Vibrational spectroscopic studies, HOMO - LUMO and First

A. Ramu1, M.K. Murali2, M.Karnan3, S.Saravanan4

1, 2 PG & Research Department of Physics, JJ.College of Arts & Science (A), Pudukkottai – 622 422, India

3, PG & Research Department of Physics,Srimad Andavan Arts&Science College (A), Thiruchirappalli - 620 005,india

4 PG & Research Department of Physics,National College (A), Thiruchirappalli - 620 001,india

1aramusir80@gmail.com, 2muralimk1970@gmail.com

Abstract - Pyrimidine is group of molecules that is part of the DNA and RNA structure. It is an aromatic heterocyclic organic compound similar to pyridine. Drugs that are similar to pyrimidine have been used to treat certain conditions including skin cancer and keratosis. The fourier transform Infrared and FT – Raman spectra of 5, 6 – Dimethyl – 2, 4 (1H, 3H) – pyrimidine dione(DMPMDN) were recorded in the solid phase. The vibrational frequencies of the DMPMDN molecule in the ground state have been calculated using density functional method B3LYP with 6-31+G(d),6–311++G(d,p) basis sets. The harmonic vibrational frequencies were calculated and scaled values have been compared with those the FT IR and FT Raman Spectra. The observed and calculated, Frequencies are found to be in good agreement. The calculated HOMO and LUMO energies show that charge transfer occurs within the molecule. The dipole moment (µ), polarizability (α) and the first order hyperpolarizability (β) values of the investigated molecule have been computed using B3LYP Method. The molecular electrostatic potential surface was mapped and studied and also Mulliken atomic charge was analyzed. The complete work has been compared with those on pyrimidinedione derivatives. Keywords - DMPMDN ,FT – IR, FT – Raman, HOMO – LUMO, First order hyper polarizability

I INTRODUCTION

Heterocyclic science plays a significant role in natural science analyzing the blend, properties, and uses of heterocycles [1]. Heterocyclic subordinates carrying at least one nitrogen atom are quite normal in a pharmaceutical and pharmaceutical intermediates products. Such frameworks promote for the general utility curative molecules, they several as dynamic pharmaceutical elements for the treatment basic ailments. Particularly the N-heterocyclic particle, for example, pyrimidine, cytosine, uracil and their subordinates are huge significance since some of them are the fundamental constituents of DNA and RNA and assume a critical part in the composition and properties of nucleic acids [2-4]. And in addition, non-Nucleoside Pyrimidine and its subordinates have been valued to their organic and pharmaceutical importance in anticancer [1-6], antiviral [7-18], antimicrobial [19-24] and antimalarial [25, 26] uses. Due to this significance, the present spectroscopic examination of one of the pyrimidine subsidiaries DMPMDN with the molecular equation C6H8N2O2 as a title molecule is taken to this determination. The DFT techniques have been advanced as fit devices for the determination of the electronic and optimized structure of molecules [31]. In the DFT approach, diverse and relation functions are explored. Among these, the B3LYP method is the most utilized since it has the capacity to imitate different molecular properties, including vibrational spectra. The joined utilization of B3LYP and other standard basis sets gives a greater exactness and computational efficiency of vibrational spectra for all the size molecules except the smaller size molecules. The aim of the present examination is to give a complete picture of the inter and intramolecular structure and vibrations of the title molecule by utilizing the FT-IR and FT-Raman vibrational spectra. For that purpose, quantum chemical calculations were done on the ground state with B3LYP/6-31+G(d,p) and 6-311++G(d,p) basis sets. The ascertained highest involved molecular orbital (HOMO) and Lowest vacant molecular orbital (LUMO) energies demonstrate that charge transfer happens in the title molecule. The dipole moment (µ), polarizability (α) and the first order hyperpolarizability (β) estimations of the research molecule have been registered in B3LYP Method and the NLO property was investigated by the same method. DFT figuring show superb vibrational frequencies of the molecules if the ascertained frequencies are scaled to make up for the inexact treatment of electron correlation. Above every parameter is accounted for and analyzed by higher and lower basis sets. The geometrical streamlining of the title molecule has been compared with other pyrimidinedione subsidiaries in light of A.Banerjee et al [32], Portalone et al [33] studies.

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order hyperpolarizabilities analysis of 5, 6 dimethyl – 2, 4,- (1H, 3H) pyrimidine dione based on Density functional theory

II MATERIAL AND EXPERIMENTAL METHODS The unadulterated sample of DMPMDN appearance white to relatively white crystalline powder was bought from the Lancaster Chemical Company (UK), with an expressed purity of 98% and it was utilized in the study without further cleansing. The FT-IR range of DMPMDN was recorded in the range 4000-400cm-1 on IFS 66V spectrometer. The FT-Raman range of DMPMDN has been recorded utilizing the 1064 nm line of a Nd:YAG LASER as excitation wavenumber in the range of 3500-100 cm-1 on a BRUKER display RFS 66V spectrometer. The detailed wavenumbers relied upon are inside 1 cm-1 with 250 mW of intensity in both the systems.

