Molecular geometry, NBO analysis, Hyperpolarizability and HOMO-LUMO energies of 2-azido-1-phenylethanone using Quantum chemical calculations

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ScienceDirect Materials Today: Proceedings 3 (2016) 3761–3769

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ICMRA 2016

Molecular geometry, NBO analysis, Hyperpolarizability and HOMO-LUMO energies of 2-azido-1-phenylethanone using Quantum chemical calculations J. Prashantha, G. Ramesha, J. Laxman Naika, Jai Kishan Ojhab and B. Venkatram Reddya* a Department of Physics, Kakatiya University, Warangal - 506009, Telangana, India Dept. of Physics, Govt. Degree & P.G. College, Mancherial - 504208, Adilabad, Telangana, India

b

Abstract

The Fourier Transform Infrared (FTIR) spectrum of 2-azido-1-phenylethanone (APE) has been recorded in the range 4000-400 cm-1 respectively. The optimized geometry of the molecule has been computed by evaluating the torsional potential energy as a function of angle of rotation about the interlinking bonds of APE using quantum chemical calculations. These calculations were carried out using density functional theory (DFT) employing B3LYP functional with 6-311++G(d,p) basis set. Stability of the molecule arising from hyper conjugative interactions, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The values of dipole moment, polarizability and hyperpolarizability were computed to determine the NLO behaviour of the molecule under study. The HOMO and LUMO energies were also evaluated for this molecule to demonstrate the chemical stability. © 2016 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of International conference on materials research and applications-2016. Keywords: 2-Azido-1-phenylethanone; FTIR spectrum; DFT; Molecular geometry; Hyperpolarizability; NBO analysis; HOMO-LUMO

1. Introduction Azide is the anion with the formula N3− which is a conjugate base of hydrajoic acid (HN 3) and is isoelectronic with CO2 and N2O. It is also a functional group in organic chemistry, RN 3 [1]. Organic azides represent a unique substance class, which is able to undergo a multitude of reactions used for a variety of applications in industry [2]. They are versatile starting materials for the synthesis of a variety of nitrogen-containing compounds that attracts _____________________________________________________________________________________________ *Corresponding author E-mail address: [email protected] (B. Venkatram Reddy)

2214-7853© 2016 Elsevier Ltd. All rights reserved. Selection and Peer-review under responsibility of International conference on materials research and applications-2016.

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attention of both organic and inorganic chemists. The first organic azide (phenyl azide) was synthesized by P. Grieß in 1864 [3, 4]. It followed the discovery of hydrogen azide and the Curtius rearrangement of acyl azides to the corresponding isocyanates by T. Curtius from 1890 to 1894 [5]. The organic azides received considerable attention in the 1950s and 1960s with new applications in the chemistry of the acyl, aryl, and alkyl azides [6, 7]. Organic azides are used for the synthesis of heterocycles (triazoles, tetrazoles, aziridines), as blowing agents, and functional groups in pharmaceuticals e.g. azidonucleosides for the treatment of AIDS [8]. The chemistry of azides has been reviewed several times; some of these overviews focus only on some special subclasses of azides [9]. The organic azides were considered by inorganic chemists as readily accessible substrates for the preparation of nitrene (imido) complexes [10]. The dominant application of azides is as a propellant in air bags. Hence, experimental and theoretical investigation of organic azides gained importance in recent years. A variety of experimental methods and techniques have been used for their structural characterization. These include IR, NMR, microwave spectroscopy, electron diffraction, mass spectrometry and ab initio quantum chemical calculations [11-16]. Rocha et al carried out the kinetic resolutions of ()--azidophenylethanols and synthesized by immobilized Candida Antarctica lipase [17]. From the above, it is clear that the study of molecular dynamics of 2-azido-1-phenylethanone (APE) is yet to appear in literature. Hence, a systematic investigation is carried out for this molecule using quantum chemical calculations by density functional theory (DFT) employing B3LYP functional with 6-311++G(d,p) basis set. The purpose of this investigation is: 1. To record FTIR spectrum of APE to get complete information on their vibrational frequencies. 2. To make DFT calculations of this molecule in order to (i) identify most stable rotational isomer in the ground state and optimize its geometry, (ii) make the NBO analysis to understand molecular structure by studying the interactions between the localized bonding and anti-bonding orbitals, (iii) obtain the values of polarizability and first order hyper polarizability to study the NLO behaviour, (iv) evaluate HOMO and LUMO energies to know the chemical stability of the molecule.

