Theoretical study on static (hyper)polarizabilities for polyimide by the elongation finite-field method

The elongation finite-field method is applied to calculate (hyper)polarizabilities of polyimides PMDA/DMDB, PMDA/ODA, and PMDA/TFDB. The nonlinear optical (NLO) properties of planar structures of three polyimides are compared to those of their twist structures. It is found that all α and γ values of the planar structures are larger than the corresponding values of the twist structures, which may be attributed to the fact that π-conjugation of twist structures is decreased compared with the planar structures. All β values of planar and twist structures oscillate regularly along with elongating the chain. Moreover, effect of two side-groups –CH₃ and –CF₃ on the NLO properties of PMDA/DMDB and PMDA/TFDB is investigated.     

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.     

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.     

Photostability of D–π–A nonlinear optical chromophores containing a benzothiazolium acceptor

For the practical application of second‐order NLO materials, not only a high molecular quadratic hyperpolarizability β but also good thermal, chemical, and photochemical stabilities are required. Most of the state‐of‐the‐art chromophores with high NLO response cannot be put to use because they are photochemically highly unstable. Good thermal and photochemical stabilities with preserved high hyperpolarizabilities can be achieved by replacement of an aromatic ring with easily delocalizable heteroaromatics, e.g., with benzothiazole. Furthermore, desirable modifications of the benzothiazole fragment lead to improvement in β values. Here we report results of a comprehensive investigation of the photochemical stability of seven D–π–A push–pull molecules based on a N‐methylbenzothiazolium acceptor and a N,N‐dimethylaminophenyl donor with a different length of conjugated bridge and different acceptor strength. The quantum yield (Φ) and the kinetic parameters of photoreactions were determined for existing photodegradation pathways on irradiation at 300–850 nm in MeOH. Trans–cis photoisomerization is proposed as a fast but inefficient photobleaching mechanism for these irradiation wavelengths. Self‐sensitized photooxidation by ¹O₂ makes very slow parallel photodegradation pathway and, albeit to small value of Φ, plays a dominant role in the photodegradation of the compounds investigated. Both structural modifications (extension of conjugated bridge and an additional acceptor group bonded to heterocycle) resulting in an increase of NLO response led to a decrease in photostability due to the self‐sensitized ¹O₂ photooxidative attack. Thus a compromise should be found between an increase in NLO response and a decrease in photostability to make a choice of studied compounds for practical applications. Copyright © 2010 John Wiley & Sons, Ltd.     

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.     

Enhanced photovoltaic performances of C219-based dye sensitisers by introducing electron-withdrawing substituents: a density functional theory study

ABSTRACT

In this work, seven novel sensitisers with the donor-acceptor-π-spacer-acceptor (D-A-π-A) structure were designed based on the C219 dye by introducing different electron-withdrawing substituents, and their photovoltaic parameters were predicted by density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations coupled with the Marcus charge transfer model. Results showed that the introduction of electron-withdrawing substituents can narrow the HOMO–LUMO gap, and remarkably enhance the dye's sunlight absorption. By exactly estimating the charge transfer rates and efficiency in electron injection and recombination processes, the photoelectric conversion efficiency (PCE) for the C219 dye was estimated to be about 7.4% under the standard AM 1.5G solar radiation, which is in excellent agreement with its measured value of 7.6%, suggesting that our calculation scheme is reliable. Moreover, we predicted that the PCE values for most designed dyes are over 10%, indicating that the molecular design strategy used by us in this work is reasonable. Especially, the PCE of dye 1, and 4 were predicted to be as high as 13.0% and 15.7% respectively, illuminating that the –CF₃ and –CN are excellent substituents. Totally, our results revealed that the dye 1 and 4 are potential candidates as efficient sensitisers, and worth further study by experiments.     

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.     

Saturated absorption experiments using a free running CW dye laser

The hyperfine structure of some new iodine lines has been observed over the tuning range of Rhodamine 6G (5800–6200 Å), using a free running, single mode cw dye laser. The resolution obtained in this experiment allowed to calculate the hyperfine constants of the excited state (³π₀⁺) of iodine with an accuracy of 2% for the quadrupole coupling constant and 50% for the magnetic one.     

Perturbative QCD results on pion production in <Emphasis Type="Italic">pp,pA</Emphasis> and <Emphasis Type="Italic">AA</Emphasis> collisions

We summarize new pQCD results on pion production in proton–proton (pp), proton–nucleus (pA) and nucleus–nucleus (AA) collisions. Our calculation introduces intrinsic parton transverse momentum (k_T) and is performed effectively at next-to-leading order (NLO), applying a K factor extracted for jet events. Two different factorization scales, Q = p_Tjet/2 and p_Tjet are used. Experimental data in pA collisions imply a preference for the latter choice at NLO level. We display our results at CERN SPS for AA collisions.     