III COMPUTATIONAL DETAILS

In this work, a thoroughgoing hypothetical count was performed using DFT/B3LYP strategy with 6-31+G(d) and 6-31++G(d,p) basis set [34] on a PC utilizing GAUSSIAN 09W [35] program bundle, achieving angle geometry enhancement [36]. The vibrational recurrence with the compound was determined alongside their IR power and Raman activity. In order to fit the theoretical figured FT-IR and FT-Raman wavenumbers to in the experimental spectra. The polarizability, first order hyperpolarizability and net dipole moment of DMPMDN have been computed utilizing a similar technique. The HOMO-LUMO investigation has been completed to clarify the electron exchanges inside the molecule. The global hardness, global softness, electronegativity and compound potential have been ascertained utilizing the highest involved molecular orbital (HOMO) and lowest vacant molecular orbital (LUMO). The entire molecular electrostatic potential (MEP) [37] of DMPMDN has been ascertained at a similar level the hypothetical. Gaussview 5.0.8 representation program [38] has been utilized to build up the MEP surface. The following equation show, the way in which value of Raman intensities [39,40] were calculated.

Ira=f(ʋ0-ʋi)4Sra/ʋi[1-exp(- hCʋi/kT)] Where ʋ0 is the energizing wavenumber of a LASER light source used while recording Raman spectra. ʋi the vibrational wavenumber of the ith typical mode h, C and k basic constants, Si is Raman activity, and f is a reasonably picked regular standardization factor for all pinnacle forces of the Raman range of DMPMDN. Vibrational mode assignments were completed using VEDA4 program composed by Jamroz[41] in the light of the rate potential vitality circulation examination.

IV RESULTS AND DISCUSSIONS

A. Geometrical Optimization

The geometry improvement of the C1 point group molecule of DMPMDN was calculated by DFT count technique with B3LYP/6-31+G(d),6-311++G(d,p) basis sets. The geometry advancement examined and was compared with XRD estimations of other uracil and uracil subsidiaries ( uracil [42], thymine [43-45], 1-methyluracil [46], 1,3-dimethyluracil [32] ).The structural diagram of the pyrimidine derivatives and the DMPMDN are shown in fig. 1 and fig. 2

C

N

N

C

C

C

O

H

H

O

CH3

CH3

a)DMPMDN

C

N

N

C

C

C

O

H

H

O

H

H

b)uracil c)1,3 Dimethyl uracil

C

N

N

C

C

C

O

CH3

CH3

O

H

H

d)1,methyluracil

C

N

N

C

C

C

O

H

CH3

O

H

H

e) 5, methyluracil

C

N

N

C

C

C

O

H

H

O

H

CH3

Fig. 1 Pyrimidinedione derivatives derivatives

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Table I shows the information on geometrical optimization of the isolated title molecule and pyrimidinedione

subordinates. From it one way reason that the DMPMDN has marginally unpredictable hexagonal structure. The title molecule, the order of the bond length is C5-C11 = C6-C15 > C4-C5 > N3-C4 > N1-C6 > N1-C2 > C2-N3 > C5-C6 > C4-O10 ≈ C2-O8 > C15-H16 = C15-H18 > C11-H14 = C11-H12 > C11-H13 ≈ C15-H17 > N3-H9 > N1-H7. the methyl group in ring structure used along with C5 and C6 atoms showed the longest bond length in that molecular structure because C-C bond shaped a nonpolar covalent bond [47] and the hyper conjugation causes the synchronization of the orbital of the methyl aggregate with the π orbital of a hetrocyclic fragrant ring [48]. This synchronizing led to discharge of electronic charge from the methyl group [49].and resulted in lengthier bond value 1.5056 Å (6-31+G(d)),1.5035 Å (6-311++G(d, p)) for C5-C11 and 1.5042 Å (6-31+G(d)),1.5016 Å (6-311++G(d, p)) for C6-C15 which concur with the other literature estimated in 1.502 Å [33], 1.5062 Å [49], 1.5095 Å [50]. N-H bond length is shorter bond length because of hydrogen holding, which causes the deliberate decreasing of the N-C bond and extends of the C=O bond [33]. The strongest double bond atoms C5=C6 bond length is shorter than the weakest single bond atoms C4-C5 [32]. In the methyl group ,C-H bond length values 1.0917 Å, 1.0962 Å, 1.0962 Å (6-31+G(d)), 1.0886 Å,1.0934 Å,1.095 Å (6-311++G(d,p)) are concurrence with the esteems in selected literature 1.09 Å [51], 1.08 Å, 1.09 Å [11], 1.09 Å [52]. Lowest angle of N1-C2-N3 caused by the focal atom C2 holding with high electronegative atom Oxygen [47]. Greater angle of C2-N3-C4 127.1509° (6-31+G(d)) and 127.2877° (6-311++G(d, p)) with the high electronegative atom Oxygen associated with two end atoms C2 and C4 [47]. This contrasts with the uracil and its subsidiaries including title molecule, there is little variance in bond length and bond angle compared with uracil molecule because of the impact of the introduction of the methyl aggregate in the ring structure[53]. In the perspective the optimized geometry of the uracil molecule, we find that the bond point subtending the substituent is 1.7° smaller for thymine, 2.3° for 1-methyluracil and 2.2° and 2.7° for 1,3-dimethyluracil [10] and 0.242° (6-31+G(d)), 0.163°( 6-311++G(d,p)) and 3.026° (6-31+G(d)), 2.923° ( 6-311++G(d,p)) for DMPMDN.

