Journal of Molecular Structure: THEOCHEM 899 (2009) 8693

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Journal of Molecular Structure: THEOCHEM

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DFT and TDDFT study on organic dye sensitizers D5, DST and DSS for solar cells
Zhang Cai-Rong a,*, Liu Zi-Jiang b,c, Chen Yu-Hong a, Chen Hong-Shan d, Wu You-Zhi e, Yuan Li-Hua a
a

Department of Applied Physics, Lanzhou University of Technology, Lanzhou, Gansu 730050, China Institute of Applied Physics and Computational Mathematics, Beijing 100088, China Institute of Electronic Information Science and Technology, Lanzhou City University, Lanzhou 730070, China d College of Physics and Electronic Engineering, Northwest Normal University, Lanzhou, Gansu 730070, China e School of Material Science and Engineering, Lanzhou University of Technology, Lanzhou, Gansu 730050, China
b c

a r t i c l e

i n f o

a b s t r a c t
The geometries, electronic structures, polarizabilities and hyperpolarizabilities, and UVvis spectra of organic dye sensitizers D5, DST and DSS were studied by using density functional theory (DFT) and time-dependent DFT. The calculated geometries indicate that the strong conjugated effects are formed in the dyes. The polarizabilities depend on the length of conjugate bridge of the dye. The features of UVvis spectra were assigned to p ! p transitions according to the qualitative agreement between experiment and the TDDFT calculations. The absorption in visible region are all photoinduced electron transfer processes, the diphenylaniline group in D5 and the aniline group in DST and DSS are main chromophore that contributed to the sensitization, the interfacial electron transfer is due to an electron injection processes from excited dyes to semiconductor conduction band. The role of different conjugate bridge in geometries, electronic structures and spectra properties were analyzed in a comparative study of the dyes. Crown Copyright 2008 Published by Elsevier B.V. All rights reserved.

Article history: Received 6 November 2008 Received in revised form 9 December 2008 Accepted 12 December 2008 Available online 24 December 2008 Keywords: Dye sensitizer Electronic structure Density functional theory Absorption spectra

1. Introduction Because of the depletion of fossil fuels, growing demand of energy, global warming and other environmental problems, the development of environmental friendly renewable energy technologies is an urgent task for our human being [1]. Among all the renewable energy technologies, the nanocrystalline dye-sensitized solar cell (DSSC) system, a kind of photovoltaic device that presented by ORegan and Grtzel in 1991, has attracted a lot of attention because of the potential application for low-cost solar electricity [25]. The main parts of DSSC are mesoporous oxide semiconductor layers that composed of nanoparticles and monolayer of dye sensitizers that attached to the surface of the semiconductor nano-lms [3]. The dye sensitizers play an important role in DSSC that have a signicant inuence on the photoelectric conversion and transport performance of electrode [69]. Up to now, two kinds of dye sensitizers, which are generally known as metal-organic complexes and metal-free organic dyes, were studied extensively. In metal-organic complexes, especially the noble metal ruthenium polypyridyl complexes, including N3 and black dye etc. that were presented by Grtzel et al., have proved to be the best dye sensitizers with overall energy conversion efciency greater than 10% under air mass (AM) 1.5 irradiation [1012]. However, the limited metal Ru will become a bottleneck of application if the DSSC is widely used in our daily
* Corresponding author. Tel.: +86 0931 2975185; fax: +86 0931 2976040. E-mail address: zhcrxy@lut.cn (Z. Cai-Rong).

