J Mol Model (2012) 18:835842 DOI 10.

1007/s00894-011-1120-6

ORIGINAL PAPER

Computational characterization of the molecular structure and properties of Dye 7 for organic photovoltaics
Jess Baldenebro-Lpez & Jos Castorena-Gonzlez & Norma Flores-Holguin & Joel Caldern-Guilln & Daniel Glossman-Mitnik

Received: 6 February 2011 / Accepted: 5 May 2011 / Published online: 20 May 2011 # Springer-Verlag 2011

Abstract Organic dyes have great potential for its use in solar cells. In this recent work, the molecular structure and properties of Dye 7 were obtained using density functional theory (DFT) and different levels of calculation. Upon comparing the molecular structure and the ultraviolet visible spectrum with experimental data reported in the literature, it was found that the M05-2X/6-31G(d) level of calculation gave the best approximation. Once the appropriate methodology had been obtained, the molecule was characterized by obtaining the infrared spectrum, dipole moment, total energy, isotropic polarizability, molecular orbital energies, free energy of solvation in different solvents, and the chemical reactivity sites using the condensed Fukui functions. Keywords Molecular structure . Polarizability . G(solv) . Chemical reactivity Abbreviations DFT Density functional theory TD-DFT Time-dependent density functional theory IR Infrared UV-vis Ultraviolet Angstrom
J. Baldenebro-Lpez : J. Castorena-Gonzlez : J. Caldern-Guilln Facultad de Ingeniera Mochis, Universidad Autnoma de Sinaloa. Prol. ngel Flores y Fuente de Poseidn, S.N, C.P. 81223 Los Mochis, Sinaloa, Mxico N. Flores-Holguin : D. Glossman-Mitnik (*) Centro de Investigacin en Materiales Avanzados, SC, Complejo Industrial Chihuahua, Miguel de Cervantes 120, Chihuahua 31109, Mxico e-mail: daniel.glossman@cimav.edu.mx

max THF HOMO LUMO G(solv) IEF-PCM

Wavelength of maximum absorption Tetrahydrofuran Highest occupied molecular orbital Lowest unoccupied molecular orbital Free energy of solvation Integral equation formalism of the polarized continuum model

Introduction Photovoltaic devices have gained wide acceptance as a clean and renewable energy source [1]. These devices are based on the concept of charge separation at an interface between two materials with different conduction mechanisms [2, 3]. One important invention in this field is the photovoltaic dye-sensitized solar cell (DSSC) [4], which has been the subject of intense research due to its ability to convert solar energy into electrical energy [5, 6], as well as its low cost compared to solar cells that use polycrystalline silicon [7]. There are four main factors that affect the performance of a DSSC: the photosensitive dye, the anode, the cathode and the electrolyte. The dye plays a crucial role in enhancing the efficiency of the cell, which is why it is one of the most intensely studied factors [8]. In the present work, a theoretical study of the molecular structure and properties of a dye (Dye 7) was performed. This dye consists of a triphenylamine molecule that serves as electron donor group [9, 10], a thiophene to adjust the absorption spectra of the molecules [11], and a cyanoacrylic acid that acts as an acceptor group[12], as shown in Fig. 1. In the investigation described below, different levels of theory were used in order to establish the most appropriate methodology to study this dye. Besides optimizing the

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Fig. 1 Molecular structure of Dye 7: triphenylamine (donor), a thiophene (to adjust the absorption spectra of the molecules) and cyanoacrylic acid (acceptor)

geometry of Dye 7, the infrared and ultraviolet spectra were presented, the dipole moment calculated, as were the total energy, isotropic polarizability, molecular orbital energies, and the free energy of solvation in different solvents;. Its chemically reactive sites were also discerned using the condensed Fukui functions.

the displayed spectra show the calculated frequencies and absorption wavelengths. The condensed Fukui functions were calculated using AOMIX molecular analysis software [34, 35], starting from single-point energy calculations.

