Electronic structure,absorption spectra,and hyperpolarisabilities of some novel push–pull zinc porphyrins. A DFT/TDDFT study

DFT/TDDFT calculations have been performed on some novel push–pull zinc porphyrins (denoted ZnPor 1, ZnPor 2, and ZnPor 3). This theoretical work aims to investigate the electronic structure, absorption spectra, and hyperpolarisabilities of these molecules. To examine the effects of the peripheral substituents on the molecular properties, zinc porphine (ZnP) and zinc tetraphenylporphine (ZnTPP) were also included in the study. The orbital energy level patterns of the substituted zinc porphyrins are indeed rather different from those of ZnP and ZnTPP. The peripheral substitution breaks the molecular D_4h symmetry of the porphyrin, thereby leading to the splitting of the absorption Q band. On the other hand, the B band in the spectra may not arise only from a single excited state; instead, it could be made up of several states that are close in energy. The calculated hyperpolarisabilities (β _vec) increase strongly from ZnPor 1 to ZnPor 2 to ZnPor3. The latter two molecules were predicted to have a large β _vec value and thus may have potential application in the development of nonlinear optical (NLO) materials.     

Nonlinear optical activity of imino-dyes with furan,thiophene or thiazole moieties as π-conjugated bridge: a computational investigation

ABSTRACT

The electronic, linear and nonlinear optical properties of some heterocycle-containing imino-dyes, namely, the synthesised dyes 1–3 and the designed dye 4, were evaluated using suitable long-range corrected DFT functionals. HOMO–LUMO gaps, dipole moments, polarisabilities, and first hyperpolarisabilities were calculated using CAM-B3LYP, ωB97XD and LC-ωPBE methods combined with the 6-311++G(d,p) basis set using CAM-B3LYP/6-31G(d,p) optimised geometries. The calculated molecular hyperpolarisabilities, µβ, increase in the order 1?<?2?<?3 as expected experimentally. The enhancement of µβ when passing from dye 1 to dye 2 is due to the replacement of furan by thiophene and the increase of µβ when passing from dye 2 to dye 3 is due to the change of the thiophene position from the acceptor side to the donor side. Interestingly, the replacement of thiophene (dye 2) by thiazole (dye 4) leads to a notable increase of the NLO response. The electronic transitions data of dyes 1–4 were calculated at the CIS/6-31G(d,p) level of theory and the predicted order 1?<?2<3?<?4 of µβ values is conveniently explained using the two-level model based on the calculation of the dipole moment absolute change, |Δµ_EG |, from the ground to the excited state. Consequently, dye 4 could be a promising candidate for organic NLO devices.     

Nonlinear optical and structural properties of M@C N endohedrals (M = Li,Ca and Sc,N = 60 and 70)

We have investigated the static (ω = 0) and frequency-dependent nonlinear optical (NLO) properties of the M@C _N endohedrals (M = Li, Ca, Sc, N = 60 and 70) using the SSH (Su–Schrieffer–Heeger) approximation and sum-over-state (SOS) approach. Also, we study the effects of displacement and alkali, alkaline earth and lanthanide metal atoms and type of cage on the hyperpolarisabilities of the M@C _N endohedrals. The hyperpolarisability magnitudes and spectra are in agreement with experiment and the work of others using the SSH approximation. Our results indicate that the cage-type effect on the NLO spectra of M@C _N endohedrals is dramatic. Also, atom type has little effect on the highest peak value. These relationships between the atom and cage type and hyperpolarisability values may be beneficial to experimentalists when designing new NLO materials with large NLO responses.     

Theoretical study on the static and dynamic first-order hyperpolarisabilities of adenine tautomers

Static and dynamic electronic and vibrational first-order hyperpolarisabilities (β) of the lowest energy neutral adenine tautomers (amine forms A7 and A9) were obtained in gaseous and aqueous phases by using Hartree–Fock, Møller–Plesset second-order and fourth-order perturbation theory (MP2 and MP4-SDQ) and conventional and long-range corrected density functional theory methods with the Dunning's correlation-consistent cc-pVDZ, aug-cc-pVDZ, aug-cc-pVTZ and d-aug-cc-pVDZ basis sets. Frequency-dependent properties were calculated at the characteristic wavelength of the Nd:YAG laser (1064 nm) for the second harmonic generation and electro-optical Pockels effect nonlinear optical processes. Solvent effects were introduced under the polarised continuum model approximation. The electronic β^e values of the investigated isomers are noticeably affected by the theoretical level, basis set and solvation. In vacuum, the static and dynamic β^e values of A9 are greater than the corresponding data of A7, whereas the contribution of the solvent significantly enhances the hyperpolarisabilities of the A7 tautomer, resulting in β^e(A9)/β^e(A7) ratios between 0.5 and 0.6. The vibrational hyperpolarisabilities of the adenine tautomers are quite close to each other.     