living [13]. On the other hand, metal-free organic dyes as sensitizers for DSSC, including cyanines, hemicyanines, triphenylmethanes, perylenes, coumarins, porphyrins, squaraines, indoline, and azulene-based dyes etc., have also been developed because of their high molar absorption coefcient, relatively simple synthesis procedure, various structures and lower cost [1416]. In contrast to the numerous experimental studies of dye sensitizers, the theoretical investigations are relatively limited. Only several groups focused on the electronic structures and absorption properties of dye sensitizers [1726], and Ru-complexes and organic dyes coupled TiO2 nanocrystalline [2730], as well as the electron transfer dynamics of the interface between dyes and nanocrystalline [3135]. Until now, it remains a severe challenge for both experiment and theory to elucidate the fundamental properties of the ultrafast electron injection [30], and to approach the satised efciency of DSSC. Further developments in dye design will play a crucial part in the ongoing optimization of DSSC [36], and it depends on the quantitative knowledge of dye sensitizer. So the theoretical investigations of the physical properties of dye sensitizers are very important in order to disclose the relationship among the performance, structures and the properties, it is also helpful to design and synthesis novel dye sensitizers with higher performance. Recently, the novel organic dyes polyene-diphenylaniline (D5), 2-((5E)-5-((2-(4-(diethylamino)styryl)thieno[3,2-b]thien-5-yl)methylene)-4-oxo-2-thioxothiazolidin-3-yl) acetic acid (DST), and 2-((5E)-5-((5-((1E)-2-(5-(4-(diethylamino)styryl)thien-2-yl)vinyl)thien-2-yl)methylene)-4-oxo-2-thioxothiazolidin-3-yl) acetic acid

0166-1280/$ - see front matter Crown Copyright 2008 Published by Elsevier B.V. All rights reserved. doi:10.1016/j.theochem.2008.12.015

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(DSS), that containing polyene-diphenylaniline, thienothiophene and thiophene segments, are synthesized, the higher solar energy to electricity conversion efciency of 5.1%, 6.23% and 3.87% were achieved, respectively [37,38]. Furthermore, the dye D5 was designed for future solid state devices with triarylamine on the basis of hole conductors [37,39]. In order to understand the sensitized mechanism, the geometries, electronic structures, along with polarizabilities and hyperpolarizabilities of the dye sensitizers D5, DST and DSS were studied by using density functional theory (DFT), and the electronic absorption spectra were investigated by using time-dependent DFT (TDDFT) calculations [4042]. 2. Computational methods The computations of the geometries, electronic structures, polarizabilities and hyperpolarizabilities, as well as electronic absorption spectra for dye sensitizers D5, DST and DSS were performed using DFT with Gaussian03 package [43]. The DFT was treated according to Beckes three parameter gradient-corrected exchange potential and the Lee-Yang-Parr gradient-corrected correlation potential (B3LYP) [4446], and all calculations were performed without any symmetry constraints by using polarized split-valence 6-31G* basis sets. The electronic absorption spectra require calculation of the allowed excitations and oscillator strengths. These calculations were carried out using TDDFT with the same basis sets and exchange-correlation functional in vacuum and solution, and the non-equilibrium version of the polarizable continuum model (PCM) [47,48] was adopted for calculating the solvent effects.

TDDFT has been used to investigate the absorption properties of clusters and molecules [1720,49,50], including Ru-polypyridine complex in water and ethanol solution [17,18] and Ru(II)L2 [L=bis(50 -methyl-2,20 -bipyridine-6-carboxylato)] in DMF solution [19]. 3. Results and discussions 3.1. The geometric structures The optimized geometries of the dyes D5, DST and DSS are shown in Fig. 1, and the selected bond lengths, bond angles and dihedral angles are listed in Table 1. The similar geometric character induces the similar corresponding geometric parameters of the dyes DSS and DST. We dene L as the distance between the C atom in carboxyl and the N atom in aniline, L could describe the length of conjugate bridge of the dyes D5, DST and DSS. The calculated L is 1.435, 1.677, 2.239 nm for D5, DST, and DSS, respectively, hence the length of conjugate bridge is increased in turn. Furthermore, for D5, the cyanoacrylic acid group was located to be coplanar with the thiophene, vinylene group, and phenyl group in conjugate bridge. For DST and DSS, the methylene-oxo-thoxothiazolidinyl group was located to be coplanar with the styryl group and thieno[b]thienyl, or thienylvinylthienyl group. Thus, the strong conjugated effects are formed. This conjugation is very helpful for efcient electron transfer in the conjugated chains. Similar geometric characters are also appeared in the dye sensitizers JK-1 and JK-2 [51], JK16 and JK17 [52,53], the dyes 1 and 2 [54,55].

