7 | 0.01311 | 3.3 | 1.08 | 0.053 | ||||||||
BD*(1) C 24 - H 28 | 0.02271 | 5.55 | 0.99 | 0.066 | |||||||||||
σ-π* | BD ( 1) C 29 - H 32 | 1.98091 | BD*( 2) C 3 - C 4 | 0.32831 | 4.65 | 0.48 | 0.046 | ||||||||
BD*( 1) C 12 - C 14 | 0.01462 | 26.51 | 1.73 | 0.191 | |||||||||||
BD*( 1) C 16 - O 17 | 0.01724 | 16.8 | 1.13 | 0.123 | |||||||||||
BD*( 1) C 24 - H 28 | 0.02271 | 9.57 | 0.96 | 0.086 | |||||||||||
BD*( 2) C 27 - C 29 | 0.33144 | 23.61 | 3.71 | 0.288 | |||||||||||
BD*( 1) C 27 - H 31 | 0.01409 | 34.65 | 4.66 | 0.359 | |||||||||||
n-σ* | LP ( 1) S 5 | 1.98351 | BD*( 1) C 3 - C 4 | 0.01512 | 2.25 | 1.32 | 0.049 | ||||||||
n-π* | LP ( 2) S 5 | 1.58098 | BD*( 2) C 3 - C 4 | 0.32831 | 27.15 | 0.24 | 0.074 | ||||||||
n-σ* | LP ( 1) O 17 | 1.969 | BD*( 1) C 14 - C 16 | 0.05431 | 2.03 | 1.23 | 0.045 | ||||||||
BD*( 1) C 16 - C 18 | 0.05908 | 5.78 | 0.22 | 0.032 | |||||||||||
BD*( 1) C 24 - H 28 | 0.02271 | 2.57 | 1.16 | 0.049 | |||||||||||
n-π* | LP ( 2) O 17 | 1.88598 | BD*( 1) C 14 - C 16 | 0.05431 | 14.61 | 0.81 | 0.098 | ||||||||
BD*( 1) C 24 - H 28 | 0.02271 | 2.64 | 0.74 | 0.04 | |||||||||||
π*-σ* | BD*( 2) C 1 - C 2 | 0.39784 | BD*( 1) C 12 - C 14 | 0.01462 | 8.28 | 33.56 | 1.036 | ||||||||
BD*( 1) C 16 - O 17 | 0.01724 | 8.11 | 32.96 | 1.013 | |||||||||||
BD*( 2) C 27 - C 29 | 0.33144 | 21.31 | 35.54 | 1.286 | |||||||||||
BD*( 1) C 27 - H 31 | 0.01409 | 8.56 | 36.49 | 1.099 | |||||||||||
BD*( 1) C 29 - H 32 | 0.01371 | 4.11 | 34.39 | 0.74 | |||||||||||
π*-π* | BD*( 2) C 3 - C 4 | 0.32831 | BD*( 2) C 16 - O 17 | 0.27328 | 0.71 | 0.02 | 0.005 | ||||||||
π*-σ* | BD*( 2) C 12 - C 14 | 0.17953 | BD*( 1) C 29 - H 32 | 0.01371 | 2.9 | 2.02 | 0.22 | ||||||||
π*-π* | BD*( 2) C 16 - O 17 | 0.27328 | BD*( 2) C 12 - C 14 | 0.17953 | 35.93 | 0.05 | 0.077 | ||||||||
BD*( 2) C 18 - C 20 | 0.13135 | 62.96 | 0.02 | 0.074 | |||||||||||
π*-π* | BD*( 2) C 18 - C 20 | 0.13135 | BD*( 2) C 27 - C 29 | 0.33144 | 1.45 | 3.19 | 0.126 | ||||||||
π*-π* | BD*( 2) C 22 - C 24 | 0.36662 | BD*( 2) C 3 - C 4 | 0.32831 | 5.26 | 0.58 | 0.084 | ||||||||
BD*( 1) C 16 - O 17 | 0.01724 | 3.86 | 1.23 | 0.141 | |||||||||||
BD*( 2) C 23 - C 25 | 0.31148 | 6.92 | 0.62 | 0.101 | |||||||||||
BD*( 1) C 24 - H 28 | 0.02271 | 3.37 | 1.06 | 0.121 | |||||||||||
π*-π* | BD*( 2) C 23 - C 25 | 0.31148 | BD*( 2) C 27 - C 29 | 0.33144 | 6.83 | 3.19 | 0.232 | ||||||||
π*-σ* | BD*( 2) C 27 - C 29 | 0.33144 | BD*( 1) C 27 - H 31 | 0.01409 | 367.87 | 0.96 | 1.273 |
E(2) means energy of hyper conjugative interaction (stabilization energy).