2. Spectral measurements The molecule 2-azido-1-phenylethanone was obtained from TCI Chemical Company, Japan and used as such for the spectral measurements. The room temperature FTIR spectrum of the molecule was recorded using Thermo Nicolet Nexus 670 spectrometer employing KBr optics in 4000-400 cm-1 region with a resolution of 2.0 cm-1.

3. Quantum chemical calculations 3.1. Molecular geometry The quantum chemical calculations of APE were carried out with Becke’s three parameter hybrid functional [18] combined with Lee-Yang-Parr correlation functional [19] employing 6-311++G(d,p) basis set. The starting point for the calculations in this type of study is to determine the most stable conformer for the molecule under investigation. Hence, the molecule was subjected to a rigorous conformational analysis, wherein torsional potential energy was computed as a function of angle of rotation around the bonds among phenyl, azide and ethanone of this molecule using Gaussian 09w software package [20] implemented on Pentium-V (3.2 GHz) Workstation. The optimized geometry was obtained by solving self-consistent field equation iteratively and the global minimum energy was found at -548.6182 Hartree for this molecule. Subsequent calculations were performed with this optimized structure shown in Fig. 1, which contains numbering of atoms also. As per the computations, the molecule APE possesses C1 point group symmetry and optimized structure shown in Fig. 1. For plotting simulated IR spectrum, a pure Lorentzian band shape was used with a full width at half maximum (FWHM) 0f 10 cm -1. The optimized structure parameters namely bond lengths, bond angles and torsional angles of APE in its most stable conformation were presented in Table 1. The experimental and simulated FTIR spectra are presented in Fig. 2. 3.2. Natural bond orbital (NBO) analysis Natural Bond Orbitals (NBO) are localized few-centre orbitals that describe the Lewis-like molecular bonding pattern of electron pairs (or of individual electrons in the open-shell case) in optimally compact form. The NBO

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analysis provides a description of the structure of a conformer by a set of localized bonding and anti-bonding orbitals; and Rydberg extra valence orbitals. It is used to find the interaction between the bond orbitals, electron

Fig.1. Optimized molecular structure with numbering of atoms

Fig. 2. FTIR spectrum of APE: a) Observed, (b) Simulated with DFT/B3LYP/6-311++G(d,p)