DFT-based study of the impact of transition metal coordination on the charge transport and nonlinear optical (NLO) properties of 2-{[5-(4-nitrophenyl)-1,3,4-thiadiazol-2-ylimino]methyl}phenol

Theoretical investigations of the impact of transition metal chelation on the electron/hole-transport and nonlinear optical (NLO) properties of 2-{[5-(4-nitrophenyl)-1,3,4-thiadiazol-2-ylimino]methyl}phenol (L) are reported herein. Calculations were carried out via density functional theory (DFT)-based methods, employing exchange–correlation functionals and basis sets of different qualities. Results have shown that free L is a moderate electron/hole-transporter, but that its Pd(II) and Pt(II) complexes are excellent hole- and electron-transport materials respectively, owing to their very small reorganisation energies and relatively large electronic coupling matrix elements or transfer integrals. These results indicate that the complexes are potentially suitable charge transport materials for the construction of organic light emitting diodes (OLEDs). Nevertheless, the results also revealed a higher NLO activity for L than its metal complexes. Interestingly, the first and second hyperpolarizabilities, along with some computed NLO properties of both L and its complexes are found to be remarkably higher than those of the prototypical push–pull molecule, para-nitroaniline. Accordingly, these compounds are potential candidates for the fabrication of optoelectronic and photonic devices for second- and third-order NLO applications. Summarily, metal chelation is found to enhance the charge transport properties in some cases, and to slightly diminish NLO response of L in all cases investigated.     

Theoretical study on the nonlinear optical properties of phenylenes and influencing factors

A systematic investigation of the hyperpolarisabilities of substituted p‐poly‐phenylenes is presented using different quantum mechanical approaches, including density functional theory and Møller–Plesset (MP2) methods. A medium‐sized basis set Hartree–Fock (HF) hyperpolarisability calculation based on either a density functional theory (DFT) or MP2 geometry gives reliable results at moderate computational costs when comparing with experimental data. A longer phenylene chain leads to a maximum in the per‐unit increase of the investigated property between 3 and 4 repeat units. Changing the underlying geometry from the minimum helix to a planar orientation leads to a significant increase in β, again dependent on the chain length. Terminal para‐substituents and their influence are studied and categorised. For push–pull groups, the substituent effects are mainly additive, allowing the design of functionalised phenylenes as molecular building blocks for nanofibres with tailored nonlinear optical (NLO) properties. Copyright © 2008 John Wiley & Sons, Ltd.     

Probe the accumulation modes of the Au–C22H14 dimer on the structure and NLO properties

In 2006, the Au–C₂₂H₁₄ with a covalent bond between an individual pentacene (C₂₂H₁₄) and a gold (Au) atom was synthesised and characterised, and its nonlinear optical (NLO) properties were explored. To further investigate the NLO properties from molecules to materials, three kinds of different dimers (Au–C₂₂H₁₄)₂ (2, 3 and 4) were designed to probe the monomer accumulation modes on the structures and NLO properties. The results indicate that Au atoms doping breaks the conjugate structures of the two pentacenes to different extent. On the other hand, their NLO properties investigated by three density functional theory methods Becke-Half-and-Half-LYP (BHandHLYP), Coulomb-attenuating method Becke-3-Lee–Yang–Parr (CAM-B3LYP) and Minnesota 2005 double the amount of nonlocal exchange (M05-2X) show the same order, and 2 has the largest first hyperpolarisability (β_tot) than the other molecules. At the same time, natural bond orbital analysis shows the Au atoms play a crucial role in pushing electron density. Meanwhile, the frontier molecular orbital analysis shows that charge transfer has occurred between the two pentacene molecules and Au atoms. As a result, the order of transition energy is opposite to the order of β_tot values. Because the pentacene is taken as a simplified fragment of the graphene, our present work may be beneficial to the development of high-performance NLO materials.     