Energy difference between donor (i) and acceptor(j) nbo orbitals.
F(i,j) is the Fock matrix element between i and j nbo orbitals.
Molecular orbital and their properties like energy are very useful to the physicists and chemists
Parameters | Values |
HOMO | -6.055 eV |
LUMO | -2.622 eV |
Energy gap | 3.432 eV |
Ionization potential (IP) | 6.055 eV |
Electron affinity (EA) | 2.622 eV |
Electrophilicity Index (ω) | 2.741 |
Chemical Potential (µ) | 4.338 |
Electronegativity (χ) | 4.338 |
Hardness (η) | -3.432 |
Softness (S) | 6.866 |
Occupancy | Orbital energies (a.u) | Orbital energies (eV) | Kinetic energies (a.u) |
O52 | -0.269 | -7.343 | 1.118 |
O53 | -0.252 | -6.858 | 2.314 |
O54 | -0.246 | -6.708 | 1.429 |
O55 | -0.241 | -6.569 | 1.348 |
O56 | -0.235 | -6.405 | 1.388 |
V57 | -0.097 | -2.646 | 1.398 |
V58 | -0.051 | -1.397 | 1.289 |
V59 | -0.025 | -0.694 | 1.244 |
V60 | 0.016 | -0.441 | 1.358 |
V61 | 0.013 | -0.373 | 0.251 |
The electronic spectra of the title moleculeis calculated using TD-DFT/B3LYP/6-311++G(d,p) basis set. The electronic transitions, positions of experimental absorption peaks, calculated absorption peaks (λmax), vertical excitation energies, oscillator strengths (f) are listed in
Calculated at B3LYP/6-311++G(d,p) | Oscillator Strength | Calculated Band gap(ev/nm) | Experimental Type Band gap (ev/nm) |
Excited State-1 | Singlet-A(f=0.0000) | 2.9436 eV/421.19 nm | |
65 -> 68 | 0.68512 | 4.164218 | |
Excited State-2 | Singlet-A(f=0.6489) | 3.6113 eV/343.32 nm | 352 π–π* |
67 -> 68 | 0.64129 | 3.432542 | |
Excited State-3 | Singlet-A(f=0.0507) | 3.6113 eV/343.32 nm | 303 π –π* |
64 -> 68 | 0.28196 | 4.289929 | |
66 -> 68 | 0.58917 | 3.960688 | |
67 -> 69 | 0.13934 | 4.689976 |
MEP indicates the net electrostatic effect produced at that point by the total charge distribution (nuclei + electron) of the molecule and correlates with dipole moments, electronegativity, partial charges and chemical reactivity of the molecules. It provides a visual method to understand the relative polarity of the molecule. The different values of the electrostatic potential represented by different colors; red represents the regions of the most negative electrostatic potential, blue represents the regions of the most positive electrostatic potential and green represents the regions of zero potential.The MEP is calculated with B3LYP/6-311++G(d,p) basis set and the MEP plot is shown in
The negative electrostatic potential corresponds to an attraction of the proton by the aggregate ED in the molecule (shades of red), while all the hydrogen atoms have positive electrostatic potential corresponds to the repulsion of the proton by the atomic nuclei (shades of blue). The MEP map shows that the negative region is mainly localized on oxygen and sulphur atoms while the positive region is localized on the surface of all the hydrogen atoms in MPPO. These regions indicate the active charge sites of the molecule. A region of zero potential envelopes the π-system of the aromatic rings
