Int. Nano Lett., Vol. 2, No. 1, January 2012, pp. 5-9.

Investigation of Optoelectronic Properties of N3 Dye-Sensitized TiO2 Nanocrystals by Hybrid Methods: ONIOM (QM/MM) Calculations
Mohsen Oftadeh*, Leila Tavakolizadeh Department of Chemistry, Payame Noor University, 19395-4697 Tehran, I.R. Iran (Received 15 December, Accepted 17March 2011) In this article, Ru(4,4-dicarboxy-2,2-bipyridine)2(NCS)2 dye (N3) and some derivatives were investigated using DFT calculations in solution to elucidate the influence of the environment and substituted groups on the electronic properties. Full geometry optimization and investigation electronic properties of N3 dye and some derivatives were performed using DFT and HF calculations. The singlet ground state geometries were fully optimized at the B3LYP/3-21G** level of theory through Gaussian 98 program. Based on the computed results, the optoelectronic properties are sensitive to chemical solvent environments. Moreover, the properties of anatase cluster (TiO2) models have been investigated and then N3 dyes have been adsorbed on TiO2 nano-particle with diprotonated states. The modified N3 dyes highly affected electronic structure. This leads to significant changes in the absorption spectra as compared to the N3 dyes. Through hybrid methods the properties of interfacial electronic coupling of the combined system were estimated. The results of some combined systems showed that the electronic coupling, lowest LUMOs and the TiO2 conduction band resided in the visible region. Keywords: DFT, Gap Energy, Sensitized Dye, Optical Properties titanium dioxide nanoparticles [8-11]. Quantum chemical calculations can provide information about geometrical and electronic structure in dyesensitized solar cells (DSSCs) [12]. The N3 dye, as shown in Fig. 1, is one conventional dye which can show optical adsorption spectra [13] related to the size and conjugation of linkers to the surface at semiconductor TiO2. Surface electron transfer accompanying the initial light absorption and excitation of ruthenium dyes often leads to efficient photo-induced charge separation across the dye and TiO2 interfaces. TiO2 can be formed in several phases such as anatas, rutaile and broklit. There are some properties of TiO2 nano-crystal such as electroopticality, low cost, chemical stability, nontoxicity, abundance, availability and lack of erosion and corrosion against light which are common in the literature [14]. The anatas crystal phase of TiO2 have octahedral structure with wide gap energy, photo-induced activity, large surface

Introduction
Photo-induced* phenomenon, based on photon absorption with enough energy, causes the excitation of electrons and then the current generation. Electron transfer (ET) at organic/inorganic interfaces plays a key role in a variety of applications including photocatalysis, photoelectrolysis, solar cells andnanoscale electronics [15]. The dye sensitized nanocrystalline solar cell, or Grtzel cell, is a popular alternative in comparison to the costly traditional solar cell [6,7]. The attached chromophore dye with tuned desired wavelength in a well-known Grtzel cell should absorb photons and generate electrons within dye-sensitized Corresponding author: E-mail: m_oftadeh@pnu.ac.ir Tel : +98 311 738 0555, Fax: +98 311 738 1002
*

Oftadeh et al. area to bulk ratio, and it can absorb UV light more than other phases. Due to the lack of anatas stability in its structure and a high degree of dangling bonds, calculation of structural and electronic properties of the large number of under coordinated atom is complicated. However, the size and complexity of TiO2 nano particles impose challenges for choosing the methods. Several titanium oxide nano crystals have been investigated in some studies [15-20]. The calculation for anatase (TiO2)5 and (TiO2)16 clusters has been performed by DFT, but because of computational demanding for large systems the semiemprical methods have been used. The (TiO2)54 cluster has large surface and more tendency toward to sphericity and it is selected as the basis for computing absorption dyes and its derivatives.