Results and discussion Molecular modeling Density functional theory (DFT) was used in this study [13]. DFT was developed by Walter Kohn in the 1960s, and was implemented in this study using the commercial software Gaussian 03W [14]. The geometry of the molecule in its fundamental state was obtained by the established technique in Gaussian 03W. The force constants and vibrational frequencies were determined by calculating analytical frequencies for stationary points obtained after optimizing the geometry. Both calculations were done at the same level of theory. The basis sets used in this study were 3-21G(d) and 6-31G(d) (for more details, see [15]). The density functionals used in this research were: BLYP [16, 18], B3LYP [1619], PBE [20, 21], PBE1PBE [21], TPSS [22], TPSSh [23] and M05-2X [24]. A detailed description of these density functionals can be found in the updated bibliography of computational chemistry [2528]. The calculation of the ultraviolet spectrum of the molecule Dye 7 was done via time-dependent DFT equations according to the method implemented in the Gaussian molecular package 03W [25, 2932]. The equations were solved for 20 excited states. The infrared (IR) and ultraviolet-visible (UV-vis) spectra were analyzed and visualized using the program SWizard [33]. In all cases, The molecular structure of Dye 7 was analyzed at different levels of theory, as mentioned above. The bond lengths obtained from our calculations as well as experimental data reported in the literature on the systems that comprise our dye are shown in Table 1 for the most representative bonds. It is clear that there is good agreement among the results obtained for different models for each bond. However, to check which methodology gives the most accurate results for the molecular structure of Dye 7, a statistical technique known as population standard deviation was applied (PSTD) to the results for the bond lengths. When applying this technique, the experimental result was used as a reference for the average value; in this way, the models that give the lowest deviation will give the best representations of our study system. It is important to note that we have not considered a tolerance level for the deviation, as our priority was to establish the model that best fits the experimental results. The results from the PSTD are shown in Table 2, which indicates that the most accurate methodology for the theoretical study is M05-2X/6-31G(d). The interatomic bond lengths () and the angles (in degrees) calculated at this level of calculation are shown in Fig. 2. A second validation of the models involved comparing the theoretical wavelengths of maximum absorption (max)

J Mol Model (2012) 18:835842 Table 1 Bond lengths calculated at different levels of theory for Dye 7, and well as experimental data reported in the literature Model BLYP/3-21G* B3LYP/3-21G* PBE/3-21G* PBE1PBE/3-21G* TPSS/3-21G* TPSSh/3-21G* M05-2X/3-21G* BLYP/6-31G(d) B3LYP/6-31G(d) C1C2 1.415 1.403 1.412 1.400 1.410 1.406 1.397 1.414 1.403 C3C4 1.404 1.394 1.401 1.391 1.401 1.397 1.390 1.404 1.394 1.400 1.390 1.399 1.395 1.390 1.397 C4C5 1.408 1.397 1.406 1.395 1.405 1.401 1.393 1.407 1.397 1.403 1.393 1.402 1.398 1.392 1.397 C1C6 1.404 1.394 1.401 1.391 1.401 1.397 1.390 1.403 1.394 1.399 1.390 1.399 1.395 1.390 1.397 C1H7 1.089 1.082 1.092 1.084 1.087 1.084 1.079 1.092 1.085 1.094 1.086 1.088 1.086 1.082 1.084

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C13H12 C13C14 C16C19 C15C17 C23C24 C24C26 1.089 1.082 1.092 1.084 1.087 1.084 1.079 1.092 1.085 1.094 1.086 1.088 1.086 1.082 1.084 1.415 1.403 1.412 1.400 1.410 1.406 1.397 1.414 1.403 1.410 1.399 1.408 1.404 1.397 1.397 1.404 1.394 1.402 1.391 1.401 1.397 1.390 1.403 1.394 1.400 1.390 1.399 1.395 1.390 1.397 1.408 1.397 1.406 1.395 1.405 1.401 1.393 1.407 1.396 1.403 1.393 1.402 1.398 1.392 1.397 1.421 1.408 1.418 1.405 1.416 1.411 1.400 1.420 1.408 1.416 1.403 1.414 1.409 1.400 1.397 1.395 1.387 1.393 1.385 1.393 1.389 1.386 1.395 1.387 1.392 1.384 1.391 1.388 1.385 1.397

PBE/6-31G(d) 1.410 PBE1PBE/6-31G(d) 1.399 TPSS/6-31G(d) TPSSh/6-31G(d) M05-2X/6-31G(d) Experimental Model BLYP/3-21G* B3LYP/3-21G* PBE/3-21G* PBE1PBE/3-21G* TPSS/3-21G* TPSSh/3-21G* M05-2X/3-21G* BLYP/6-31G(d) 1.408 1.404 1.397 1.397