The calculation of atomic charges plays an important role in the application of quantum mechanical calculation to molecular system
Atoms | Charges | Atoms | Charges |
1C | 0.519 | 17O | -0.2251 |
2C | 0.0009 | 18C | -0.3645 |
3C | -0.2145 | 19H | 0.1716 |
4C | -0.0636 | 20C | -0.2478 |
5S | -0.5428 | 21H | 0.1456 |
6H | 0.1464 | 22C | 0.9651 |
7H | 0.2521 | 23C | 0.1338 |
8C | -0.9824 | 24C | -0.7922 |
9H | 0.1601 | 25C | -0.3845 |
10H | 0.1602 | 26H | 0.1524 |
11H | 0.1602 | 27C | -0.1456 |
12C | 0.219 | 28H | 0.1564 |
13H | 0.1608 | 29C | -0.1516 |
14C | -0.1696 | 30H | 0.1636 |
15H | 0.1724 | 31H | 0.1782 |
16C | 0.1067 | 32H | 0.1589 |
The various thermodynamic parameter are computed by B3LYP/6-311++G(d,p) basis set and are listed in
S0m = 0.98075 + 0.00414T - 3.65824 x 10-5 T2 (R2 = 0.9999)
C0p,m = 6.04475 + 0.02552T +2.25471x 10-5 T2 (R2 = 0.9992)
ΔH0m = 4.00201 + 0.169T + 1.49276x 10-5 T2 (R2 = 0.9994)
Parameters | B3LYP/6-311++G(d,p) |
Total Energies | -1091.71 |
Zero-point Energy | 158.198 (Kcal/Mol) |
Rotational constants (GHZ) | 1.013 |
0.156 | |
0.135 | |
Entropy | |
Total | 135.128 |
Translational | 42.498 |
Rotational | 33. 969 |
Vibrational | 58.661 |
T (K) | S (J/mol.K) | Cp (J/mol.K) | ddH (kJ/mol) |
100 | 376.62 | 119.6 | 8.02 |
200 | 481.8 | 194.81 | 23.62 |
298.15 | 575.09 | 278.44 | 46.82 |
300 | 576.82 | 280.01 | 47.34 |
400 | 668.56 | 359.67 | 79.42 |
500 | 756.18 | 425.73 | 118.81 |
600 | 838.65 | 478.52 | 164.12 |
700 | 915.71 | 520.88 | 214.17 |
800 | 987.59 | 555.43 | 268.04 |
900 | 1054.72 | 584.04 | 325.06 |
1000 | 1117.53 | 608.01 | 384.69 |
The above data can be used to compute other thermodynamic energies according to the well-known relationships of thermodynamic functions and to predict the directions of chemical reactions
A complete vibrational analysis had been carried out for the first time to the molecule MPPO. The bond parameters and vibrational wavenumbers agreed well with experimental results. The first order hyperpolarizability (β0 = 10.2328x10-30esu) of MPPO was calculated and found to be twenty seven times greater than that of urea and hence the molecule had moderate NLO activity. The considerabledecrease of the lone pair orbital occupancy (1.581e) of LP(2)S5was due to more E(2) energy transfer to anti-bonding orbital C3-C4. The Homo-Lumo energy gap was calculated about 3.4327 eV, which explain the eventual charge transfer occur within the molecule and also enhanced the biological activity. The recorded UV-Vis. spectral values agreed with calculated values. The λmax (352) was assigned to π-π* type. Furthermore, the MEP and Mulliken atomic charges had been calculated and also plotted. The good correlations between the statistical thermodynamics and temperature were also established.