(a)

(b) Fig. 1.The structural formulae of N3 dye (a) and its substituted derivatives (b) with X= CH3, C2H5, NH2, N(CH3)2, F and Cl

The N3 dye and its derivatives are probably the most well-known of sensitized dyes which transfer electron by adsorbing sunlight followed by electron injection to the conduction band of TiO2 so the gap energy will be increased [21,22]. The electron transfer depends on different parameters, for example the type of attaching such as bridge, chelat ing, mono dentate, which are shown in Fig. 2 [23,24]. The dye is adsorbed in a prototype binding of the two carboxylic acid anchor groups of one of the bpirridyn ligands in a bridging bi-dentate adsorption mode. Fig. 2 shows types of attaching anchor groups on the adsorbant layer [4]. The purpose of this paper is to investigate the role of accepter and donor groups on N3 dyes, and also to understand the electron transfer phenomena, variation of gap energy, geometrical and electronic coupling among the parts in the combined system, (TiO2)54-N3 derivatives.

obtained by DFT and supported by HF calculations. The singlet ground state geometries were fully optimized at the B3LYP/3-21G** level of theory. All calculations were performed with Gaussian 98 program [25].
molecular adsorption H C O Ti OH O H C OH Ti O Ti

H C OH O Ti

H C OH Ti

MHa monodentate through Co

MHb monodentate through OH

BH bidentate chelating

BBH bidentate bridging

dissociative adsorption H H C O Ti M(H) monodentate ester type O O Ti B(H) bidentate chelating C O Ti Ti BB(H) bidentate bridging O H C O

Computational method
Through density function theory the full geometry optimization and investigation of the electronic properties of N3 dye and some derivatives were performed [12]. The results were

Fig. 2. The types of attaching anchor groups on the adsorbent layer [4].

Investigation of Optoelectronic Properties of N3 Dye-Sensitized TiO2 Nanocrystals by Hybrid Methods The variation of gap energies were investigated by inserting electron donor groups such as: CH3, C2H5, NH2, N(CH3)2 or electron accepter groups such as F and Cl on the position related to carboxylat on N3 dye as shown in Fig. 1. To compare of the results all calculations were first done in gas phase and then in solvent. In this study, PCM model of ethanol (dielectric constant, , =25) and acetonitrile (=37) were used. Since the DFT calculation of the large clusters are very costly, the (TiO2)54 nanocrystals have been optimized by MSINDO semiemprical method [3]. Further, we used the integrate B3LYP: ZINDO1 approach for the combined dyes and (TiO2)54 cluster systems and some of dye derivates. To evaluate the accuracy of the proposed hybrid method results, the combined system of N3 and (TiO2)54 have been optimized via DFT method by a 16 core supercomputer. The time consuming of the each calculation was about two months.

Table 1. The calculated HOMO, LUMO (in Hartree), gap energy, and absorption threshold by DFT at B3LYP/3-21G** level of theory for N3-X dye (X is the substituted groups by one of the hydrogen on pyridine besides of carboxylat group) in the gas phase, in ethanol and acetonitrile phases. Gas Phase -X HOMO LUMO GAP (v) -0.1063 0.1085 1.494 (nm) 830 822 792 788 770 828 838 HOMO Ethanol LUMO GAP (ev) (nm) HOMO Acetonitrile LUMO GAP (ev) 2.136 2.109 2.008 1.996 1.462 2.059 2.008 (nm) 581 588 614 621 848 602 618

-H -CH3 -C2H5 -NH2

-0.1976 -0.1943 -0.1867 -0.1872 -----0.1942 -0.1928

-0.1202 2.105 620 -0.1178 2.082 595 -0.1164 1.913 648 -0.1145 1.978 626 -------------

-0.1988 -0.1955 -0.1910 -0.1881 -0.1592 -0.1980 -0.1981

-0.1203 -0.1179 -0.1172 -0.1147 -0.1055 -0.1223 -0.1243

-0.1726 -0.1172 1.508 -0.1627 -0.1052 1.565 -0.1696 -0.1117 1.574

-N(CH3)2 -0.1613 -0.1022 1.609 -F -Cl -0.1741 -0.1191 1.498 -0.1741 -0.1197 1.479

-0.1216 1.977 627 -0.1232 1.894 654

Results and discussion

The computational results for N3 dyes and some derivatives which were performed by B3LYP method and 3-21G** basis set in both gas and solvent phases have are presented in Table 1. A visual comparison of the HOMO and LUMO of N3 and some of its derivatives in the gas, acetonitrile and ethanol phases shows an increasing and obvious shifting in absolute energy and reveal a clear difference in the energetic ordering of the frontier orbitals in different environments.