Fig. 1. Optimized geometrical structures of dyes D5, DST and DSS with atomic serial numbers. (The blue colored spheres: N; the yellow colored spheres: S; the red colored spheres: O; the larger dark colored spheres: C; the smaller light colored spheres: H). (For interpretation of the references to colour in this gure legend, the reader is referred to the web version of this article.)

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Table 1 Selected bond lengths (in nm), bond angles (in degree) and dihedral (in degree) of the dyes D5, DST and DSS. D5 619 1019 1319 2627 320 2122 61910 61913 32021 262728 261910 6191315 27283132 0.141 0.143 0.143 0.142 0.145 0.144 120.6 120.7 127.4 129.9 32.7 46.7 0.0 DST 23 34 36 912 2022 2223 2630 236 91213 202223 272630 23610 25263031 0.147 0.146 0.139 0.145 0.143 0.137 0.145 118.2 127.7 132.8 118.9 176.0 95.9 DSS 23 34 36 912 3435 2022 2630 236 91213 333435 202223 23610 25263031 0.147 0.147 0.139 0.145 0.144 0.143 0.145 118.1 127.7 125.9 132.7 177.1 96.3

Fig. 2. The frontier molecular orbital energies of the dyes D5, DST and DSS.

3.2. Electronic structures and charges Natural Bond Orbital (NBO) analysis was performed in order to analyze the charge populations of the dyes D5, DST and DSS. For the dye D5, the natural charges of cyaniarylic acid, thiophene, vinylene and diphenylaniline are 0.18, 0.08, 0.04, and 0.06e, respectively. Thus, the natural charges of donor (diphenylaniline group), bridge (vinylene thiophene) and acceptor (cyaniarylic acid) are 0.06, 0.12 and 0.18e, respectively. While for DST, the natural charges of acetic acid, diethylamino, styryl, thieno[b]thienyl, oxothioxothiazolidinyl and methylene groups are 0.28, 0.00, 0.11, 0.08, 0.53 and 0.07e, respectively. Similarly, for DSS, the natural charges of acetic acid, diethylamino, styryl, thienylvinylenethienyl, oxo-thioxothiazolidinyl and methylene groups are 0.28, 0.01, 0.09, 0.10, 0.53 and 0.07e, respectively. The above data reveal that the diethylamino group in DST and DSS is not an effective electron donor unit, the electron donor unit is styryl group, and the oxo-thioxothiazolidinyl group is a strong pull-electron group. The dye sensitizers D5, DSS and DST are all donor-bridge-acceptor system. Furthermore, the natural charges of donor and acceptor for D5 are larger than that of similar dye sensitizers 2 [55], JK17 [53]. This indicates that there are some electrons transferred from the electron donor group to the electron acceptor group through chemical bonds, thus the electron-hole pair was formed in the molecule. The frontier molecular orbitals (MO) energies of the dyes D5, DST and DSS are shown in Fig. 2. For D5, the highest occupied MO (HOMO), lying at 5.14 eV, is a delocalized p orbital over the cyano group through diphenylaniline. The HOMO-1, lying 0.84 eV below the HOMO, is a delocalized p orbital over the entire molecule. While the HOMO-2 and HOMO-3, lying 1.83, 1.92 eV below the HOMO, respectively, are p orbitals that localized in benzene ring. Whereas, the lowest unoccupied MO (LUMO), lying at 2.66 eV, is p orbital that localized in cyanoacrylic acid, vinylene thiophene, and phenyl in aniline. The LUMO+1, lying about 1.31 eV above the LUMO, is also a p orbital that is similar to LUMO. The MOs that calculated with B3LYP/6-31+G* are very similar to the present calculations [37]. As to the