Table 1: Optimized geometrical parameters of APE delocalization, bond bending effect, intramolecular charge transfer (ICT) and identification of hydrogen bonding [21]. In C1-C2 C1-C2-C3 120.224 C1-C3-C3-C4 0.0 recent years, the charge delocalization C2-C3 C2-C3-C4 120.091 C2-C3-C4-C5 0.0 patterns and the chemical reactivity of C3-C4 C3-C4-C5 120.044 C3-C4-CC6 0.0 polyatomic molecules have been focused C4-C5 C4-C5-C6 119.990 C6-C1-C2-H7 179.0 widely. The information about the charge C5-C6 C1-C2-H7 120.408 C1-C2-C3-H8 -180.0 delocalization and the chemical reactivity is C6-C1 C2-C3-H8 119.796 C2-C3-C4-H9 -180.0 being helpful to the pharmacists to design C2-H7 C3-C4-H9 119.961 C3-C4-C5-H10 -180.0 new type drugs. The natural bond orbital C3-H8 C4-C5-H10 120.054 C4-C5-C6-H11 - 179.0 (NBO) analysis is an effective tool for the C4-H9 C5-C6-H11 121.064 C5-C6-C1-C12 -178.0 elucidation of residual resonance C5-H10 C6-C1-C12 117.958 C2-C1-C12-O13 -171.0 delocalization effects of a molecule and it C6-H11 C1-C12-O13 121.800 C6-C1-C12-C14 -176.0 also illustrates the deciphering of the C1-C12 C1-C12-C14 120.113 C1-C12-C14-H15 177.0 molecular wave function in terms of Lewis C12-O13 C12-C14-H15 106.645 C1-C12-C14-H16 -65.0 structure, charge, bond order, bond type, C12-C14 C12-C14-H16 109.335 C1-C12-C14-N17 56.0 hybridization, resonance, donor-acceptor C14-H15 C12-C14-N17 110.594 C12-C14-N17-N18 156.0 C14-H16 C14-N17-N18 115.665 C14-N17-N18-N19 -178.0 interaction, etc [22]. In the NBO analysis C14-N17 N17-N18-N19 173.492 O13-C12-C14-N17 0.0 [23- 25], the electron wave functions are N17-N18 H16-C14-H15 109.243 * * interpreted in terms of a set of occupied N18-N19 H15-C14-N17 109.243 * * Lewis type (bond or lone pair) and a set of * O13-C12-C14 118.019 * * unoccupied non-Lewis (anti-bond or * H16-C14-N17 109.783 * * Rydberg) localized NBO orbitals. The delocalization of electron density (ED) between these orbitals corresponds to a stabilizing donor acceptor interaction. Second order perturbation theory has been employed to evaluate the stabilization energies of all possible interactions between donor and acceptor orbitals in the NBO basis. The interaction results in a loss of occupancy from the localized NBO of the idealized Lewis structure into an empty non-Lewis orbital. The delocalization effects (or donor acceptor charge transfers) can be estimated from the off-diagonal elements of the Fock matrix in the NBO basis. Bond

Bond length length (Å) (in Å) Å) 1.401 1.392 1.393 1.396 1.388 1.403 1.081 1.083 1.084 1.084 1.083 1.491 1.215 1.534 1.091 1.098 1.481 1.229 1.134 * *

Bond angle

Value 0 (in ) (in )

Torsional angle

Value 0 (in (in ) )

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The natural bond orbital (NBO) calculations were performed using NBO 3.1 program [26] as implemented in the Gaussian09W software at the DFT/B3LYP level using 6-311++G(d,p) basis set in order to understand various second order interactions between the filled orbitals of one subsystem and vacant orbitals of another subsystem. The output obtained by second order perturbation theory is used for identifying the significant delocalization effects. The strength of these delocalization interactions E(2) are estimated by the equation [23, 25] E(2) = ΔEij = where qi is the donor orbital occupancy, Ei and Ej are the diagonal elements; and Fij is the off-diagonal NBO Fock matrix element. The larger the E(2) value, the more intensive is the interaction between electron donors and acceptors, i.e. the more electron donating tendency from electron donors to acceptors and greater the extent of conjugation of the whole system. The possible intensive interactions between donors and acceptors in the molecule APE are presented in Table 2. The molecular interaction is formed by the orbital overlap between σ(C-C) and σ*(C-C) bond orbital which results in intra-molecular charge transfer (ICT) causing stabilization of the molecule. The large interaction energy value is the indicator of the weakening the respective bonds. The strong intra-molecular hyper conjugate interaction energy between σ and σ* electrons was found as 4.05 and 2.85 Kcal/mol due to interaction of σ(C1-C2) → σ*(C1-C6,C2-C3), respectively in APE. The inter molecular hyper conjugative interaction energies due to σ(C2C3) → σ*(C1-C2) and σ(C3-C4) → σ*(C2-C3) are obtained as 3.19 and 2.38 Kcal/mol, respectively. The calculated stabilization energies due to π electron delocalization around a bond that is distributed to π* anti-bonding orbitals and the computed interaction energies between σ→ σ* orbitals for the molecule can be seen from Table 2. The stabilization energies due to charge transfer from lone pair of Oxygen and Nitrogen to various other bonds that elongate and weakening the bonds in this molecule can also be observed from this table.