The results show that the substituted groups do not have an important role in transferring of the absorption wavelength from UV to visible region in the gas phase. Moreover, the groups have a few influences on the decrease of N3 gap energy. The energy silently decreases in solvent environment so that the difference between gas and solvent environment is about 0.5 eV for all groups. The solvent effect on the gap energy variation occurs through interaction of dye and ethanol or acetonitrile molecules. It shows a significant influence on the optical properties of these complexes by the environment, so that the

Oftadeh et al. wavelength of N3 complexes is shifted from 830 to 580 nm by inclusion of the solvent. The range of variation of optoelectronic properties is taken into account under a model for complexes with along conjugated whether the theoretical modeling is capable of providing a physically realistic description of the complexes with extended conjugation.
Table 2. The calculated gap energy, and absorption threshold by ZINDO1 of theory for combined system of N3-X dyes (X is the substituted groups by one of the hydrogen on pyridine besides of carboxylat group) and (TiO2)54 cluster in the gas phase. molecules (TiO2)54 (TiO2)54 + N3 (TiO2)54 + N3 + F (TiO2)54 + N3 + Cl (TiO2)54 + N3 + CH3 (TiO2)54 + N3 + C2H5 (TiO2)54 + N3 + NH2 (TiO2)54 + N3 + N(CH3)2 GAP (ev) 3.97 1.54 4.21 6.6 2.7 2.5 1.6 0.3 (nm) 313 800 295 93 445 490 780 4353

Conclusion
In order to significant experimental efforts to develop DSSCs and related photo electrochemical devices, the quantum chemical calculations were performed to provide a better theoretical understanding of the basic physical and chemical processes at dye-sensitized semiconductors. As shown before, the modified N3 dyes have highly affected the electronic structure. This leads to significant changes in the absorption spectra as compared to the N3 dyes. The optical absorption spectra are related to environment and are not probably related to the type of X-substituted groups. The results of combination system showed that the electronic coupling of the lowest dye LUMOs and the TiO2 conduction band is negligible. Moreover, the lowest LUMO dye and TiO2 band conduction, using hybrid method and the electronic structure, agree with the experiment evidence. Finally, the absorption wavelength of some substituted dyes of combined system is located in the visible area.

Acknowledgement
The authors would like to greatly appreciate to Dr. H.S. Wahab from Baghdad University of technology for his instructions.

Using the integrate B3LYP: ZINDO1 approach, the results of combined systems of N3 dyes and some of derivatives with (TiO2)54 cluster are summarized in Table 2. The table shows that some of the absorption wavelengths of a combined system are located in the visible area. Furthermore, the computed results by the mentioned methods for heterogeneous super molecule are given in Table 3. However the gap energy almost differs among ONIOM and DFT, ONIOM results are well in the agreement with our expectation.
Table 3. The calculated gap energy and the adsorption wavelength of combined system of N3 and (TiO2)54 cluster in the gas phase by ONIOM and B3LYP methods. Method ONIOM B3LYP GAP (ev) 1.54 3.93 (nm) 800 320

References
[1] S. Ferrere, B.A. Gregg, J. Phys. Chem. B 105 (2001) 7602. [2] P .A. Derosa, J.M. Seminario, J. Phys. Chem. B 105 (2001) 471. [3] B. ORegan, M. Grtzel, Nature 353 (1991) 737. [4] J. Pan, G. Benko, Y.H. Xu, T. Pascher, L. C. Sun, V. Sundstrom, T. Polivka, J. Am. Chem. Soc. 124 (2002) 13949. [5] V. Biju, M. Micic, D.H. Hu, H.P. Lu, J. Am. Chem. Soc. 126 (2004) 9374. [6] B. ORegan, M. Grtzel, Nature 353 (1991) 6346. [7] R.D. McConnell, Renewable Sustainable Energy Rev. 6 (2002) 273.