dye DST, the HOMO, lying at 4.97 eV, is a delocalized p orbital over the oxo-thioxothiazolidinyl group through aniline. The HOMO-1, lying 0.83 eV below the HOMO, is similar to HOMO. The HOMO-2, lying 1.24 eV below the HOMO, is localized in thieno[b]thienyl group. But the HOMO-3, lying 1.53 eV below the HOMO, is localized in oxo-thioxothiazolidinyl group, especially the lone pair orbital in S29 atom. While the LUMO, lying at 2.74 eV, is a p orbital that mainly localized in vinylene, thieno[b]thienyl, and oxo-thioxothiazolidinyl group. The LUMO+1, lying about 1.20 eV above the LUMO, is also p orbital that is similar to LUMO. For the dye DSS, the HOMO is lying at 4.80 eV and the LUMO is lying at 2.84 eV, the HOMO-1 $ LUMO+1 and HOMO-3 are similar to that of DSS if the thienyl-vinylene-thienyl group in DSS was substituted for the thieno[b]thienyl group in DST. But the HOMO-2 for DSS is p orbital that is primarily composed of aniline, vinylene, thienyl-vinylene-thienyl and oxo-thioxothiazolidinyl group. The HOMOLUMO gap of the dye D5, DST and DSS in vacuum is 2.48, 2.23 and 1.96 eV, respectively. The smaller HOMOLUMO gap of the dye DSS is resulted from the thienylvinylenethienyl group. It induces that the density of states near fermi level of the dye DSS is more abundant than that of the dye DST. While the calculated HOMO and LUMO energies of the bare Ti38O76 cluster as a model for nanocrystalline are 6.55 and 2.77 eV, respectively, resulting in a HOMOLUMO gap of 3.78 eV, the lowest transition is reduced to 3.20 eV according to TDDFT, and this value is slightly smaller than typical band gap of TiO2 nanoparticles with nm size [20]. Furthermore, the HOMO, LUMO and HOMOLUMO gap of (TiO2)60 cluster is 7.52, 2.97, and 4.55 eV (B3LYP/VDZ), respectively [56]. Taking into account of the cluster size effects and the calculated HOMO, LUMO, HOMOLUMO gap of the dyes D5, DSS and DST, Ti38O76 and (TiO2)60 clusters, we can nd that the HOMO energies of these dyes fall within the TiO2 gap. The above data also reveal the sensitized mechanism: the interfacial electron transfer between semiconductor TiO2 electrode and the dye sensitizers D5, DST and DSS are electron injection processes from excited dyes to the semiconductor conduction band. This is a kind of typical interfacial electron transfer reaction [57]. 3.3. Polarizability and hyperpolarizability Polarizabilities and hyperpolarizabilities characterize the response of a system in an applied electric eld. They determine not only the strength of molecular interactions (such as the longrange intermolecular induction, dispersion forces, etc.) as well as the cross sections of different scattering and collision processes, but also the nonlinear optical properties (NLO) of the system [58,59]. It has found that dye sensitizer hemicyanine system, which has good NLO property, usually possesses good photoelectric conversion performance [60]. In order to investigate the relationships among photocurrent generations, molecular structures and NLOs, the polarizabilities and hyperpolarizabilities of the dyes D5, DST and DSS were calculated. Finite led (FF), sum-over states method based on TDDFT (SOS), and coupled-perturbed HF (CPHF) method could be used to compute polarizabilities and hyperpolarizabilities. However, the use of FF, SOS and CPHF methods with large sized basis sets for dye

