Proceedings of the 9th WSEAS International Conference on APPLIED COMPUTER SCIENCE

A Computational Study on Structural, Electronic and Nonlinear Optical Properties of Furylpyridine Molecules
MEHMET BAHAT, EMRE YRK Physics Department Gazi University Science and Art Faculty, 06500, Ankara TURKEY bahat@gazi.edu.tr
Abstract: - Furylpyridines are composite molecules having two subsystems as pyridine and furan molecules connected together by a single bond. The constituting subsystems pyridine and furan molecules can rotate along the single bond linking them together. Firstly, the equilibrium geometries of furylpyridines have been obtained through geometry optimization using density functional theory at the B3LYP/ 6-311++G(2d,p) level. The conformational analysis of six compounds have been studied as a function of inter-rings C-C dihedral angle varying between 0 and 180o with a step of 15o at the B3LYP/ 6-311++G(2d,p) level of theory. The study of linear and nonlinear optical properties of molecules are important for design and construction of new optical devices that might be useful in electronic communication and photonic treatments. Therefore, we have calculated releated physical quantities such as dipole moments, HOMO-LUMO energies, molecular static polarizabilities, polarizability anisotropy, and first hyperpolarizabilities at the optimized geometries. Key-Words: - Furylpyridine, Density functional theory, conformational analysis, B3LYP, Nonlinear optical properties

1 Introduction
-conjugated polymers with electronic and optical functionalities have been attracting much attention. Especially, -conjugated polymers consisting of sixmembered, and five-membered aromatic units such as benzene, pyridine, thiophene and pyrrole units have been attracting strong interest [1,2]. Also their derivatives constitute an important class among conjugated polymeric materials are promising for electronic and nonlinear optical technology [3]. When two aromatic -conjugated units connected together by a single bond they produce new composite molecules such as biphenyl, bithiophene, phenylthiophene etc. The constituting molecules can rotate around the single bond linking them together. Therefore the evaluation of single- bond torsional potentials in organic molecules is critical for understanding the structure and relative energetics of the low- lying rotational isomers. The quantitative evaluation of torsional potentials in conjugated systems poses particularly difficult problems from the experimental as well as from theoretical side. For most of the conjugated molecules listed above, either experimental or theoretical investigations have been reported addressing the torsional potential of biphenyl [5,6], 2,2- bithiopene [7], 2,2- bipyridine [5,8], bifuran [9].

A detailed review of literature can be found in these references. In addition to torsional conformation behaviour, the study of electronic, linear and nonlinear optical properties of molecules are important for design and construction of new electronic and optical devices. Therefore, a number of experimental and especially theoretical investigations in nonlinear optical properties have been published for biphenyl [10,11], 2,2- bithiopene [7], phenylpyridines [12]. Furylpyridines are composite molecules having two subsystems pyridine and furan molecules connected together by a single bond. As mentioned above, the constituting subsystems pyridine and furan molecules can rotate freely around the single bond linking them together. A little study has been devoted to furylpyridines in the literature. The synthesis and some physical characterizations of furylpyridines have been studied by several authors [13,14,15]. The furylpyridine based structures have interested in the synthesis and function of biological molecules [16]. Theoretically, some physical properties of furylpyridines and their derivatives have been investigated using semiempirical AM1, PM3 and MNDO quantum-chemical methods [17].

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Proceedings of the 9th WSEAS International Conference on APPLIED COMPUTER SCIENCE

In principle, theoretical computations can provide a detailed description of the whole torsional potential, electronic and nonlinear optical properties. For conformational analysis of biphenyl, a detailed review of literature can be found in a paper by Grein[6]. DFT methods somewhat overestimate the delocalisation energy[18], and therefore, produce slightly more planar structures. The dipole polarizabilities of benzene, furan and thiophene were done at the B3LYP/6-311++G(2d,p) level of theory by Hinchliffe et. al. [19]. Their results lie within experimental error ranges. One of important physical quantity in molecular electronic technology is electronic energy (band) gap. The molecular orbital calculations can be perform to estimate the energy band gaps; it is calculated by taking the difference between the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies. Concerning the poly thienylfuran, a reasonable result of energy band gap is obtained from a B3LYP/ 6-311++G(2d,p)// B3LYP/6-31G(d) calculation [20]. The purpose of this work is two fold. Firstly, the conformational behaviour depending on torsional angle is investigated for six furylpyridine isomers. Secondly, electronic and NLO properties such as dipole moment, HOMO-LUMO energy, polarizability, anisotropic polarizability and first hyperpolarizability were also investigated for all furylpyridine isomers

1 ( xx + 3

yy

+ zz

(2)

1 2 2 2 12 = (xx yy) + (xx zz) + (yy zz) 2

(3)
12

( + + )2 +( + + )2 + xxx xyy xzz yyy yzz yxx tot = 2 ( zzz + zxx + zyy )