C26-C30 C24-H27 C2-N33 1.425 1.089 1.448 1.411 1.082 1.434 1.422 1.407 1.421 1.415 1.402 1.423 1.091 1.083 1.087 1.084 1.079 1.092 1.085 1.093 1.085 1.088 1.085 1.082 1.084 C40-C42 1.412 1.397 1.411 1.395 1.409 1.403 1.387 1.410 1.396 1.408 1.393 1.406 1.400 1.387 1.370 1.436 1.424 1.440 1.434 1.426 1.439 1.427 1.428 1.417 1.431 1.426 1.418 1.418 C35-H44 1.094 1.086 1.096 1.087 1.091 1.088 1.082 1.095 1.088 1.097 1.088 1.090 1.088 1.084 1.099

C30-C34 C34-C35 C34-H36 C35-C37 C37-C38 C37-S39 1.459 1.371 1.095 1.444 1.412 1.764 1.456 1.355 1.088 1.442 1.397 1.741 1.454 1.452 1.455 1.454 1.462 1.455 1.453 1.449 1.449 1.451 1.451 1.459 1.475 C42-C45 1.425 1.421 1.422 1.419 1.422 1.421 1.428 1.426 1.423 1.422 1.421 1.423 1.422 1.430 1.475 1.369 1.352 1.368 1.361 1.343 1.374 1.358 1.370 1.353 1.369 1.362 1.346 1.334 C45-C46 1.383 1.367 1.380 1.363 1.379 1.372 1.353 1.389 1.372 1.385 1.367 1.384 1.376 1.358 1.334 1.098 1.089 1.093 1.090 1.084 1.097 1.089 1.098 1.090 1.092 1.089 1.086 1.099 C46-C48 1.417 1.411 1.412 1.408 1.413 1.411 1.413 1.427 1.424 1.422 1.420 1.423 1.422 1.428 1.475 1.440 1.440 1.441 1.441 1.450 1.443 1.442 1.438 1.439 1.439 1.440 1.450 1.475 C46-C49 1.488 1.477 1.481 1.472 1.480 1.476 1.473 1.492 1.483 1.486 1.479 1.484 1.481 1.482 1.475 1.412 1.395 1.410 1.403 1.386 1.410 1.396 1.408 1.392 1.406 1.400 1.386 1.370 C48-N50 1.182 1.168 1.183 1.167 1.181 1.175 1.159 1.179 1.165 1.179 1.164 1.176 1.170 1.157 1.172 1.748 1.726 1.750 1.740 1.721 1.766 1.743 1.748 1.727 1.748 1.739 1.723 1.714 C49-O51 1.244 1.231 1.243 1.228 1.243 1.237 1.224 1.230 1.216 1.227 1.212 1.226 1.220 1.209 1.200

C38-C40 C38-H41 1.409 1.088 1.404 1.080 1.405 1.401 1.405 1.404 1.409 1.405 1.400 1.400 1.397 1.400 1.398 1.404 1.423 C49-052 1.400 1.376 1.390 1.366 1.394 1.383 1.366 1.375 1.353 1.364 1.343 1.366 1.356 1.342 1.334 1.090 1.081 1.085 1.082 1.076 1.091 1.084 1.092 1.084 1.087 1.084 1.080 1.079 O52-53H 1.010 0.996 1.008 0.992 1.005 0.999 0.991 0.986 0.975 0.985 0.972 0.983 0.978 0.971 0.970

B3LYP/6-31G(d) 1.410 PBE/6-31G(d) 1.419 PBE1PBE/6-31G(d) 1.405 TPSS/6-31G(d) TPSSh/6-31G(d) M05-2X/6-31G(d) Experimental Model BLYP/3-21G* B3LYP/3-21G* PBE/3-21G* PBE1PBE/3-21G* TPSS/3-21G* TPSSh/3-21G* M05-2X/3-21G* BLYP/6-31G(d) B3LYP/6-31G(d) PBE/6-31G(d) PBE1PBE/6-31G(d) TPSS/6-31G(d) TPSSh/6-31G(d) M05-2X/6-31G(d) Experimental 1.418 1.412 1.401 1.397 C42-S39 1.781 1.758 1.763 1.742 1.765 1.756 1.735 1.784 1.761 1.765 1.743 1.765 1.756 1.739 1.714

838 Table 2 Results of the population standard deviation for the bond lengths obtained with different models Model BLYP/3-21G* B3LYP/3-21G* PBE/3-21G* PBE1PBE/3-21G* TPSS/3-21G* TPSSh/3-21G* M05-2X/3-21G* BLYP/6-31G(d) B3LYP/6-31G(d) PBE/6-31G(d) PBE1PBE/6-31G(d) TPSS/6-31G(d) TPSSh/6-31G(d) M05-2X/6-31G(d) Population standard deviation 0.0258 0.0189 0.0236 0.0175 0.0232 0.0203 0.0150 0.0238 0.0171 0.0214 0.0159 0.0204 0.0179 0.0130