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molecules are too expensive. Here, we compute the polarizabilities and the rst hyperpolarizabilities as a numerical derivative of the dipole moment using B3LYP/6-31G(d). The denitions [58] for the isotropic polarizability is

absorption bands with longer wavelength in visible region are weaker than that with shorter wavelength in visible or near-UV region, and the absorption bands of DSS have red-shift relative to that of DST. These tendencies (the calculated line shape and relative

a aXX aYY aZZ

the polarizability anisotropy invariant is

1 3

Da

" #1 2 aXX aYY 2 aYY aZZ 2 aZZ aXX 2 2

and the average hyperpolarizability is

bjj

1X biiZ biZi bZii 5 i

Tables 2 and 3 list the values of the polarizabilities and hyperpolarizabilities of the dyes D5, DST and DSS. In addition to the individual tensor components of the polarizabilties and the rst hyperpolarizabilities, the isotropic polarizability, polarizability anisotropy invariant and hyperpolarizability are also calculated. The calculated isotropic polarizability of D5, DST and DSS is 510.6, 611.2 and 802.9 a.u., respectively. However, the calculated isotropic polarizability of JK16, JK17, dye 1 and dye 2 is 759.9, 1015.5, 694.7 and 785.7, respectively (B3LYP/6-31G*) [53,55]. The above data indicate that the donor-conjugate p bridge-acceptor (D-p-A) chain-like dyes have stronger response for external electric eld. Whereas, for dye sensitizers D5, DST, DSS, JK16, JK17, dye 1 and dye 2, on the basis of the published photo-to-current conversion efciencies, the similarity and the difference of geometries, and the calculated isotrpic polarizabilities, it is found that the longer the length of the conjugate bridge in similar dyes, the larger the polarizability of the dye molecule, and the lower the photo-to-current conversion efciency. This may be resulted from that the longer conjugate p bridge enlarged the delocalization of electrons, thus it enhanced the response of the external eld, but the enlarged delocalization may be not favorable to generate charge separated state effectively. So it induces the lower photo-to-current conversion efciency. 3.4. Electronic absorption spectra and sensitized mechanism The UVvis spectra of the dyes D5, DST and DSS were measured in MeCN, THF and THF solution, respectively, and it is found that the absorption bands centered at 476, 488 and 513 nm in visible region, respectively [37,38]. In order to understand electronic transitions of D5, DST and DSS, TDDFT calculations on electronic absorption spectra in vacuum and solvent were performed, the 50 lowest spin-allowed singletsinglet transitions were taken into account. The results are shown in Fig. 3. It is seen that, for D5, DST and DSS, the

Table 2 Polarizability (a) of the dyes D5, DST and DSS (in a.u.). Dyes D5 DST DSS

aXX
986.6 355.0 1468.1

aXY
129.2 152.5 179.2

aYY
317.2 1295.7 252.0

aXZ
32.7 3.0 628.7

aYZ
72.1 177.2 27.6

aZZ
228.1 183.0 688.4

a
510.6 611.2 802.9

Da
718.1 1037.4 1067.0

Fig. 3. Calculated electronic absorption spectra of the dyes D5, DST and DSS.

Table 3 Hyperpolarizability (b) of the dyes D5, DST and DSS (in a.u.). Dyes D5 DST DSS bXXX 57714 546 111120 bXXY 10854 1481 9563 bXYY 1483 10110 962 bYYY 16 74831 146 bXXZ 710 214 64628 bXYZ 569 1590 5173 bYYZ 232 11733 517 bXZZ 456 235 38289 bYZZ 129 1774 2780 bZZZ 17 239 22953 b== 575 7311 52859