(4)

within the framework of density functional theory

at the B3LYP/ 26]. 6-311++G(2d,p) level of theory [21-

Accurate calculation of dipole polarizabilities requires the use of extended basis sets. Pople-type 6-311++g(2d,p) basis set is contain polarization and diffuse functions on all atoms[21-23]. Full geometry optimization of furylpyridines was performed. For the optimized structures, to characterize the nature of stationary point, harmonic vibrational analysis was performed subsequently on each optimized structure. Individual torsion potentials were obtained for each molecule as a function of inter-ring C-C dihedral angle which was varied between 0 and 180o in 15o steps. The dipole moment, static polarizability, first static hyperpolarizability and HOMO-LUMO frontier molecular orbital energy calculations are performed. All calculations were performed using density functional theory through B3LYP functional using 6-31++G(d,p) basis set[2426]. All calculations were performed using Gaussian 03W package program [27].

3 Results and Discussion

In this section we present conformational analysis, electronic and nonlinear optical properties of six furylpyridine isomers, with cis and trans conformers, calculated at the B3LYP/6-31++G(2d,p) level of theory. According to our knowledge, there are no experimental data for the studied compounds for comparision. Furylpyridine molecules have the general structure shown in Fig.1.

2 Methodology
The interaction of a molecular system with a uniform external electric field (E) induces a dipole moment i ( E ) , which is represented as a power series in terms of the components of the electric field Ej in the following expression [1],

i ( E ) = i 0 + ij E j +
ij

1 ijk E j Ek + ... 2 jk

(1)

In this expression, i0 is the permanent dipole moment, ij is the linear polarizability, and ijk is the first hyperpolarizability, the origin of the NLO response. The complete equation for calculating the magnitudes of mean static dipole polarizability (), anisotropic polarizability () and total first static Fig. 1. The structure and numbering of atoms of furylpyridines (cis-conformer).

hyperpolarizability( tot ) is given by (1),

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Proceedings of the 9th WSEAS International Conference on APPLIED COMPUTER SCIENCE

Pyridine and furan molecules can rotate around the central C-C bond in furylpyridine molecules. Therefore, the conformational behaviour of title compounds is defined by the dihedral angle between the two rings. Fig.2 shows the torsional behavior of title compounds with the dihedral angles.
9 8 Torsional barrier (kcal/m ol) 7 6 5 4 3 2 1 0 -1 0 50 100 150 200 Dihedral angle (degrees) 2-(2-Furyl)pyridine 2-(3-Furyl)pyridine 3-(2-Furyl)pyridine 3-(3-Furyl)pyridine 4-(2-Furyl)pyridine 4-(3-Furyl)pyridine

Analysis of the dipole polarizability listed in Table 1, the values ranges from 114.17 au. to 121.89 au. Table 1. B3LYP/6-311++G(2d,p) calculated dipole moment, HOMO-LUMO (H-L) energy gap, dipole moment, polarizability, anisotropic polarizability and first hyperpolarizability of furylpyridines
Dipole H-L (D) (eV)
Cis-2-(2Furyl)pyridine Trans-2-(2Furyl)pyridine Cis-3-(2Furyl)pyridine Trans-3-(2Furyl)pyridine Cis-4-(2Furyl)pyridine Trans-4-(2Furyl)pyridine Cis-2-(3Furyl)pyridine Trans-2-(3Furyl)pyridine Cis-3-(3Furyl)pyridine Trans-3-(3Furyl)pyridine Cis-4-(3Furyl)pyridine Trans-4-(3Furyl)pyridine
2.2661 1.1725 3.0293 2.2902 3.3712 3.3709 2.3238 4,57 4,55 4,58 4,59 4,62 4,62 4,89

(au.)
121.89 121.83 120.56 120.63 120.30 120.30 115.80

(au.)
74.88 75.09 60.64 60.41 60.19 60.19 57.28

(au.)
989.77 947.08 820.19 790.01 874.01 874.01 651.77

Fig. 2. Torsional profile of furylpyridines. Energies are relative to minimum The above torsional profile results suggest the following observations. For 3-(3-furyl)pyridine, the conformers with two heterocycles in cis position show slight inter-ring twist and the other one with trans heterocycles tend to planar structure. 3-(3furyl)pyridine has a minimum at a dihedral angle of 29o for cis conformer. A planar trans conformer was confirmed as a transition state with an imaginary frequency -46 cm-1, locates 0.4 kcal/mol higher in energy than cis conformer. Our B3LYP/6-31++G(2d,p) calculation predicts the trans conformation to be the most stable configuration of other furylpyridines. Also, the electronic potential energy surface of 3-(3-furyl)pyridine is rather flat, the energy difference among critical points being within 2.7 kcal/mol, suggesting a high degree of conformational flexibility. It is true also for 4-(3-furyl)pyridine compound. It is noted that, the trans-3-(3-furyl)pyridine deviates slightly from the planarity with a torsional angle by approximately 5o. The other compounds have the planar cis and trans conformers. The calculated values of HOMO-LUMO energy gap, dipole moment (), dipole polarizability (), anisotropic polarizability and values of title compounds are shown in Table 1. From Table 1, some conclusions on electronic and NLO properties of title compounds can be drawn as follows. The difference in the HOMO-LUMO energy gap values ranges from 4.55 eV for trans-2-(2furyl)pyridine to 5.18 eV for trans-3-(3-furyl)pyridine.