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for Dye 7 obtained using the models with the value obtained experimentally in research conducted by Zhang et al. [4]. In their research, they found that max occurred at 432 nm in the solvent tetrahydrofuran (THF). Knowing this fact, it was possible to re-validate which of the models best represented our molecular system. Thus, the UV-vis spectrum of Dye 7 in THF solvent was calculated at the B3LYP/6-31G(d), BLYP/6-31G(d), M05-2X/6-31G(d), PBE1PBE/6-31G(d), PBE/6-31G(d), TPSS/6-31G(d) and TPSSh/6-31G(d) levels of theory using time-dependent DFT (TD-DFT). The results obtained are shown in Fig. 3. The calculated UV-vis spectra are provided in Table 3, and it is quite apparent that the closest theoretical value of max to the experimental one is 444.44 nm, which was afforded by M05-2X/6-31G(d). The calculated value of max is an important parameter which indicates that this molecular system should be considered for use as a functional material (a dye in this case) in a DSSC, as the value of this parameter for Dye 7 falls within the range of the solar spectrum of visible light [36]. At all of the levels of theory tested, the observed signal corresponded to the HOMO (highest occupied molecular orbital) to LUMO (lowest unoccupied molecular orbital) transition. Table 4 shows the results of TD-DFT calculations performed using the functional M05-2X and the basis set 6-31G(d), including the electronic state transitions, their corresponding wavelengths (in nm) and energies (in eV), as well as their assignments in terms of the orbitals involved in the transitions. Taking into account the results for the molecular structure and UV-vis spectrum calculations, it is clear that the functional M05-2X and the basis set 6-31G(d) is the

most appropriate level of calculation to perform the rest of the characterization of Dye 7. The infrared spectrum (IR) for Dye 7 calculated with M052X/6-31G(d) is shown in Fig. 4. The vibrational bands were assigned using the molecular visualization software for Windows ChemCraft. CS stretching is observed as a peak at 584 cm1. At 796 cm1, a peak due to vibrations of carbonchain hydrogens out of the plane of the aromatic rings can be seen, while another peak due to the corresponding vibrations for the bending of CH in thiophene is present at 1091 cm1. Vibrations due to the bending of the bond OH produce a peak at 1236 cm1. Other intense peaks include those due to the stretching of the CN bond in the amine and the CC in the thiophene occurring at 1392 cm1 and 1521 cm1 respectively; meanwhile, at 1677 cm1, a peak due to the double-bond stretching of C(45)=C(46) is noted. The peak at 1872 cm1 represents the stretching of the double bond C=O, while the vibration at 2417 cm1 corresponds to the stretching of the triple bond CN. The CH vibrations for the aromatic rings occur at 3244 cm1, and stretching of the OH bond is observed at 3784 cm1. The molecular dipole moment is an experimental measure of the charge distribution in a molecule. The precision of the global distribution of electrons in a molecule is difficult to quantify, since it involves all multipoles. In this calculation, the values of the total energy of the system, the total dipole moment and the isotropic polarizability in the fundamental state obtained at the M05-2X/6-31G(d) level of calculation are 1736.99 a.u., 6.7374 debye and 433.06 bohr3. Moreover, the calculated energies of the HOMO and LUMO are 6.29 eV and 1.85 eV, respectively. These results are of great importance, since they can be used during synthesis to determine the solubility and chemical reactivity of the molecule, and they can also be employed in organic electronics and photovoltaics, as reported in different works [3739]. The free energy of solvation G(solv) of the molecule was calculated for Dye 7 using M05-2X/6-31G(d) coupled with the integral equation formalism of the polarized continuum model (IEF-PCM) for different solvents. The solubility of a molecule depends on several kinetic and thermodynamic factors. However, the magnitude and sign of G(solv) can be used as an approximate index of solubility. In this sense, a negative sign and a large magnitude indicates increased solubility. The results of this calculation for the studied molecule can be summarized as follows: cyclohexane = 1.85 kcal mol1, chloroform = 4.68 kcal mol1, water= 5.02 kcal mol1, THF = 5.30 kcal mol1, acetone = 12.86 kcal mol1, ethanol= 14.43 kcal mol1 and methanol= 15.03 kcal mol1. Based on these results, it appears that the molecule under investigation will be most soluble in methanol and ethanol.