TABLE I.

Geometrical optimization and comparison with pyrimidine derivatives

5,6-dimethyluracil 1-methyluracil[33] Thymine[33] Uracil[33] 1,3-dimethyluracil [32] Bond length(Å)

6-31+G(d) 6-311++G(d,p) Neutron diff X-ray X-ray X-ray

N1,C2 1.3858 1.385 1.379 1.358 1.371 1.375 N1,C6 1.3918 1.3904 1.369 1.384 1.359 1.378 N1,H7 1.0123 1.0095 - 0.82 0.84 - C2,N3 1.3811 1.3801 1.377 1.361 1.377 1.380 C2,O8 1.2225 1.2147 1.228 1.244 1.215 1.225 N3,C4 1.4046 1.4041 1.384 1.401 1.371 1.399 N3,H9 1.015 1.0123 1.043 0.83 0.88 C4,C5 1.4696 1.4686 1.440 1.453 1.430 1.437 C4,O10 1.2262 1.2187 1.241 1.225 1.245 1.227 C5,C6 1.3629 1.3583 1.357 1.343 1.340 1.331 C5,C11 1.5056 1.5035 - 1.502 - - C6,C15 1.5042 1.5016 - - - - C11,H12 1.0962 1.0933 - - - - C11,H13 1.0917 1.0886 - - - -

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C11,H14 1.0962 1.0934 - - - - C15,H16 1.098 1.095 - - - - C15,H17 1.089 1.086 - - - - C15,H18 1.098 1.095 - - - - Bond angle(°) C2,N1,C6 125.628 125.6106 121.31 122.5 122.7 120.8 C2,N1,H7 114.4245 114.4654 - - - - C6,N1,H7 119.9475 119.924 - - - - N1,C2,N3 112.6934 112.5568 115.57 115.5 114.0 116.7 N1,C2,O8 123.0677 123.1588 122.17 122.4 123.7 122.9 N3,C2,O8 124.2389 124.2844 - - - 121.8 C2,N3,C4 127.1509 127.2877 126.54 126.3 126.7 124.7 C2,N3,H9 116.3095 116.2394 - - - - C4,N3,H9 116.5396 116.4729 - - - - N3,C4,C5 115.6967 115.5302 114.74 115.1 115.5 114.9 N3,C4,O10 119.7353 119.881 119.82 119.2 119.2 119.6 C5,C4,O10 124.568 124.5888 -- - - 125.5 C4,C5,C6 118.658 118.737 119.35 118.4 118.9 120.4 C4,C5,C11 115.1996 115.2031 - - - - C6,C5,C11 126.1424 126.06 - - - - N1,C6,C5 120.1731 120.2777 122.48 122.3 123.2 122.4 N1,C6,C15 113.1623 113.1953 - - - - C5,C6,C15 126.6647 126.527 - - - - C5,C11,H12 110.4773 110.3826 - - - - C5,C11,H13 112.7594 112.7371 - - - - C5,C11,H14 110.477 110.4031 - - - - H12,C11,H13 108.2994 108.3823 - - - - H12,C11,H14 106.287 106.3196 - - - - H13,C11,H14 108.296 108.3801 - - - - C6,C15,H16 110.473 110.321 - - - - C6,C15,H17 112.2364 112.2179 - - - - C6,C15,H18 110.4741 110.324 - - - - H16,C15,H17 107.9718 108.1043 - - - - H16,C15,H18 107.5514 107.6135 - - - - H17,C15,H18 107.9691 108.11 - - - -

B. Frontier Orbital Energy Gap:

The Frontier molecular orbital hypothesis is one of the molecular orbital hypothesis. The HOMO and LUMO may center around the Frontier molecular orbital hypothesis, however they are not always included in the study of compound reactivity. Symmetry has vital to play in this hypothesis. On the off chance that the right symmetry is absent in the response, it might move to the following most noteworthy HOMO and next least LUMO to complete the procedure.