Table 2: The Second-order perturbation energies E(2) (in Kcal/mol) corresponding to the important charge transfer interactions (donor-acceptor) in APE NBO(i)

Type

ED/e

NBO(j)

Type

ED/e

E(2)a

C1-C2

σ

1.97521

π

1.63452

C1-C6

σ

1.97335

C1-C12

σ

1.97822

C2-C3

σ

1.97919

C1-C6 C1-C12 C2-C3 C2-H7 C3-H8 C6-H11 C12-O13 C3-C4 C5-C6 C12-O13 C1-C2 C1-C12 C2-H7 C5-C6 C6-H10 C12-C14 C1-C2 C1-C6 C2-C3 C5-C6 C12-O13 C1-C2 C1-C12 C2-H7 C3-H8

σ* σ* σ* σ* σ* σ* σ* π* π* π* σ* σ* σ* σ* σ* σ* σ* σ* σ* σ* σ* σ* σ* σ* σ*

0.02281 0.06475 0.01585 0.01438 0.01375 0.01444 0.00981 0.31720 0.28177 0.12669 0.02328 0.06475 0.01438 0.01472 0.01402 0.06297 0.02328 0.02281 0.01585 0.01472 0.00981 0.02328 0.06475 0.01438 0.01373

4.05 1.68 2.85 1.02 2.22 2.08 1.82 18.10 20.03 19.49 3.98 1.86 2.50 2.66 2.30 2.08 2.17 1.84 2.11 2.29 1.03 3.19 1.05 2.73 2.29

E(j)-E(i)b (a.u.) 1.26 1.14 1.28 1.15 1.14 1.16 1.30 0.28 0.29 0.27 1.26 1.13 1.14 1.28 1.14 1.05 1.23 1.23 1.24 1.25 1.26 1.27 1.14 1.15 1.15

F (i, j)c (a.u.) 0.064 0.039 0.054 0.031 0.045 0.044 0.044 0.065 0.069 0.069 0.063 0.041 0.048 0.052 0.046 0.042 0.046 0.042 0.046 0.048 0.032 0.057 0.056 0.031 0.029

Venkatram Reddy et al, Materials Today: Proceedings 3 (2016) 3761–3769 C2-H7

σ

1.97793

C3-C4

σ

1.98321

π

1.64517

C3-H8

σ

1.98026

C4-C5

σ

1.98019

C4-H9

σ

1.98064

C5-C6

σ

1.97974

π

1.65190

C5-H10

σ

1.98037

C6-H11 C12-O13

σ σ

1.97823 1.99472

π

1.97090

C12-C14

σ

1.98114

C14-H15

σ

1.98491

C14-H16

σ

1.96907

C14-N17

σ

1.93450

N18-N19

σ π

1.99206 1.99585

δ

1.99530

LP(1)O13

1.97907

LP(2)O13

1.88910

LP(1)N17

1.97201

LP(2)N17

1.79491

C1-C2 C2-C3 C3-H8 C2-C3 C3-H8 C4-H10 C1-C2 C5-C6 C1-C2 C4-C5 C3-C4 C3-H8 C5-C6 C6-H11 C2-C3 C5-C6 C1-C6 C1-C12 C4-C5 C4-H9 C6-H11 C1-C2 C3-C4 C1-C6 C3-C4 C1-C2 C1-C2 C1-C12 C14-H16 C14-N17 C1-C2 C1-C6 N17-N18 LP N17 C1-C12 LPN17 C12-O13 C12-O13 C12-O13 C12-O13 N18-N19 N18-N19 N18-N19 N17-N18 LPN17 N18-N19 C14-N17 N17-N18 C1-C12 C12-C14 C1-C12 C12-C14 C12-C14 C14-H15 N18-N19 N18-N19 C14-C15 C14-H16 N18-N19