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strength) agree well with that of experiment. Compared with the results of experiment [37,38], the results of TDDFT have appreciable red-shift, and the degree of red-shift in solvent is more signicant than that in vacuum. Similar results are also found for several dye sensitizers [19,6163]. The discrepancy between experiment and TDDFT calculations may be attributed to two aspects [53]. The rst involves DFT, it always give smaller gap of materials [64], and thus generate smaller excited energies, especially larger conjugate system and charge transfer complex in excited states [65]. The other is solvent effects. Solvent, especially polar solvent such as MeCN and THF, could affect the geometry and electronic structure as well as the properties of molecule through the long-range interaction between solute molecule and solvent molecule, thus solvent effects induce the lower energy of the solute molecules, and generate more signicant red-shift for absorption bands. So it is very difcult to make the theoretical calculation be consistent with the experimental data quantitatively. Though the discrepancy is existed, the TDDFT calculations are capable of describing the spectral features of D5, DST and DSS because of the qualitative agreement of line shape and relative strength as compared with experiment. The HOMOLUMO gap of D5, DST and DSS in solvent (D5: HOMO = 4.96 eV, LUMO = 2.68 eV, HOMOLUMO gap is 2.28 eV; DST: HOMO = 4.89 eV, LUMO = 2.83 eV, HOMOLUMO gap is 2.06 eV; DSS: HOMO = 4.72 eV, LUMO = 2.91 eV, HOMOLUMO gap is 1.79 eV) are smaller than that in vacuum. The above data indicate that the solvent effects stabilize the LUMO and destabilize the HOMO of the dyes, so it induces the red-shift of the absorption as compared with that in vacuum. In order to obtain the microscopic information about the electronic transitions, we check the corresponding MO properties. The absorption in visible and near-UV region is the most important

region for photo-to-current conversion, so only the singlet ! singlet transitions of the absorption bands with the oscillator strength larger than 0.01 and the wavelength longer than 300 nm were listed in Table 46. Fig. 4 shows the isodensity plots of the frontier MOs of the dyes D5, DST and DSS. For D5, the transition energies and oscillator strengths that were calculated by using B3LYP/631+G* in vacuum agree well the results of B3LYP/6-31G* in vacuum (see Table 4). The absorption band near 603 nm of simulated spectra in MeCN resulted from the electron transitions from initial state that is mainly contributed by the HOMO to nal state that is mainly contributed by the LUMO. While the absorption band near about 415 nm is composed by the second transition. For this transition, the starting orbitals are the two HOMOs and the nal states involve the rst two LUMOs. On the basis of the above analysis of transitions and MOs, the two absorption bands of the D5 in visible region are typical p ! p transitions. Furthermore, the transitions of the absorption bands in visible region are mainly related to HOMO-1 $ LUMO+1. In these transitions, the initial states are mainly related to the MOs that localized in electron donor groups, while the nal states are mainly related to the MOs that localized in electron acceptor groups. This indicates that the absorptions are photoinduced electron transfer processes, thus the excitations generate charge separated states. It is worthy to be noted that the HOMO-3 $ HOMO of the D5 are related to the diphenylaniline group, so this group is major chromophore that contributed to the sensitization of photo-to-current conversion processes. For DST, the absorption band near 661 nm of simulated spectra in THF resulted from the electron transitions from initial state that is mainly contributed by the HOMO to nal state that is mainly contributed by the LUMO. While the absorption band near about 456 nm is composed by the second transition. For this transition,

Table 4 Computed excitation energies, electronic transition congurations and oscillator strengths (f) for the optical transitions with f > 0.01 of the absorption bands in visible and nearUV region for the dye D5 in MeCN. State 1 Congurations composition with |CI Coeff.| > 0.2 (corresponding transition orbitals)a 0.658(117!118) Excitation energy (eV/nm) 2.06/603 2.31/537b 2.26/548c 2.99/415 3.15/393b 3.10/399c 3.38/366 3.91/317 4.01/309 4.01/309 4.04/307 4.07/305 4.13/300 f 1.2152 1.1457b 1.17c 0.7704 0.7917b 0.78c 0.1035 0.0326 0.0169 0.0568 0.0715 0.0315 0.0643

0.628(116!118); 0.214(117!119)

3 6 7 8 9 10 11
a b c

0.627(117!119) 0.594(117!120); 0.524(113!118); 0.430(117!121); 0.456(112!118); 0.627(110!118); 0.494(112!118);

0.322(114!118) 0.254(111!118); 0.252(116!119) 0.370(111!118); 0.294(113!118) 0.412(117!121); 0.254(111!118) 0.203(116!119) 0.428(111!118); 0.240(117!121)

HOMO is No.117 orbital. Calculated by using TD B3LYP/6-31G* in vacuum. Calculated by using TD B3LYP/6-31+G* in vacuum [18].