N1,

C2

N1,

C6

N1,

H7

C2,

N3

C2,

O8

N3,

C4

N3,

H9

C4,

C5

C4,

O10

C5,

C6

C5,

C11

0.8

0.9

1.0

1.1

1.2

1.3

1.4

1.5

1.6

1.7

1.8

Bond

Length

A

6-31+G(d) 6-311++G(d,p) 1-methyluracil Thymine[ Uracil 1,3-dimethyluracil

Fig. 3 Bond length comparison of pyrimidinedione derivatives

N1,

C6

C2,

N1,

C6

C2,

N1,

H7

C6,

N1,

H7

N1,

C2,

N3

N1,

C2,

O8

N3,

C2,

O8

C2,

N3,

C4

C2,

N3,

H9

C4,

N3,

H9

N3,

C4,

C5

N3,

C4,

O10

C5,

C4,

O10

C4,

C5,

C6

C4,

C5,

C11

C6,

C5,

C11

N1,

C6,

C5

112

114

116

118

120

122

124

126

128

130

Bo

nd

An

gle

6-31+G(d) 6-311++G(d,p) 1-methyluracil Thymine[ Uracil 1,3-dimethyluracil

Fig. 4 Bond angle comparison of pyrimidinedione derivatives

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The energy gap of the frontier orbital provides for indicates the compound reactivity and kinetic steadiness of the molecule. The little energy gap is highly polarizable and is by and large connected with a more chemical reactivity and minimum kinetic stability is named as soft molecule [54]. The frontier molecular orbital assumes an essential part in the electric and optical properties [55]. The HOMO– LUMO partition is the aftereffect of free intramolecular charge exchange from the end-topping electron-contributor gatherings to the proficient electron-acceptor bunches through p-conjugated reaction [56]. HOMO and LUMO is negative, which shows that the concentrated compound is steady [57]. For understanding different parts of pharmacological science including drug plan and the conceivable eco-toxicological qualities of the medication molecule, a few new compound a reactivity descriptors have been suggested. DFT based investigation have used to comprehend the molecular reactivity by ascertaining the global hardness (η), compound potential (μ) and electrophilicity (ω). Utilizing frontier orbital energies, the electron affinity (A) and ionization energy (I) can be calculated as [58-61],

I = - EHOMO, A = - ELUMO,

η = (- EHOMO + ELUMO)/2

μ = (EHOMO + ELUMO)/2

ω= μ2/2η.

Electrophilicity data show about both electron exchange (compound potential) and steadiness (hardness) and is a superior signifier of global chemical reactivity. softness is a property of a chemical substance that estimates the degree of substance reactivity. It is a complementary of hardness.

S=1/η

These parameters are relating to calculated and compared by using DFT calculation with B3LYP/6-31+G(d), 6-311++G(d,p) basis sets (Table II).The result reveals that the chemical potential of the title compound is negative and it means that the compound is stable. It does not decompose spontaneously into the elements it is made up of. The hardness indicates the resistance the deformation of the electron cloud of chemical systems under low perturbation encountered during the chemical process. The principle of hardness works in chemistry and physics but it is not physically observable. soft systems are huge and tremendously polarisable, at the same time as hard sytems are particularly small and plenty much less polarisable.

Table II.

Homo- Lumo Energy Gap and chemical properties of DMU

Parameters 6-31+G(d) (eV) 6-311++G(d,p) (eV)

Homo(I) -6.791692328 -6.825706573 Lumo(A) -1.363835168 -1.389958108 Energy gap(∆E) 5.42785716 5.435748465 Electronegativity 4.077763748 4.10783234 Global hardness 2.71392858 2.717874232 Global softness 272.836978 272.4408891 Chemical potential -4.077763748 -4.10783234 Electriphilicity 3.063484666 3.104317031 SCF -493.4782149(a.u) -493.6050998(a.u)

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C. NLO Properties Nonlinear optics seeks to understand the reacting of lightmatter collaborations when the material's reaction is Nonlinear, when connected to electromagnetic field [62]. The nearness of conjugated electrons of the aromatic ring is caused by first order first order hyperpolarizability [63].When the framework is connected to an electricfield, polarizability and first order hyperpolarizabilty are observed this shows the quality of molecular interaction, cross segments of various scrambling and impact forms and the NLO properties of the system [64].

Lumo = -1.3638eV

∆E=5.4278eV

Homo = -6.7916eV

6-31+G(d) 6-311++G(d,p)

Lumo= -1.3899eV

∆E= 5.4357eV

Homo= -6.79169eV

Fig. 6. DOS spectrum of DMPMDN

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The first order hyperpolarizability (βtot ) is a third rank tensor that can be delineated by the 3X3X 3 the lattice. The 27 parts of the 3 D grid can be diminished to 10 segments because of the Klein man symmetry [65,66]. The segments of β are characterized as coefficient in the Taylor arrangement development of the vitality in the extrernal electric field. At the point when the electrical field is feeble and homogenous, this extension progresses toward becoming,

E=E0 - µαFα - 1/2ααβFαFβ - 1/6βαβϒFαFβFϒ + …

Where E0 is the vitality of the unperturbed atoms, Fα the field at the source µα, ααβ and βαβϒ are the segments of dipole moment, polarizability and the first order hyper polarizabilities. The aggregate static dipole moment (µ), polarizability(α), anisotropy polarizability (∆α) and the mean first first order hyperpolarizability (βtot ) utilizing x,y,z, The segments are characterized as follows [67],

µ=(µx2+µy

2+µz2)1/2

α=(αxx+αyy+αzz)/3

∆α=(αxx-αyy)2+(αyy-αzz)2+6αxx

2)1/2/21/2

βx=(βxxx+βxyy+βxzz)

βy=(βyyy+βxxy+βyzz)

βz=(βzzz+βxxz+βyyz)

βtot=(βx2+βy

2+βz2)1/2

Since the estimations of the polarizability and the first order hyper polarizability of the Gussian 09W yield are

accounted for in a.u (atomic unit), the computed esteems of polarizability, first order hyperpolarizability have been converted over into esu(electrostatic unit) (α:1a.u=0.148X10-24 esu and β:1a.u=8.639X10-33 esu). As can be found in Table III, the figured estimation of the titled compound is more noteworthy that of urea as indicated by first order hyper polarizability, The title compound might be potential candidate in the advancement of NLO materials.