1.7901 4,97 115.72 57.26 1.8139 4,94 114.65 55.59 2.5129 5,18 114.17 46.39 2.4926 5,03 114.46 61.17 2.4932 5,03 114.47 61.19

717.76 529.79 480.06 578.01 579.85

It seems that, the NLO properties are sensitive to positional substitution. The polarizability, anisotropic polarizability and first hyperpolarizability values for 3-furylpyridines are larger than the corresponding values for 2-furylpyridines.The maximum value of the first hyperpolarizability is about twice of minimum value of it. Trans-3-(3Furyl)pyridine has minumum values of polarizability, anisotropic polarizability and first hyperpolarizability while it has one of the high values of dipole moment and energy gap.

4 Conclusion
In this study, we investigated the torsional potential energy curves, electronic and nonlinear optical properties such as HOMO-LUMO energy gap, dipole moment, dipole polarizability, anisotropic polarizability and first hyperpolarizability values for six furylpyridine molecules with the cis and the trans conformers at the B3LYP/6-311++G(2d,p) level of

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Proceedings of the 9th WSEAS International Conference on APPLIED COMPUTER SCIENCE

theory. Our results showed that the planar structure is global minimum for furylpyridines except 3-(3-furyl)pyridine. The cis conformers and trans conformers show different electronic and optical properties. These results should be helpful in further research on furylpyridines in molecule based technologies. Acknowledgement: This work was funded by Gazi University (BAP: 05/2007-15 and 2008-15). References: [1] P. N. Prasad, D.J. Williams, Introduction to Nonlinear Optical Effects in Organic Molecules and Polymers, Wiley, 1990. [2] J.L. Bredas, R.R. Change, Conjugated Polymeric Materials: Opportunities in Electronics, Optoelectronics and Molecular Electronics, NATO ASI Series. E, Vol.182, Kluwer, 1990. [3] D.S. Chemla, J. Zyss, Nonlinear Optical Properties of Organic Molecules and Crystals, Academic Press, 1987. [4] P.N. Prasad, D.R. Ulrich, Nonlinear Optics and Electroactive Polymers, Plenum, 1988. [5] A. Gller, U.W. Grummt, Torsional barriers in biphenyl, 2,2-bipyridine and 2-phenylpyridine Chem. Phys. Lett., 321 (2000) 399. [6] F. Grein, New theoretical studies on the dihedral angle and energy barriers of biphenyl, J. Mol. Struc.(Theochem), 624 (2003) 23-28. [7] V. Lukes, M. Breza, S. Biskupic, Structure and electronic properties of bithiophenes. I. Torsional dependence, J. Mol. Struct. 618 (2002) 93-100. [8] A. Gller, U.W. Grummt, Detailed energy decomposition of the rotational barrier in 2,2bipyridine: a density functional study, Chem. Phys. Lett. 354 (2002) 233-242. [9] H.A. Duarte, H. Duani, W.B. Almedia, Chem. Phys. Lett., 369 (2003) 233. [10]M.Rumi and G. Zerbi, Conformational dependence of linear and nonlinear molecular optical properties by ab initio methods: the case of oligo-pphenylenes, Chem. Phys., 242 (1999) 123-140. [11]S. T. Howard, I. A. Fallis, D. J. Willock, Polarizability anisotropies of cyano-substituted azulene, biphenyl, 2,2-bipyridyl and naphtalane, Mol. Phys., 97 (1999) 913-918. [12]H. Alyar, M. Bahat, E. Kasap, Z. Kantarci, Torsional barriers and nonlinear optical properties of 2-, 3-, 4-phenylpyridine molecules, Czech. J. Phys., 56 (4) (2006) 349-358.

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[24] A. D. Becke, Density functional Exchange energy approximation with correct asymptotic behaviour, J. Chem. Phys., 98 (1993) 5648-5652. [25] C. Lee, W. Yang, R. G. Parr, Development of the Colle-Salveti correlation energy formula into a functional of the electron density, Phys. Rev. B., 37 (1988) 794. [26] B. Miehlich, A. Savin, H. Stoll, H. Preuss, Results obtained with the correlation energy density functional of Becke and Lee, Yang and Parr, Chem. Phys. Lett., 157 (1989) 2000-2007. [27] M.J. Frisch et. al., Gaussian 03W, Revision C01, Gaussian, Inc., Pittsburgh PA, 2003.

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