Computational study of linear and nonlinear optical properties of substituted thiophene imino dyes using long-range corrected hybrid DFT methods

The molecular structures, linear and nonlinear optical properties of a series constituted by four R-substituted thiophene imino dyes, namely A(R?=?SO₂Me), B(R?=?SO₂Ph), C(R?=?NO₂), and D(R?=?C₂(CN)₃) were analysed using CAM-B3LYP, ωB97XD and LC-ωPBE hybrid DFT functionals in combination of the 6-311++G(d,p) standard basis set. The dipole moments, polarisabilities, HOMO-LUMO energy gaps, maximum absorption wavelengths and first hyperpolarisabilities were calculated in the gas phase and the obtained results are in good agreement with experimental NLO activity order A?<?B?<?C. Compared to synthesised dyes A-C, the designed dye D presents a longer maximum absorption wavelength and a lower HOMO-LUMO gap because of the appreciable stabilisation of its LUMO energy. These results were confirmed by the calculation of the total second-order stabilisation energy E⁽²⁾ defined in the context of the NBO population analysis. Consequently, dye D is predicted to exhibit a higher first hyperpolarisability in comparison with dyes A-C. This result can be justified by the enhanced intramolecular charge transfer in dye D due to the stronger electron-withdrawing ability and the cumulative action of the long π-conjugation of the tricyanovinyl moiety. The very high total hyperpolarisability (27 times greater than that of para-nitroaniline) of the designed dye D suggests its promising use in organic NLO devices.     

Potential use of small basis set on the calculations of electronic properties of some four-membered heterocycles: a conformational study

The potential use of small basis sets upon a low level of theory was studied on the calculations of electronic properties (dipole moment, static polarisability and static hyperpolarisabilities) of a series of 16 four-membered heterocycles with an exocyclic double bond at the position 3 (1–16). First, the calculations were performed within the Hartree–Fock (HF) approximation using 6-31G, 6-31G(d,p) and 6-31+G(d,p) as basis sets for the different conformational states of each molecule, and the results obtained were compared with the MP2/6-31+G(d,p) results reported. In the second place, in order to know the real potential of HF calculations, these were compared with those calculated using larger approaches such as MP2/6-311+G(d,p), MP2/aug-cc-pVDZ, CCS/6-311+G(d,p), CCS/aug-cc-pVDZ, CCS/aug-cc-pVTZ, CCSD/6-31+G(d) and CCSD/cc-pVDZ, taken into account only the planar and equilibrium geometries of each molecules. The HF approaches permit us to obtain a good qualitative representation of the dipole moment as a function of puckering angle in comparison with MP2, CCS and CCSD levels for all tested molecules. However, only HF/6-31+G(d,p) provides quantitative values of dipole moment for the heterocycles 1, 5 and 13 in comparison with MP2, CCS and CCSD levels. On the other hand, the polarisability and hyperpolarisabilities were quite sensitive to the quality of level of theory and basis sets. In particular, HF/6-31+G(d,p) predicted a representative approximation of alpha for the molecule 16 in comparison with larger methods as MP2/aug-cc-pVDZ, CCS/aug-cc-pVDZ and CCS/aug-cc-pVTZ, while a detailed analysis showed that HF can be used in the calculation of alpha for the molecules 3, 7, 11 and 15, but it requires the use of extended basis sets. Also, HF/6-31+G(d,p) predicted values of beta very similar to those calculated at the MP2 and CCSD levels used, for the planar and equilibrium geometry of the molecules 10 and 14. Furthermore, HF/6-31+G(d,p) described a representative dependence of this property with the puckering angle for the heterocycles 9, 10 and 14, compared with the MP2 curves.     

NLO characteristics of D-π-A coumarin-thiophene bridged azo dyes by Z-scan and DFT methods

ABSTRACT

The structural, electronic, intramolecular charge transfer (ICT) and nonlinear optical (NLO) properties of the donor-π-acceptor (D-π-A) azo linked dyes bearing coumarin thiophene bridge with different acceptors were inspected by Z-scan and DFT methods. The dye 3a exhibits bathochromic absorption maxima (649 and 650?nm) in the near IR region in DMF and DMSO. The dye 3a holds low HOMO–LUMO gap elucidated by CV and DFT indicating strong ICT character. The thermal stability is high for 3a and it shows enhanced NLO property by Z-scan and DFT methods as predicted in both global and range-separated hybrid functionals. The molecular geometry was optimised using B3LYP/6-311?+?g(d,p). The ICT characteristics are correlated with NLO properties obtained by Z-scan and DFT techniques.     