Second-harmonic generation in poled films of nonlinear optical polymer composites

The second-harmonic generation (SHG) has been measured for studying the molecular ordering and its relaxation process in poled states of two different nonlinear optical (NLO) polymer composites.p-Nitroaniline (pNA) and the azo dye Disperse Orange 3 (DO3) are uniformly dispersed in photopolymer matrices followed by poling. Two different composites made-up of 1 wt% of pNA and 2.5 wt% of DO3 are poled at 200 MV m^-1 and 80 MV m^-1, respectively. One of the second-order NLO coefficients,d ₃₃, was found to be 0.27 pm V^-1 for the pNA-doped film and 0.20 pm V^-1 for the DO3-doped film. While for the latter the ratiod ₃₃/d ₃₃ (3.1) is consistent with the value of 3 in the low-field approximation, for the former the value of 3.5 indicates that higher-order effects of the poling field play a significant role in the NLO process. It is suggested that the SHG relaxation dynamics is also closely related to the UV absorption of the NLO molecules in a photopolymer matrix.     

The Skyrme model with a U*(1) gauged Wess‐Zumino term in a noncommutative spacetime

The Skyrme model is generalized for a noncommutative spacetime with the Weyl‐operators of SU(2) matrices and the corresponding star‐product. The unitary condition and the topological current can be extended to star‐exponential matrices. The Wess‐Zumino term which breaks unphysical symmetries of the Skyrme action is gauged with the U_*(1) group to allow for electromagnetic processes in a noncommutative spacetime. Apart from corrections to the anomalous decay γ→π⁰π⁺π^– in commuting spacetime, the additional anomalous process γ→π⁰π⁰π⁰ is found in the U_*(1) gauged Wess‐Zumino action for a noncommutative spacetime.     

Investigation of the polyetherketone guest–host DR1/PEK-c polymer films by real-time monitoring of the second-harmonic generation

The real-time monitoring of the second-harmonic generation (SHG) was used to optimize the poling condition and to study the nonlinear optical (NLO) properties of the polyetherketone (PEK-c) guest–host polymer films. The high second-order NLO coefficient χ₃₃⁽²⁾=11.02 pm/v measured at 1.064 μm was achieved when the weight percent of DR1 guest in the polymer system is 20%. The NLO activity of the poled DR1/PEK-c polymer film can maintain more than 80% of its initial value when temperature is under 100°C, and the normalized second-order NLO coefficient can maintain more than 85% after 2400 s at 80°C.     

Synthesis and luminescent properties of carbazole end-capped phenylene ethynylene compounds

A class of highly fluorescent and stable carbazole end-capped phenylene ethynylene compounds have been synthesized and the comparative photophysical studies are presented. These compounds exhibit intense violet-blue emission in CH₂Cl₂ solution (λ_max^em≈383–420 nm, Φ_F≈0.36–0.88, τ_F≈1.14–6.63 ns), and show a red-shifted emission in the solid state relative to that in solution. The extent of the shift is highly dependent on the nature of the substituents and the π-conjugation length of phenylene ethynylene component. Their photophysical properties and structural characterization have been investigated with the aim to provide a basis for elucidating the structure–property correlations and developing new blue-emitting materials in organic light-emitting diodes (OLEDs).     

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.     

Redox and photoisomerisation switching the second-order nonlinear optical properties of a tetrathiafulvalene derivative across ten stable states: a DFT study

A molecular switch having large contrast on the second-order nonlinear optical (NLO) properties has been studied based on tetrathiafulvalene (TTF)-π-polynitrofluorene (PTF) molecule. It can afford to switch second-order NLO response across 10 stable states by an effective combination of its photoisomerisation and redox properties. According to density functional theory (DFT) finite field calculations (BHandHLYP/CAM-B3LYP/LC-BLYP/6-31g(d)), the redox-active TTF, TCNQ (7,7′,8,8′-tetracyano-p-quinodimethane) units, and a photoisomerised chromophore (thiophene derivative of perfluorocyclopentene) act as the tuning centre to switch second-order NLO responses. Meanwhile, time-dependent DFT method has been employed to calculate excited-state nature for getting more insights of the second-order NLO responses.     

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.     