σ* σ* σ* σ* σ* σ* π* π* σ* σ* σ* σ* σ* σ* σ* σ* σ* σ* σ* σ* σ* π* π* σ* σ* σ* σ* σ* σ* σ* π* σ* σ* π* σ* π* σ* π* σ* π* σ* δ* σ* σ* π* π* σ* σ* σ* σ* σ* σ* σ* σ* σ* δ* σ* σ* π*

0.02328 0.01585 0.01373 0.01585 0.01373 0.01402 0.37092 0.28177 0.02328 0.01661 0.01617 0.0373 0.01472 0.01444 0.01585 0.01472 0.02281 0.06475 0.01661 0.01339 0.01444 0.37092 0.31720 0.02281 0.01617 0.02328 0.02328 0.06475 0.0675 0.02145 0.02328 0.02281 0.02665 0.31720 0.06475 0.31720 0.00981 0.12669 0.00981 0.12669 0.03464 0.20305 0.03464 0.02665 0.31720 0.47927 0.02145 0.02445 0.06475 0.06297 0.06475 0.06297 0.06297 0.01519 0.03464 0.03464 0.01519 0.02239 0.44927

4.35 3.71 2.74 2.38 2.53 2.34 22.64 17.49 3.86 3.69 2.55 2.39 2.72 2.40 3.83 3.66 3.03 2.84 2.69 2.28 1.04 18.78 21.87 3.80 3.65 4.65 1.35 1.31 4.73 1.63 2.06 2.22 2.13 1.03 3.61 3.09 1.41 4.30 1.01 1.53 4.07 10.22 5.75 5.77 10.41 4.26 4.74 1.82 1.97 1.19 18.17 20.70 1.13 1.71 12.84 13.17 2.61 6.60 132.54

1.09 1.10 0.97 1.28 1.15 1.15 0.28 0.29 1.08 1.09 1.28 1.14 1.29 1.16 1.10 1.11 1.27 1.14 1.28 1.15 1.16 0.28 0.28 1.08 1.09 1.08 1.65 1.52 0.41 0.75 0.69 1.21 1.19 0.30 0.97 0.30 1.13 0.55 1.31 0.73 1.45 0.75 1.81 1.72 0.23 0.44 0.81 1.06 1.13 1.05 0.71 0.63 0.78 0.81 1.16 0.46 0.61 0.60 0.20

3765 0.025 0.025 0.021 0.053 0.029 0.046 0.072 0.064 0.058 0.057 0.051 0.047 0.053 0.047 0.058 0.057 0.055 0.051 0.052 0.046 0.031 0.065 0.070 0.057 0.056 0.063 0.042 0.040 0.043 0.031 0.034 0.046 0.045 0.031 0.054 0.053 0.036 0.045 0.033 0.030 0.069 0.081 0.092 0.089 0.087 0.044 0.056 0.039 0.043 0.032 0.103 0.103 0.028 0.035 0.114 0.070 0.041 0.064 0.147

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16.08

1.16

0.122

a

3.3. Polarizability and first order hyperpolarizability Non-linear optical (NLO) materials find applications in wide area like telecommunications, signal processing and optical inter-connections, in providing key functions of frequency shifting, optical switching, optical logic and optical memory [27-29]. NLO material gives rise to new fields when interacts with the incident electromagnetic field that undergoes a change in phase, frequency, amplitude or other propagation characteristics [30]. NLO behaviour of a material can be studied by measuring the total dipole moment and first order hyperpolarizability. The non-linear optical response of an isolated molecule in an electric field can be expressed as a Taylor series expansion of the total dipole moment, t, induced by the field: t = 0 + ijEj + ijk EjEk +.... where, 0 is the permanent dipole moment, ij are the components of polarizability,  ijk are the components of the first order hyperpolarizability. Table 3: Values of dipole moment, µt (in Debye); polarizability, αt (in 1.4818 x 10-25 cm3); hyperpolarizability, βt (in 10-30 cm5/e.s.u); and frontier molecular orbital parameters of APE Type of component βxxx βxxy βxyy βyyy βxxz βxyz βyyz βxzz βyzz βzzz βt µx µy µz µt xx xy yy  xz yz zz αt ∆α