Structural,electrical and optical properties of gamma irradiated methyl para-hydroxy benzoate single crystals

ABSTRACT

Nonlinear optical materials (NLO) have been garnering attention due to their role in optical data storage, optical communication and laser technology. Organic crystals have emerged as an extremely important class of NLO materials, since their NLO properties compare very well with traditional inorganic NLO materials like KCl, LiNbO₃, KDP (potassium dihydrogen phosphate), etc. They offer the additional advantage that they can be grown relatively inexpensively from solution close to room temperature, unlike the inorganic NLO materials which are grown from high temperature melts. In the present work, organic transparent single crystals of methyl para-hydroxy benzoate (MHB) were grown by slow evaporation solution growth technique (SEST) from aqueous solution at room temperature. The changes in structural, electrical and optical properties of gamma irradiated MHB single crystals were studied using X-ray diffraction (XRD), UV–Visible absorption spectroscopy, Photo-luminescence (PL), Fourier transform infrared (FTIR) spectroscopy and AC conductivity measurements at room temperature. The polished MHB single crystals were irradiated with gamma rays of doses 10 and 15 kilogray (kGy). From the XRD analysis, it was observed that gamma irradiation for these doses drastically decreases the crystallinity. The optical absorption constants were examined by UV-Visible absorption spectroscopy, measured over the wavelength range of 200–800?nm, at normal incidence. The optical band gap as estimated from the Tauc plot ((αhν)² vs hν) was found to be reduced with increasing gamma irradiation doses. PL spectra showed emission at wavelengths of 361?nm (3.43?eV) and 452?nm (2.74?eV), with enhanced intensities for the irradiated crystals. FTIR spectroscopy was utilised to identify the functional groups of MHB and indicated the rupture of specific types of bonds with gamma irradiation. Apart from that, the enhancement of AC conductivity with gamma irradiation was also observed for the gamma irradiated crystals.     

Closed loops theory on the third-order nonlinear optical property of α- and β- isomers of [M8O26]4−: a TDDFT study

The third-order nonlinear optical (NLO) property of the α- and β- isomers of [Mo₈O₂₆]^4? polyoxometallate ion were studied by DFT/TDDFT method. The second static hyperpolarisabilities, γ_iiii, γ_iijj and γ_mean were calculated by finite-field method as an extension of the usual DFT run, and the results suggest that without any ligands coordinated, the two isomer molecules in high symmetry own modestly large γ values (γ_mean ～5×10^?32esu, 3×10^?32esu, respectively), and the electronic properties of the two isomers were also studied by DFT method for the discussion of the origination of the NLO response, especially the unique effect of the molecular orbital ‘closed loops' on the NLO response.     

Linear and non-linear optical properties of hetero-cyclic aromatic polymers

We investigated linear and non-linear optical properties of non-fused and fully fused hetero-cyclic thiophene, selenophene and pyrrole oligomers. We found that these oligomers show relatively better environmental stability in their fused form than non-fused geometry. Linear extrapolation of calculated energy gap between highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) in the polymer limit exhibits extremely good agreement with experimentally reported band gap for thiophene, selenophene and pyrrole oligomers in their non-fused form. The lowest singlet dipole allowed excited state was calculated using time-dependent density functional theory and extrapolated optical gap estimated were in good agreement with experimental observation. Static linear and first hyperpolarisabilities were also studied as a function of chain length for donor–acceptor substituted polymers. The (hyper)polarisabilities are increasing as a function of chain length in both forms although the non-fused pyrrole oligomers show slow variation. Our study on hyperpolarisability also shows that donor–acceptor substituted non-fused selenophene oligomers are most promising candidates to contribute significantly in non-linear photonics and all fully fused hetero-cyclic oligomers show strong NLO responses.     

聚合物薄膜中生色团分子间的相互作用对其宏观二阶非线性的影响

制备了3-(1,1-二氰基噻吩)-1-苯-4,5-二羟基-H-噻唑(DCNP)与聚醚醚酮(PEK-c)组成的主客掺杂聚合物薄膜,用Maker条纹法测量了不同掺杂浓度下薄膜的二阶非线性系数χ₃₃⁽²⁾.实验结果表明,聚合物中生色团的含量高到一定程度,其宏观二阶非线性随生色团含量的增加反而下降.本文在考虑聚合物中生色团分子相互作用的情况下,修正了聚合物宏观二阶非线性与生色团的含量之间的关系,此时聚合物宏观二阶非线性与生色团的含量已非简单的正比关系.讨论了生色团分子间 关键词：     

Computational study of chiral molecules with high intrinsic hyperpolarizabilities

We have investigated the electronic transition, chiroptical properties, and the second-order nonlinear optical (NLO) properties of eight novel chiral diborate compounds and elucidated structure–property relationships from the micromechanism. These compounds show calculated first hyperpolarizabilities (β) ranging from 2738.52 to 83976.45?×?10^?33?esu, which means that subtle structural modifications can substantially enhance the first hyperpolarizability. The cooperativity of intramolecular charge transfer and an effective way to enhance the NLO response were also systemically investigated. The linear correlation between the first hyperpolarizability and the inverse of the electronic transition energy suggests that the electronic transition energy plays a key role in determining the NLO response. These compounds have the potential to be excellent second-order NLO materials from the standpoint of the large β values, high transparency and the intrinsic non-centrosymmetry. The electronic transition and chiroptical properties have been assigned and analysed. The main UV–visible absorption features are best described as π?→?π* transitions. Moreover, the effects of different functionals and basis sets on the first hyperpolarizability were investigated.     