Investigation of Optoelectronic Properties of N3 Dye-Sensitized TiO2 Nanocrystals by Hybrid Methods [8] N.A. Anderson, T.Q. Lian, Ann. Rev. Phys. Chem. 56 (2005) 491. [9] L.G.C. Rego, V.S. Batista, J. Am. Chem. Soc. 125 (2003) 7989. [10] W. Stier, W.R. Duncan, O.V. Prezhdo, SPIE Proc. 5223 (2003) 132. [11] W.R. Duncan, W.M. Stier, O.V. Prezhdo, J. Am. Chem. Soc. 127 (2005)7941. [12] M.J. Lundqvist, Quantum chemical modeling of dye-sensitized titanium dioxide, Ph.D thesis, Uppsala University, Sweden, 2006. [13] A. Aghtar, The making of the dyesensitized solar cell with nanoparticles TiO2 for using in the photocatalytic oxidationreduction reactions, M.S.C dissertation, Payame Noor University (PNU), Shiraz, Iran, 2009. [14] U. Diebold, Appl. Phys, A 76 (2003) 681. [15] M. Nilsing, S. Lunell, P. Persson, L. Ojama, Surf. Sci. 582 (2005) 49. [16] T. Homann, T. Bredow, K. Jug, Surf. Sci. 555 (2004) 135. [17] A. Vittadini, A. Selloni, F.P. Rotzinger, M. Gra1tzel, J. Phys. Chem. B 104 (2000) 1300. [18] M. Nilsing, P. Persson, L. Ojamae, Chem. Phys. Lett. 415 (2005) 375. [19] D. Rappoport, N.R.M. Crawford, F. Furche, K. Burke, in: E.I. Solomon, R.B. King, R.A. Scott (Eds.), Computational Inorganic and Bioinorganic Chemistry, Wiley, Chichester, 2008. [20] M.K. Nazeeruddin, F. De Angelis, S. Fantacci, A. Selloni, G. Viscardi, P. Liska, S. Ito, B. Takeru, M. Gra tzel, J. Am. Chem. Soc. 127 (2005) 16835. [21] H.S. Wahab, T. Bredow, S.M. Aliwi, J. Mol. Struct. THEOCHEM 863 (2008) 84. [22] M.J. Lundqvist, M. Nilsing, P. Persson, S. Lunell, Int. J. Quantum Chem. 106 (2006) 3214. [23] M.J. Lundqvist, E. Galoppini, G.J. Meyer, P. Persson, J. Phys. Chem. A 111 (2007) 1487. [24] M.F. Iozzi, Theoretical models of the interaction between organic molecules and semiconductor surfaces, Ph.D Thesis, Napoli University, Italy, 2006 . [25] M.J. Frisch, G.W. Trucks, H.B. Schlegel, P.M.W. Gill, B.G. Johnson, M.A. Robb, J.R. Cheeseman, T. Keith, G.A. Petersson, J.A. Montgomery, K. Raghavachari, M.A. AlLaham, V.G. Zakrzewski, J.V. Ortiz, J.B. Foresman, J. Cioslowski, B.B. Stefanov, A. Nanayakkara, M. Challacombe, C.Y. Peng, P.Y. Ayala, W. Chen, M.W. Wong, J.L. Andres, E.S. Replogle, R. Gomperts, R.L. Martin, D.J. Fox, J.S. Binkley, D.J. Defrees, J. Baker, J.P. Stewart, M. Head-Gordon, C. Gonzalez, J.A. Pople, Gaussian 98, Revision D.2; Gaussian, Inc.: Pittsburgh, PA, 1999.