Table III. NLO Properties of DMU

Parameters 6-31+G(d) 6-311+G(d,p) µx 2.4771 2.4825

µy 4.6026 4.5092

µz 0.0003 0.0001

αXX -68.5831 -68.2406

αYY -58.481 -58.4092

αZZ -59.2025 -59.1072

αXY 6.3881 6.3622

αXZ -0.0006 -0.0003

αYZ -0.0005 0.0015

βXXX 47.4096 47.2442

βYYY 40.0081 39.4081

βZZZ 0.0009 0.0068

βXYY -21.6958 -21.1341

βXXY -4.5039 -4.6637

βXXZ 0.0034 0.0003

βXZZ -2.795 -2.9071

βYZZ -1.8261 -1.9079

βYYZ 0.0011 -0.0078

βXYZ -0.0001 0.0011

µ 5.2268 debye 5.1473 debye

α 62.0888 a.u(or) 9.1891X10-24esu 61.919 a.u (or) 9.1640X10-24esu

∆α 119.1898 a.u 118.57748 a.u

βtot 40.736787 a.u(or) 0.3519X10-30esu 40.20715 a.u (or) 0.3473X10-30esu

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D. MEP

Molecular elecstrostatic potential(MEP) characterized as the vital cooperation between the electrical charges of the molecule [68], it outlined the charge conveyance of the molecule. MEP graph is normally used to demonstrate this process and collaboration of the hydrogen holding of molecule [69], which relates with electronegativity, dipolemoment and chemical reactivity [70]. The electron acceptor and donor of the molecule is clarified by shading the sign of the MEP diagram [71]. The negative range of the molecule is solid in red shading, it is positive is in blue colour. Green, yellow are moderate. The order red>orange>yellow>green>blue explains the negativity of the molecule. The MEP graph gives us the physiochemical properties of molecule [72]. The MEP diagram of the title molecule is showed in figure 7.The electron density of this molecule lies between the -6.642eX10-2 to 6.642eX10-2. Among molecules the MEP shows that the oxygen atoms O10 and O8 occur in more negative regions. The approximate surface map value (smv) of this atoms respectively -0.043, -0.052. Two methyl groups carbon atoms has small variation in smv. The approximate smv of C11 is 0.018 and 0.038 for C15 atom. Blue and green indicate that C15 has a larger positive region than C11, Similarly the H7 atom has larger positive region than H9 atom. The hetrocyclic ring occurs in greenish area. This indicate that the ring region has more positive than the oxide group and while it is smaller than the methyl and hydrogen group.

E. Mulliken atomic charge Atomic behavior and Reactivity depends on atomic charges and charge exchange. Mulliken populace examination is

utilized to study the atomic charge in the molecule [73]. The difference between the MEP and the Mulliken atomic charge is that the Mulliken atomic charge indicates the net atomic populace in the molecule yet MEP Yield out of the particle [74]. The atomic charges affect dipolemoment, polarizability, electronic structure, vibrational spectra of the molecule [75] .

The Mulliken populace examination figured by the B3LYP technique are presented in Table 4 and figure 4. The Mulliken analysis clearly shows that, among the atoms, the N atoms (N1,N3), present in the ring structure and oxygen atoms (O8,O10) connected in the ring system has highest negative charge. All the hydrogen atoms including those in the methyl groups are positive charge with slight variation 0.4458-0.1862 for the 6-31+G(d) and 0.3430-0.0956 for 6-311++G(d,p) in the basis set. Especially hydrogen connected with the nitrogen atom in the ring has a greater positive charge. All the carbon atoms C2, C4, C5, C6 has the positive charge except the methyl group carbon atom C11, C15 which has a negative charge and that value is greater than that of other negatively charged atoms.

Table IV.

Mullikan atomic charge

Atom 6-31+G(d) 6-311++G(d,p) N1 -0.7051 -0.3749 C2 0.6363 0.36853 N3 -0.7059 -0.39673 C4 0.7263 0.13973 C5 0.8560 0.35673 C6 0.1317 0.38866 H7 0.4459 0.34305 O8 -0.5162 -0.34602 H9 0.4543 0.36645 O10 -0.5192 -0.32153 C11 -0.9115 -0.88369 H12 0.2385 0.18182 H13 0.1862 0.09563

Fig. 7. MEP diagream for 5,6dimethyl-2,4-(1h,3h )pyrimidinedione.