Table 5 Computed excitation energies, electronic transition congurations and oscillator strengths (f) for the optical transitions with f > 0.01 of the absorption bands in visible and nearUV region for the dye DST in THF. State 1 2 4 5 6 7 8 10
a

Congurations composition with |CI Coeff.| > 0.2 (corresponding transition orbitals)a 0.647(130 ! 131) 0.617(129 ! 131); 0.256(130 ! 132) 0.611(130 ! 132) 0.669(128 ! 131) 0.642(130 ! 133) 0.627(126 ! 131); 0.236(129 ! 132) 0.658(130 ! 134) 0.608(129 ! 132)

Excitation energy (eV/nm) 1.88/661 2.72/456 3.05/407 3.19/388 3.52/353 3.53/351 3.65/340 3.90/318

f 1.5758 0.6274 0.1532 0.0480 0.1262 0.0168 0.0274 0.0329

HOMO is No. 130 orbital.

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Table 6 Computed excitation energies, electronic transition congurations and oscillator strengths (f) for the optical transitions with f > 0.01 of the absorption bands in visible and nearUV region for the dye DSS in THF. State 1 2 3 5 6 12 13 16 17
a

Congurations composition with |CI Coeff.| > 0.2 (corresponding transition orbitals)a 0.653(144 ! 145) 0.612(143 ! 145); 0.597(144 ! 146); 0.607(142 ! 145); 0.658(144 ! 147) 0.563(137 ! 145); 0.443(144 ! 149); 0.410(142 ! 146); 0.478(134 ! 145); 0.274(144 ! 146) 0.230(143 ! 145) 0.257(143 ! 146) 0.316(144 ! 149) 0.302(137 ! 145); 0.203(138 ! 145) 0.366(134 ! 145); 0.259(136 ! 145) 0.372(142 ! 146)

Excitation energy (eV/nm) 1.63/762 2.37/523 2.67/465 3.08/403 3.21/387 3.78/328 3.87/320 4.09/303 4.11/302

f 1.5854 0.9319 0.2407 0.0759 0.1577 0.1323 0.0349 0.0234 0.0171

HOMO is No.144 orbital.

Fig. 4. Isodensity plots (isodensity contour = 0.02 a.u.) of the frontier orbitals of the dyes D5, DST and DSS.

the starting orbitals are the two HOMOs and the nal states involve the rst two LUMOs. On the basis of the above analysis of transitions and MOs, the two absorption bands of the DST in visible region are typical p ! p transitions. Furthermore, the transitions of the absorption bands in visible region are mainly related to HOMO-1 $ LUMO+1. In these transitions, the initial states are mainly related to the MOs that delocalized over the oxo-thioxothiazolidinyl group through aniline, while the nal states are mainly related to the MOs that localized in vinylene, thieno[b]thienyl, and oxo-thioxothiazolidinyl group. This indicates that the absorptions are photoinduced electron transfer processes, thus the excitations generate charge separated states. The differences among the HOMO-2 $ LUMO+1 of the DST indicate that the aniline group is major chromophore that contributed to the sensitization of photo-to-current conversion processes. Similarly, the differences among the HOMO-2 $ LUMO+1 of the DSS also indicate that the aniline group is major sensitized chromophore of photo-to-current conversion. Compared with the dye DST, the thienylvinylenethienyl group in the DSS generates more abundant distributions of the frontier MOs and the smaller HOMOLUMO gap. This is just the reason of