Value with B3LYP/6-311++G (d,p) 410.9477 112.5004 93.1804 33.8803 24.3064 26.1490 26.4635 -65.1224 -8.9509 81.1724 478.5622 au (or) 4.1342×10-30 cm5/esu -1.9513 -1.7735 1.3751 2.9739 170.8144 1.2969 120.5818 5.0828 -4.8812 72.1655 121.1872 85.4372

Frontier molecular orbital parameter HOMO energy LUMO energy Frontier molecular orbital energy gap Ionization energy (I) Electron affinity (A) Global hardness (η) Chemical potential (µ) Global electrophilicity power (ω)

Value(in eV) -0.30351 -0.22303 0.08048 0.30351 0.22303 0.04024 -0.26327 0.86122

The first order hyperpolarizability is a third rank tensor. Hence, it contains 27 components represented by a 3 x 3 x 3 matrix. Due to Klienman symmetry [31], the 27 components get reduced to 10 components (xyy = yxy = yyx= yyz = yzy = zyy;….. Similarly other permutation of x, y, z subscripts also take same value). These components are: xxx , xxy , xyy, yyy , xxz , xyz, yyz , xzz, yzz , zzz They can be calculated using the following equation [32]: i = iii + (1/3) i≠j(ijj + jij + jji) The total static dipole moment (t), the isotropic (or average) linear polarizability (t), the anisotropy of

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polarizability (), and the mean first order hyperpolarizability (t), using the x, y, z components are defined as: t = (x2 + y2 + z2)1/2 t = (xx + yy+ zz)/3  = 2-1/2 [(xx - yy)2 + (yy - zz)2 + (zz - xx)2 + 6xx2 ]1/2 t = (x2 + y2 + z2)1/2 where, x = xxx + xyy + xzz y = yyy + xxy + yzz z = zzz + xxz + yyz The value of hyperpolarizabilty of a molecule is a measure of NLO activity. It is associated with intramolecular charge transfer that arises from the electron cloud movement through -conjugated framework of electrons [33]. Consequently, DFT has been employed to study the NLO behavior of some materials [34, 35] in our earlier work. DFT/B3LYP/6-311++G(d,p) level of theory has been used to compute the total molecular dipole moment (t) and its components; total molecular polarizability (t) and its components; and first order hyperpolarizability (t) and its components. The results are reported in Table 3. The NLO behaviour of a molecule is normally determined by comparing its total molecular dipole moment (t) and mean first order hyperpolarizability with corresponding values of Urea for which t is 1.3732 Debye and t is 0.3728 x 10-30 cm5/esu. For the molecule APE, the value of t is 2.9739 Debye and t is 4.1342 x10 -30 cm5/esu. From the above values, it can be seen that the values of t and t of APE are greater than that of Urea. Hence, it demonstrates that APE exhibits NLO properties. 3.4. Frontier molecular orbitals Molecular orbitals and their properties are used to explain several types of reaction and for predicting the most reactive position in conjugated systems [36]. The highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) are the most important orbitals in a molecule. The eigen values of HOMO and LUMO and their energy gap reflect the biological activity of the molecule. A molecule having a small frontier orbitals gap is more polarizable and is generally associated with a high chemical reactivity and low kinetic stability [37-39]. The HOMO energy characterizes the ability of electron giving, where as the LUMO characterizes the ability of electron accepting. On the other hand LUMO energy is directly related to electron affinity [40, 41]. Fig. 3. Frontier molecular orbitals of APE