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H14 0.2385 0.18187 C15 -1.2493 -0.60185 H16 0.2349 0.17203 H17 0.2238 0.15800 H18 0.2348 0.17220

F. Vibrational assignment The 18 atoms containing molecule DMPMDN has 48 typical modes of vibrations, 33 inplane vibrations and lingering 15 out of plane vibrations and this is concurrence with C1 symmetry. The 48 vibrations are for the most part dynamic in the IR and Raman vibration spectra of the title molecule is noncentrosymmetric. The add up to vibrations were performed based on the trademark vibration of CH3, NH, C=O and hetrocycle ring modes. All qualities recorded alongside PED appear in Table V. PED qualities are figured by the VEDA program. The assignments in the light of the detailed writing and Gaussview representation to are presented.

Table V.

Experimental and Calculated Vibrational frequencies (cm-1), IR and Raman Intensities (kmmol-1 ),Vibrational assignment along with PED Value.

Mode Experimental Frequency

6-31+G(d) 6-311++G(d,p) Vibration assignment PED% Frequency Intensity Frequency Intensity

Ft-IR Raman scaled cal IR Raman Scaled cal IR Raman 1 3535 3545 3619 8.68 10.23 3590 3626 9.20 1.40 Ʋ N1 , H7 100

2 3428 3523 3596 7.71 11.08 3565 3601 8.32 1.53 Ʋ N3 , H9 100

3 3154 3122 3187 1.54 11.54 3133 3165 1.27 1.53 Ʋ C15 , H17 89

4 3142 3087 3151 2.01 8.01 3101 3132 1.78 1.06 Ʋ C11 , H13 81

5 3041 3104 1.26 17.84 3052 3083 1.27 2.45 Ʋ C11 , H12 Ʋ C11 , H14

50 50

6 2924 3028 3091 1.14 20.84 3042 3073 1.04 2.89 Ʋ C15 , H16 Ʋ C15 , H18

50 50

7 2910 2996 3058 2.53 48.62 3010 3040 2.19 7.46 Ʋ C11 , H12 Ʋ C11 , H13 Ʋ C11 , H14

43 14 43

8 2838 2982 3044 2.56 44.14 2997 3027 2.24 6.72 Ʋ C15 , H16 Ʋ C15 , H18

47 47

9 1766 1803 100 17.02 1778 1796 100 2.29 Ʋ O8 , C2 72

10 1714 1714 1750 75.52 48.18 1726 1743 74.92 6.18 Ʋ O10 , C4 78

11 1643 1644 1660 1695 11.17 34.81 1670 1687 12.40 5.76 Ʋ C5 , C6 66

N1

C2

N3

C4

C5

C6

H7

O8

H9

O10

C11

H12

H13

H14

C15H16

H17

H18

-1.0

-0.5

0.0

0.5

1.0

6-31+G(d) 6-311++G(d,p)

Fig. 8. Mullikan atomic charge of DMPMDN

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12 1535 1528 1492 1523 1.50 27.46 1494 1509 5.92 3.49 Β H7 , N1 , C2 Β H16 , C15 , H18