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Fig. 2 Interatomic bond distances () and bond angles (in degrees) for Dye 7 obtained at the M05-2X/6-31G(d) level of calculation

The HOMO and LUMO orbitals of Dye 7 calculated at the M05-2X/6-31G(d) level of theory are shown in Fig. 5. The HOMO orbital density is located over the double bonds of the carbon chain and the nitrogen (N33); meanwhile, the density of the LUMO orbital is concentrated over the CC single bonds. This provides a good idea of the reactivity of the molecule. The reactive sites can be identified through these orbital densities. The calculated HOMO and LUMO

densities shown in Fig. 5 indicate that electrophilic attack may occur preferentially at the C=C double bonds or at N33, while nucleophilic attack occurs at CC single bonds. The condensed Fukui functions can also be used to determine the reactivity of each atom in the molecule. The corresponding condensed Fukui functions are fk qk N 1 qk N (for nucleophilic attack), fk qk N qk N 1 (for electrophilic attack) and fk0

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Fig. 3 Ultraviolet-visible (UV-vis) spectrum of Dye 7 calculated using time-dependent DFT (TD-DFT) with the basis set 6-31G(d) and the functionals used in this research Table 3 Values of the wavelength of maximum absorption by Dye 7 calculated using the various models tested Model BLYP/6-31G(d) B3LYP/6-31G(d) PBE/6-31G(d) PBE1PBE/6-31G(d) TPSS/6-31G(d) TPSSh/6-31G(d) M05-2X/6-31G(d) Experimental max (nm) 500.00 598.80 495.05 564.97 480.77 666.67 444.44 432.00

qk N 1 qk N 1=2 (for radical attack), where qk is the effective Mulliken charge of atom k in the molecule. The calculations of the condensed Fukui functions for nucleophilic and electrophilic attacks were performed using AOMIX (a molecular analysis program), which gave the following results: fk 0:1876 and fk 0:1906. Electrophilic attack will occur at atoms that produce a negative charge, and where the Fukui function fk is a maximum. This value confirms that the most probable site of electrophilic attack is N33. Nucleophilic attacks, on the other hand, will occur at atoms that produce a positive charge and where the Fukui function fk is a maximum.

Table 4 Electronic transition states of Dye 7 (calculated with TD-DFT at the M05-2X/6-31G(d) level of theory) State 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 Wavelength (nm) 444.1 325.2 295.5 280.2 271.3 268.1 252.1 250.8 243.4 241 239.2 234.1 227.8 223.2 221 215.4 209.6 206.6 206 203.1 Energy (eV) 2.79 3.81 4.2 4.42 4.57 4.62 4.92 4.94 5.09 5.15 5.18 5.3 5.44 5.55 5.61 5.76 5.92 6 6.02 6.1 f 1.7821 0.0338 0.2897 0.0564 0.2703 0.0851 0.0215 0.0052 0.0001 0.0261 0.0028 0.0824 0.001 0.0095 0.0054 0.0469 0.0093 0.0012 0.0678 0.0158 Assignment (H = HOMO,L = LUMO) S H-0L+0(+73%) H-1L+0(11%) S H-1L+0(+61%) H-0L+1(+12%) H-0L+0(+8%) S H-0L+1(+64%) H-0L+0(12%) H-1L+0(9%) S H-0L+2(+79%) S H-0L+3(+81%) H-1L+3(+8%) S H-7L+0(+71%) H-4L+0(+12%) S S S S S S S S S S S S S S H-0L+5(+33%) H-0L+4(9%) H-6L+0(+8%) H-1L+1(+8%) H-3L+0(+6%) H-1L+1(+18%) H-4L+0(12%) H-0L+5(12%) H-7L+0(+9%) H-0L+4(6%) H-9L+0(+67%) H-9L+8(12%) H-9L+1(9%) H-0L+6(+57%) H-4L+0(+10%) H-1L+6(+8%) H-3L+3(5%) H-1L+1(+24%) H-4L+0(+23%) H-2L+0(14%) H-0L+4(11%) H-0L+6(8%) H-3L+0(+40%) H-0L+5(24%) H-6L+0(+14%) H-0L+7(+47%) H-1L+7(39%) H-0L+4(+49%) H-1L+1(+26%) H-0L+1(+7%) H-2L+0(+68%) H-4L+0(+17%) H-6L+0(+51%) H-3L+0(33%) H-5L+0(+88%) H-5L+1(+6%) H-1L+10(+17%) H-15L+0(16%) H-0L+10(12%) H-9L+8(6%) H-8L+0(+42%) H-4L+1(+15%) H-10L+0(13%) H-4L+0(+6%) H-1L+2(+35%) H-2L+3(10%) H-2L+2(+6%) H-0L+5(+6%)