For understanding various aspects of pharmacological sciences including drug design and the possible ecotoxicological characteristics of the drug molecules, several new chemical reactivity descriptors have been proposed. Conceptual DFT based descriptors have helped in many ways to understand the structure of the molecules and their reactivity by calculating the chemical potential, global hardness and electrophilicity. Using the HOMO and LUMO orbital energies, the ionization energy(I) = -EHOMO; electron affinity (A) = -ELUMO; global hardness (η) = (EHOMO+ ELUMO)/2 and chemical potential (µ) = (EHOMO+ELUMO)/2 can be determined [42]. Parr et al. [43] proposed the global electrophilicity power of a ligand as ω = µ 2/2η. The frontier molecular orbital parameters, computed with DFT/B3LYP/6-311++G(d,p) level of theory, for APE are presented in Table 3 and illustrated in Fig. 3. It is seen that the chemical potential of the titled molecule is negative which demonstrates that the compound is stable [44]. The energy band gap between HOMO and LUMO shows of the molecule APE is low which demonstrates that the chemical reactivity is high since it is energetically favorable to add electron to high-lying LUMO by extracting electrons from low-lying HOMO [45, 46].

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Conclusion Geometry optimization has yielded structure parameters and the molecule APE assumed C1 point group symmetry. The NBO analysis was made to understand the molecular structure by studying the interaction between the localized bonding and anti-bonding orbitals; electron delocalization and intra-molecular charge transfer (ICT). The study of dipole moment and hyper polarizability demonstrates that the molecule APE exhibits NLO property, and hence it may be a potential applicant in the development of NLO materials. The small band gap between the frontier molecular orbitals demonstrates that the molecule APE has high chemical reactivity. Acknowledgement The financial support from University Grants Commission, New Delhi, India (F. No. 41-960/2012 (SR), dt.26/7/2012) is gratefully acknowledged. The authors are thankful to the Sophisticated Analytical Instrumentation Facility (SAIF), IIT Madras, Chennai, India for the spectral measurements. References [1] S. Bräse, C. Gil, K. Knepper, V. Zimmermann, Angew. Chem. 117 (2005) 5320-5374; Angew. Chem. Int. Ed. 44 (2005) 5188-5240. [2] S. Bräse, K. Banert, Organic Azides, Syntheses and Applications, John Wiley & Sons Ltd., Chichester, 2010. [3] a) E. F. V. Scriven, K. Turnbull, Chem. Rev., 88 (1988) 297-368; b) G. L’abbé, Chem. Rev. 69 (1969) 345-363. [4] a) P. Grieß, Philos. Trans. R. Soc. London, 13 (1964) 375-384; b) P. Grieß, Justus Liebigs Ann. Chem., 135 (1865) 121. [5] a) T. Curtius, Ber. Dtsch. Chem. Ges., 23 (1890) 3023-3033; b) T. Curtius, J. Prakt. Chem., 50 (1894) 275-294. [6] P. A. S. Smith, Org. React. 