17 14

13 1482 1513 5.65 24.29 1479 1494 4.54 3.75 Β H12 , C11 , H14 Β H13 , C11, H12 Β H14 , C11 , H13

31 12 11

14 1499 1478 1509 1.61 12.34 1471 1486 1.48 1.49 Β H17 , C15 , H16 Β H18 , C15 , H17 Τ H17,C15,C6,N1

37 37 14

15 1492 1469 1500 7.16 7.72 1467 1482 3.65 0.65 Β H16 ,C15 , H18 Β H17 , C15 , H16 Β H18 , C15 , H17

23 13 13

16 1456 1466 1497 0.32 4.09 1457 1472 0.36 0.61 Τ H13 ,C11,C5, C6 Β H13 , C11, H12 Β H14 , C11 , H13

10 37 37

17 1429 1422 1452 1.03 20.17 1416 1430 2.12 2.28 Β H12 , C11 , H14 Β H13 , C11, H12 Β H14 , C11 , H13 Β H16, C15 , H18

31 16 16 21

18 1384 1363 1410 1439 10.76 4.28 1410 1424 16.59 0.14 Ʋ N1 , C2 Β H7 , N1 , C2

10 14

19 1331 1401 1430 7.82 15.67 1398 1412 1.83 1.74 Ʋ N1 , C2 Β H16 , C15 , H18

16 10

20 1313 1295 1383 1412 0.49 10.40 1391 1405 0.58 1.95 Β H9 , N3 , C4 68

21 1223 1208 1291 1318 4.52 17.91 1293 1306 4.63 2.39 Ʋ N3 , C2 Β C5 , C6, N1 Β H7 , N1 , C2

14 12 19

22 1196 1188 1200 1225 4.38 4.63 1200 1212 5.59 0.68 Ʋ N1 , C6 Ʋ C11 , C5

41 24

23 1134 1120 1171 1195 3.79 2.80 1171 1183 2.72 0.52 Ʋ N3 , C4 Ʋ C15 , C6 Ʋ C11 , C5

31 13 15

24 1044 1033 1114 1137 1.50 3.54 1116 1127 1.81 0.45 Τ H12,C11,C5,C6 Ʋ C15 , C6

15 16

25 965 925 1056 1078 0.00 0.41 1056 1067 0.01 0.15 Τ H13 ,C11,C5,C6 Τ H17, C15,C6 , N1

30 13

26 929 917 1041 1063 0.04 1.02 1040 1050 1.80 1.49 Τ H18 ,C15,C6, N1 Τ H13,C11 ,C5 , C6 Τ H17,C15,C6, N1

10 18 19

27 884 1038 1060 1.75 12.61 1039 1049 0.03 0.09 Τ H16,C15,C6,N1 Τ H18,C15,C6, N1 Ʋ N1 , C2

14 13 12

28 804 957 977 0.64 2.20 961 971 0.72 0.42 Ʋ N3 , C2 Τ H16, C15,C6,N1 Τ H18,C15,C6, N1 Ʋ N1 , C2

13 14 14 18

29 777 924 943 0.90 4.80 927 936 1.00 0.63 Β C2 , N1 , C6 Ʋ C5 , C6 Τ H12,C11,C5, C6 Τ H14 , C11,C5, C6 Ʋ C15 , C6

13 10 14 14 14

30 750 752 756 772 1.30 0.93 763 771 1.33 0.11 Β N3 , C2 , N1 Β C5 , C6, N1 Β C2 , N1 , C6 Ʋ C11 , C5

30 11 12 30

31 714 746 762 0.23 1.87 757 765 1.17 0.38 ϒ O10, N3 ,C5 ,C4 ϒ O8 , N1,N3 , C2

71 13

32 634 635 723 738 6.84 0.09 745 753 5.39 0.00 ϒ O8 ,N1 , N3 , C2

82

33 607 616 667 681 10.92 3.93 657 664 10.99 0.46 Τ H9,N3 ,C4, C5 85

34 567 613 626 0.24 7.13 622 628 0.26 0.87 β O8 , C2 , N3 Β O10 , C4 , N3

30 29

35 529 606 619 0.10 100.00 611 617 0.07 13.77 Β C4 , N3 , C2 Ʋ N3 , C2 Ʋ C15 , C6

20 16 13

36 526 561 573 3.60 0.06 555 561 1.57 0.02 Τ H7, N1 ,C2 , N3 63

37 476 510 521 1.28 17.97 515 520 1.33 2.42 Β C5 , C6, N1 Β C2 , N1 , C6 Ʋ C15 , C6

12 32 10

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38 469 460 504 515 4.17 8.75 505 510 5.57 0.90 ϒ C15,N1 ,C5 , C6 Τ H7, N1 , C2 , N3 Τ H17, C15,C6, N1

36 27 12

39 384 452 461 1.59 28.84 456 461 1.59 3.80 Β C4 , N3 , C2 Β N3 , C2 , N1 Β C5 , C6, N1 Ʋ C11 , C5

11 34 25 10

40 381 389 2.28 8.63 387 391 2.20 1.26 Ʋ N3 , C4 Β O8 , C2 , N3 Β O10 , C4 , N3 Β C4 , N3 , C2

10 28 26 12

41 316 332 339 0.33 10.56 334 337 0.27 1.37 Β C11 , C5 , C4 Β C15 , C6 , N1

32 45

42 303 309 0.23 2.57 306 309 0.25 0.35 Β C11 , C5 , C4 Β C15 , C6 , N1

40 20

43 192 300 306 0.06 1.33 297 300 0.05 0.47 ϒ C11,C6,C4 , C5 62

44 163 166 169 0.12 5.46 163 165 0.11 1.06 Τ C5,C6 , N1, C2 Τ C4, N3, C2 , N1 ϒ C15, N1,C5 , C6

48 10 24

45 141 144 0.11 12.29 136 137 0.12 1.31 Τ N3 , C2 , N1 , C6 Τ C5 , C6, N1, C2 Τ C4,N3 ,C2 , N1

23 12 55

46 101 103 0.00 6.60 98 99 0.01 0.92 Τ N3,C2 , N1 , C6 Τ C5 , C6, N1, C2 Τ C4, N3 ,C2 ,N1

47 19 23

47 72 74 0.01 10.29 60 61 0.02 9.44 Τ H13,C11, C5 , C6 Τ H16, C15,C6 , N1 Τ H18,C15 ,C6 , N1 Τ H17,C15,C6,N1

11 21 21 30

48 62 63 0.03 73.09 19 19 0.02 100 Τ H12, C11,C5, C6 Τ H14, C11,C5 , C6 Τ H13,C11,C5 , C6

23 23 19

Ʋ-stretching, B-Inplane bending, ϒ-Outplane bending,T-Ttorsional

Due to the anhormonicity, the ascertained frequencies are greater, when compared with vibrational frequencies figured at B3LYP in DFT strategy[76]. Scaling condition is utilized to lessen the variety among computed and experimental esteems which is made by various methods. current investigation has used following equation, C=wiyi/yi

2 Average C value is the scaling factor, wi is the experimental frequency, yi is the calculated frequency. The scaling

factor for the 6-31+G(d) basis set is 0.9196+0.06 and that the 6-311++G(d,p) basis set is 0.9300+0.06 correction, Calculated frequency values are correlated with the experimental frequency that’s called scaled frequency. In this work low PED value (below 10) and corresponding vibrational frequency are left out. On observed vibrational frequencies, It is seen that same group does not have the same accurate vibration frequency. It varies at very small amount of frequency value. Frequency value is dependent on the position of the molecules present in the structure[77]. But the molecular vibrational frequency is well within the ranges recorded in literature value. The comparison of other pyrimidinedione derivatives frequencies are shown in Table VI.