Synthesis and Characterization of Nonlinear Optical Polymers Containing Carbazole and Disperse Red Dye

Dye‐containing nonlinear optical (NLO) polymers were synthesized: (1) poly(3‐(2‐(3‐(2‐isocyanatopropan‐2‐yl)phenyl)‐2‐methylpropyl)‐4‐methyl‐1‐phenylpyrrolidine‐2,5‐dione), P[(DR1,Cz)MSt‐PMI], and (2) poly(9‐vinyl‐9H‐carbazole‐co‐disperse red 1), PAV[DR1‐Cz]. The synthesized NLO polymers were characterized by ¹H‐NMR, IR, and UV–VIS spectroscopy; differential scanning calorimetry (DSC); and thermogravimetric analysis (TGA). The electro‐optic (EO) coefficients (r₃₃) and their NLO properties were evaluated by simple reflection and the Maker fringe method. The EO coefficients of P[(DR1,Cz)MSt‐PMI] and PAV[DR1‐Cz] were measured at 632.8 nm to be 106 and 46.6 pm/V, respectively. The second harmonic generation (SHG) coefficient (d₃₃) of P[(DR1,Cz)MSt‐PMI] was measured to be 71.25 pm/V.     

Third-order nonlinear optical properties of Bi2S3 and Sb2S3 nanorods studied by the Z-scan technique

Bismuth sulfide (Bi₂S₃) and antimony sulfide (Sb₂S₃) nanorods were synthesized by hydrothermal method. The products were characterized by UV-vis spectrophotometer, X-ray powder diffraction (XRD) and transmission electron microscope (TEM). Bi₂S₃ and Sb₂S₃ nanorods were measured by Z-scan technique to investigate the third-order nonlinear optical (NLO) properties. The result of NLO measurements shows that the Bi₂S₃ and Sb₂S₃ nanorods have the behaviors of the third-order NLO properties of both NLO absorption and NLO refraction with self-focusing effects. The third-order NLO coefficient χ⁽³⁾ of the Bi₂S₃ and Sb₂S₃ nanorods are 6.25×10⁻¹¹ esu and 4.55×10⁻¹¹ esu, respectively. The Sb₂S₃ and Bi₂S₃ nanorods with large third-order NLO coefficient are promising materials for applications in optical devices.     

Theoretical characterisation of highly efficient dye-sensitised solar cells

Molecular electronic structure calculations, employing density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methodologies, have been carried out to improve the performance of the synthesised dye YD2-o-C8 which is characterised by 11.9%–12.7% efficiencies. We aimed to narrow the band gap of YD2-o-C8 to extend the light-harvesting region to near-infrared (NIR). This was done by incorporating Cd instead of Zn onto the porphyrin ring and elongating the length of π-conjugation by adding ethynylene link and anthracene unit, so that the performances of the suggested cells could be expected to exceed the 11.9%–12.7% efficiencies with TiO₂, ZnO₂, and WO₃ oxide electrodes. The effects of modifying the central metal and elongating the length of π-conjugation on cell performance are confirmed in terms of frontier molecular orbital (FMO) energy gaps, density of states (DOS), molecular electrostatic potentials (MEPs), non-linear optical (NLO) properties, ultraviolet–visible (UV–vis) electronic absorption, and ¹H nuclear magnetic resonance chemical shifts. Increasing the length of π-conjugation of the D–π–A dyes leads to increasing the DOS near Fermi levels, more active NLO performance, strong response to the external electric field, delocalisation of the negative charges near the anchoring groups, deep electron injection, suppressing macrocycle aggregation, active dye regeneration, and inhibited dye recombination. The calculated band gap/eV of the present DMP-Zn is correlated with the experimental (E_1/2(oxidation)–E_1/2(reduction)/V) potentials of the identical YD2-o-C8. A co-sensitiser is suggested for NIR sensitisation (550–950 nm) to increase the power-to-conversion efficiency beyond 14%.