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its isotropic polarizability, its molecular orbitals and its infrared spectrum were calculated using M05-2X/6-31G(d). The free energy of solvation G(solv) of the molecule, calculated using the same level of theory along with the integral equation formalism of the polarized continuum model (IEF-PCM), indicates that the molecule is potentially soluble in methanol and ethanol. The M05-2X/6-31G(d) methodology can be used as an useful tool for studying the molecular structure and electronic properties of Dye 7, as well as other structures derived from it.
Acknowledgments This work was made possible by the support of Universidad Autnoma de Sinaloa through the Facultad de Ingeniera Mochis, by the PROFAPI2010/033 project, Centro de Investigacin en Materiales Avanzados, S.C. (CIMAV), and Consejo Nacional de Ciencia y Tecnologa. Fig. 4 Infrared spectrum of Dye 7 calculated at the M05-2X/6-31G(d) level of theory

References Thus, the atom most likely to suffer a nucleophilic attack is C45.
1. Grtzel M (2006) Photovoltaic performance and long-term stability of dye-sensitized meosocopic solar cells. C R Chimie 9:578583. doi:10.1016/j.crci.2005.06.037 2. Grtzel M (2003) Dye-sensitized solar cells. J Photochem Photobiol C 4:145153. doi:10.1016/S1389-5567(03)00026-1 3. Grtzel M (2004) Conversion of sunlight to electric power by nanocrystalline dye-sensitized solar cells. J Photochem Photobiol A 164:314. doi:10.1016/j.jphotochem.2004.02.023 4. Fan Z, Yan H, Jin S, Xiao Z, Wei L, Chun M, Yong H, Mao F, Zhishan B, Qing M (2009) Triphenylamine-based dyes for dyesensitized solar cells. Dyes Pigments 81:224230. doi:10.1016/j. dyepig.2008.10.012 5. Hwang S, Lee J, Park C, Lee H, Kim C, Park C, Lee M, Lee W, Park J, Kim K, Park N, Kim C (2007) A highly efficient organic sensitizer for dye-sensitized solar cells. Chem Commun 2007:48874889. doi:10.1039/b709859f 6. Buscaino R, Baiocchi C, Barolo C, Medana C, Grtzel M, Nazeeruddin M, Viscardi G (2008) A mass spectrometric analysis of sensitizer solution used for dye-sensitized solar cell. Inorg Chim Acta 361:798805. doi:10.1016/j.ica.2007.07.016 7. Tachan Z, Rhle S, Zaban A (2010) Dye-sensitized solar tubes: a new solar cell design for efficient current collection and improved cell sealing. Sol Energ Mater Sol Cells 94:317322 8. Shen P, Liu Y, Huang X, Zhao B, Xiang N, Fei J, Liu L, Wang X, Huang H, Tan S (2009) Efficient triphenylamine dyes for solar cells: effects of alkyl-substituents and -conjugated thiophene unit. Dyes Pigments 83:187197. doi:10.1016/j.dyepig.2009.04.005 9. Chang Y, Chow T (2009) Dye-sensitized solar cell utilizing organic dyads containing triarylene conjugates. Tetrahedron 65:47264734 10. Casanova D, Rotzinger F, Grtzel M (2010) Computational study of promising organic dyes for high-performance sensitized solar cells. J Chem Theor Comput 6:12191227. doi:10.1021/ct100069q 11. El-Shishtawy R (2009) Functional dyes, and some hi-tech applications. Int J Photoenergy 2009:121. doi:10.1155/2009/ 434897 12. Hagberg D, Edvinsson T, Sun L (2006) A novel organic chromophore for dye-sensitized nanostructured solar cells. Chem Commun 22452247. doi:10.1039/b603002e 13. Parr R, Yang W (1989) Density-functional theory of atoms and molecules. Oxford University Press, Oxford

Conclusions In this work, a general comparison of the optimizations of the molecular structure and the ultraviolet spectrum in THF solvent achieved with different density functionals and basis sets was performed. This comparison indicated that the functional that gave results that were closest to the experimental results was M05-2X, along with the basis set 6-31G(d), so this level of theory was then used to study Dye 7 molecule, which is intended for use in photovoltaic devices. The total energy of this system, its dipole moment,

Fig. 5 HOMO and LUMO orbitals of Dye 7 calculated at the M052X/6-31G(d) level of theory

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