Table VI

Comparison of fundamental IR frequencies of different uracil bases (cm-1)

5,6DMPMDN M.Graindourze et al[77] Exp 6-31+G(d) 6-311++G(d,p) uracil 1-me-u 3-me-u 1,3-dime-u 5-me-u ν N1H 3535 3545 3590 3485 - 3480 - 3480 ν N3H 3428 3523 3565 3435 3429 - - 3434 ν C2O - 1766 1778 1764 1737 1745 1725 1768 ν C4O 1714 1714 1726 1706 1704 1698 1690 1712 ν C=C 1643 1660 1670 1643 1650 1648 1656 1684 δ N1H 1535 1492 1494 1472 - 1425 - 1472 δ N3H 1313 1383 1391 1389 1358 - - 1405 δ C2O - 613 622 537 514 540 537 541 δ C4O - 381 387 393 388 400 404 391 γ C4O 714 746 757 804 802 805 803 764 γ C2O 634 723 745 757 760 756 765 754

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γ N1H 526 561 555 551 - 555 - 545 γ N3H 607 667 657 662 659 - - 662

ν-stretching, δ-Inplane bending, γ-Outplane bending.

Fig. 9 FT-IR frequency comparison of pyrimidinedione derivatives

Fig. 10 FT-IR spectrum of DMPMDN Fig. 11 FT-Raman spectrum of DMPMDN

Experiment

6-311++G (d,p)

6-31+G (d)

400cm-1 4000cm-1

6-31+G(d)

Expriment

6-311++G(d,p)

3500cm-1 100cm-1

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For the task of electron donating the methyl group frequencies [78], Nine basics are related to every methyl group, symmetric and asymmetric stretching, two types of deformation. The C-H linear vibration in methyl group occurs in the range 3000 - 2900 cm-1 [76]. The DMPMDN molecule has two methyl molecules with ring structure. The methyl groups vibrational frequencies depend upon the connecting atom. For example, the stretching frequency of C-OCH3 is higher than that of C-CH3

[79]. The C-H vibration frequencies also differ in their position. Aromatic and aliphatic rings have different C-H stretching frequencies [80] In this investigation two sp3 methyl groups are connected with C5, C6 atoms which are placed in aromatic hetrocyle ring.K.Parimala et al [81] assigned asymmetric C-H stretching frequency band at 2943 cm-1,2896 cm-1 and,2940 cm-

1,2900 cm-1 respective in the FT-IR and FT-Raman. Other literature values assigned to the frequency band stretching for CH3 molecule is 2833cm-1, 2875cm-1, 2991cm-1 in FT-IR 2937, 2975 cm-1 in FT-Raman[76], 2967 cm-1, 2925 cm-1 in FT-IR, 2976 cm-1, 2930 cm-1 in FT-Raman(82). In this investigation all the vibration frequencies of the methyl group are in accordance with literature values those found in the characteristic group frequency as shown in Table 5 . These observation imply that the methyl group has played a considerable role in the change of frequencies [77]. The calculated values by B3LYP methods are fit with experimental values. NH stretching is in the region 3500-3400cm-1 [83] and theoretically assigned at 3490cm-1 and 3458cm-1 [84]. In this molecule, the couple of NH stretching modes are they differ in their assigned value because of the influence of C=O and methyl substitution [77]. Which is essentially a pure group modes [85,86-89]. All the vibration frequency modes of NH in DMPMDN are fit with the literature values. The carbonyl group stretching modes are recorded at 1600-1750cm-1 [90] For the title molecule,the carbonyl stretching modes are show in table 5 .they are good agreement with this expected values. C= C absorbs strongly at 1600-1500cm-1 in pyrimidines and in the C-N absorption range at 1520-957 cm-1 (IR),1164-935cm-1(theoretical) [91]. The reported values of the current investigation are correlated with the literature values.

V.CONCLUSION FT-IR and FT-Raman spectrum of DMPMDN molecule was recorded and studied experimentally. The density functional theory calculation was conducted on B3LYP/6-31+G(d) and B3LYP/6-311++G(d,p) basis sets. The HOMO and LUMO analyze were used to determine the charge transfer within the molecule. Molecular electrostatic potential was studied by DFT/B3LYP method and analyzed. The first order hyperpolarizability of the title compound is calculated at 0.3519X10-30esu, 0.3473 X10-30esu with respect to B3LYP/6-31+G(d), 6-311++G(d,p) basis sets. This result indicates the DMPMDN molecule and its derivatives are an attractive object for future studies of Nonlinear optical properties. The comparison study of DMPMDN with its derivatives revealed that the methyl group substitution made a small variation in geometrical optimyzation and vibrational assignment.

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