absorption bands of the dye DSS has a red-shift relative to the dye DST. Usually, if the absorption bands are close to infrared region, it is expected that the dyes have higher photo-to-current efciency. But the experiment reported that the conversion efciency of the dye DSS is lower than that of the dye DST. What is the reason about this? The thienylvinylenethienyl group is more exible than the thieno[b]thienyl group, and it may be induced DSS isomers with no-planar conjugate bridge though the isomerization is not taken into account the present calculation. The no-planar conjugate bridge is not favorable to electron transport from the electron donor to semiconductor surface. Furthermore, the thienylvinylenethienyl group changes the absorption properties of the dye DSS more suitable for sun spectrum, but it is also enlarged the distance between electron donor group and semiconductor surface, and therefore reduces the possibility of a dye p orbital delocalized on the nanocrystalline surface, and decreases the electronic coupling between the chromophore and TiO2 substrates [29]. The weak electronic coupling may result in electron injection times that are slow. On the basis of above analysis, the thienylvinylenethienyl group in DSS decreased the electron injection rate relative to the thieno[b]thienyl group in DST, thus induced the smaller short circuit

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photocurrent density Jsc (15.23 mA cm2 for the dye DST, 10.64 mA cm2 for the dye DSS [38]) and open circuit photovoltage Voc (0.73 V for the dye DST, 0.70 V for the dye DSS [38]), and then gave lower conversion efciency. On the other hand, the excited state oxidation potential of dye DST is more negative than that of dye DSS [38], it may be favor the electron injection process, and thus the larger Jsc and Voc were generated. So we can concluded that the appropriate conjugate bridge in dye sensitizer is also very important for improve the performance of DSSC. The above analysis could also elucidate why the conversion efciency of the dye JK16 is higher than that of the dye JK17, and the conversion efciency of the dye 1 is higher than that of the dye 2. 4. Conclusions The geometries, electronic structures, polarizabilities and hyperpolarizabilities of the dyes D5, DST and DSS were studied by using density functional theory with hybrid functional B3LYP, and the UVvis spectra were investigated by using TDDFT methods. The calculated geometric characters indicate that the strong conjugated effects across the conjugated bridge are formed in the dyes D5, DST and DSS. The NBO results suggest that dyes D5, DST and DSS are all D-p-A systems, and the electron donor is diphenylaniline, styryl and styryl groups, respectively, the conjugated bridge is vinylene thiophene, thieno[b]thienyl and thienylvinylenethienyl, respectively, the oxo-thioxothiazolidinyl group in DST and DSS is a strong pull-electron group. The calculated polarizabilities of the dyes indicate that the longer the length of conjugate bridges for the similar dyes, the larger the polarizability of the dye molecule, and the lower the photo-to-current conversion efciency. The features of electronic absorption spectra in visible and near-UV region were assigned, and the absorptions are all ascribed to p ! p transitions according to the qualitative agreement between the experiment and the TDDFT calculations. The absorption bands in visible region of the dyes D5, DST and DSS are all photoinduced electron transfer processes, thus the excitations generate charge separated states, and the diphenylaniline group in D5 and the aniline group in DST and DSS are main chromophore that contributed to the sensitization of photo-to-current conversion processes, the interfacial electron transfer between semiconductor TiO2 electrode and the dye sensitizers D5, DST and DSS is electron injection processes from excited dyes to the semiconductor conduction band. In virtue of the comparative analysis of geometries, electronic structures and spectra properties between the dyes DST and DSS, the role of thienyl-vinylene-thienyl and thieno[b]thienyl groups are cognized as followings: the longer conjugated bridge enlarged the distance between electron donor group and semiconductor surface, reduced the electronic coupling, decreased the electron injection rate and change the excited state oxidation potential, then resulted in lower conversion efciency. So it indicates that the choice of the appropriate conjugate bridge in dye sensitizer is very important for improve the performance of DSSC. Acknowledgements This work supported by National Natural Science Foundation of China (Grant No. 10647006), Prominent Youth Foundation (Grant No.Q200704) and Scientic Developmental Foundation of Lanzhou University of Technology. Zhang C.R. would like to thank professor Liang W.Z. (USTC), and Gansu Supercomputer Center is also appreciated. References
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