3 (1946) 337-349. [7] J. H. Boyer, F. C. Canter, Chem. Rev. 54 (1954) 1-57. [8] T. S. Lin, W. H. Prusoff, J. Med. Chem. 21 (1978) 109-112. [9] T. Patonay, K. Konya and E. Juhasz-Toth, Chem. Soc. Rev. 40 (2011) 2797. [10] D. E. Wigley, K. D. In Karlin, Ed, Progress in Inorganic Chemistry, Vol. 42, Wiley, New York, p 239, 1994. [11] M. Machado and J. M. Kenny, Rubber Chem. Tech. 74 (2001)198. [12] (a) D. Magan Kanjia, J. Manson, I. A. Stenhouse, R. E. Banks and N. D. Venayak, J. Chem. Soc., Perkin Trans. 1 (1981) 975, (b) H. Dahn, V. V. Toan and P. Pechy, Magn. Reson. Chem. 33 (2001) 686. [13] N. Heineking and M. C. L. Z. Gerry, Naturforschung A 44 (1989) 669. [14] R. Haist, H. G. Mack, C. O. Della Vedova, E. H. Cutin and H. Oberhammer, J. Mol. Struct., 445 (2001) 197. [15] R. T. M. Fraser, N. C. Paul and M. J. Bagley, Org. Mass Spectrom. 7 (2001) 83. [16] (a) S. Sklenak, A. Gatial and S. Biskupic, J. Mol. Struct. (Theochem) 397 (2001) 249, (b) L. Parkanyi and G. Besenyei, J. Mol. Struct. 691 (2001) 97. [17] L. C. Rocha, I. G. Rosset, G. Z. Melgar, C. Raminelli, A. L. M. Porto and A. H. Jeller, J. Braz. Chem. Soc. Vol. 24. 9 (2013)1427 [18] A. D. Becke, J. Chem. Phys. 98 (1993) 5648. [19] C. Lee, W. Yang and R. G. Parr, Phys. Rev. B 37 (1988) 785. [20] M. J. Frisch, G. W. Trucks et al, Gaussian, Inc., Wallingford CT, 2009. [21] L. Rajith, A. K. Jissy, K. G. Kumar, A. Datta, J. Phys. Chem. C, 115 (2011) 21858- 21864 [22] E. D. Glendening, C. R. Landis and F. Weinhold, WIREs Comput Mol Sci, 2 (2012) 1. [23] A. E. Reed, L. A. Curtiss, F. Weinhold, Chem. Rev., 88 (1988) 899-926. [24] J. P. Foster, F. Weinhold, J. Am. Chem. Soc., 102 (1980) 7211–7218. [25] J. Chocholousova, V. V. Spirko, P. Hobza, Phys. Chem. Chem. Phys. 6 (2004) 37-41. [26] E. D. Glendening, A. E. Reed, J. E. Carpenter, F. Weinhold, NBO Version 3.1, TCI, University of Wisconsin, Madison, 1998. [27] V. M. Geskin, C. Lambert, J. L. Bredas, J. Am. Chem. Soc., 125 ( 2004) 15651-15658. [28] M. Nakano, H. Fujita, M. Takahata, K. Yamaguchi, J. Am. Chem. Soc., 124 (2002) 9648-9655. [29] D. Sajan, H. Joe, V. S. Jayakumar, J. Zaleski, J. Mol. Struct., 785 (2006) 43-53. [30] Y. X. Sun, Q. L. Hao, W. X. Wei, Z. X. Yu, L. D. Lu, X. Wang, Y. S. Wang, J. Mol. Struct: THEOCHEM, 904 (2009) 74-82. [31] D. A. Klienman, Phys. Rev., 1962, 126, 1977. [32] R. Zhang, B. Du, G. Sun, Y. X. Sun, Spectrochim. Acta A, 2002, 75, 1115. [31] M. Arivazhagan, S. Jeyavijayan, Spectrochim. Acta A. 79 (2011) 376-383. [32] N. Prabavathi, N. Senthil Nayaki, B. Venkatram Reddy, Spectrochim. Acta A, 136 (2015) 1134-1148. [33] J. Laxman Naik, B. Venkatram Reddy, N. Prabavathi, J. Molecular Structure, 1100 (2015) 43-58. [34] N. Choudhary, S. Bee, A. Gupta, P. Tandon, Comp. Theor. Chem. 1016 (2013) 8-21. [35] N. Sinha, O. Prasad, V. Naryan, S.R. Shukla, J. Mol. Simul. 37 (2011) 153-163. [36] D.F.V. Lewis, C. Loannides, D.V. Parke, Xenobiotica 24 (1994) 401-408. [37] D. Koser, C. Albayrak, Spectrochim. Acta 78 (2011)160-167. [38] G. Gece, Corros. Sci. 50 (2008). 2981-2992. [39] K. Fukui, Science 218 (1982) 747-754. [40] T.A. Koopmans, Phsics 1 (1993) 104-113. [41] R.J. Parr, L.V. Szentpaly, S. Liu, J. Am. Chem. Soc. 121(1999) 1922-1924.

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