Solvatochromism as an efficient tool to study N,N‐dimethylamino‐ and cyano‐substituted π‐conjugated molecules with an intramolecular charge‐transfer absorption

A representative data set has been gained by the measurement of the electronic absorption spectra of 12 systematically selected push–pull systems with an intramolecular charge‐transfer (CT) absorption and the general structure D–π–A (D = donor, A = acceptor) featuring electron‐withdrawing CN groups, electron‐donating N(CH₃)₂ groups, and various π‐conjugated backbones in 32 solvents with different polarities. The longest‐wavelength absorption maxima λ_max and the corresponding wavenumbers $\tilde {v}_{{\rm max}} $ were evaluated from the UV/Vis spectra measured in 32 well‐selected solvents. The D–π–A push–pull systems were further characterized by quantum‐chemical quantities and simple structural parameters. Structure–solvatochromism relationships were evaluated by multidimensional statistic methods. Whereas solvent polarizability and solvent cavity size proved to be the most important factors affecting the position of λ_max, the solvent polarity was less important. The most important characteristics of organic CT compounds are the energy of the LUMO, the permanent dipole moment, the COSMO (COnductor‐like Screening MOdel) area, the COSMO volume, the number, and ratio of N,N‐dimethylamino and cyano groups, and eventually the number of triple bonds (π‐linkers). A relation between the first‐order polarizability α, the longest‐wavelength absorption maxima λ_max, and the structural features has also been found. The higher‐order polarizabilities β and γ are not related to the observed solvatochromism. Copyright © 2010 John Wiley & Sons, Ltd.     

Transport studies of carbon-rich a-SiC x :H film through admittance and deep-level transient spectroscopy measurements

An intrinsic, carbon-rich a-SiC _x :H thin film, prepared by the plasma-enhanced chemical vapour deposition (PECVD) technique, has been studied mainly by AC admittance and small-pulse deep-level transient spectroscopy (DLTS) measurements on an Al/a-SiC _x :H/p-Si metal–insulator–semiconductor (MIS) structure. The effects of measurement temperature, voltage and small-signal AC modulation frequency on the MIS capacitor are qualitatively and quantitatively described. The kinetics of charge injection from the silicon substrate into the a-SiC _x :H film, as a function of temperature and voltage bias stresses, are reported. Nearest-neighbour and variable-range hopping mechanisms are considered. An activation energy of ～?0.09?eV, and a density of states (DOS) of about 10¹⁹?cm^?3/eV were found. The value of the DOS is in agreement with the effective interface DOS of above 10¹²?cm^?2/eV assessed by both capacitance and DLTS measurements. The frequency (or temperature) dependence of the MIS capacitor over the whole DC voltage range is considered in detail. Single- and double-step carrier exchange mechanisms between the a-SiC _x :H film and the silicon substrate, in the accumulation and depletion voltage regimes, respectively, are proposed.     

Structural dynamics of 4‐cyanobenzaldehyde in S2(ππ*) state

The excited state structural dynamics of 4‐cyanobenzaldehyde (p‐CNB) were studied by using the resonance Raman spectroscopy and the quantum mechanical calculations. The experimental A‐ and B‐band absorptions were, respectively, assigned to the major n_O → π₃* and π₂ → π₃* transitions according to the B3LYP‐TD/6‐31G(d) and CIS/6‐31G(d) computations, and the resonance Raman spectra. It was determined that the actual S₂(π₂π₃) state was in energy lower than S₃(π₁π₃), which was just opposite to the B3LYP‐TD/6‐31G(d) calculated order of the S₂(π₁π₃) and S₃(π₂π₃). The vibrational assignments were carried out for the A‐ and B‐band resonance Raman spectra. The B‐band resonance Raman intensities of p‐CNB were dominated by the C2–C3/C5–C6 symmetric stretch mode ν₈, the overtones nν₈ and their combination bands with the ring C–H bend mode ν₁₇, the C9–N10 stretch mode ν₆, the C7–O8 stretch mode ν₇ and the remaining modes. The conical intersection between S₁(n_Oπ₃) and S₂(π₂π₃) states of p‐CNB was determined at complete active space self‐consistent field (CASSCF)(8,7)/6‐311G(d,p) level of theory. The B‐band short‐time structural dynamics and the corresponding decay dynamics of p‐CNB were obtained by analysis of the resonance Raman intensity pattern and CASSCF computations. The resonance Raman spectra indicated that CI[S₁(n_Oπ₃)/S₂(π₁π₂π₃π₄)] located nearby the Franck–Condon region. The excited state decay dynamics evolving from the S_{2, FC}(π₂π₃) to the S₁(n_Oπ₃) state was proposed. Copyright © 2013 John Wiley & Sons, Ltd.     

Linear and nonlinear optical properties of dye-doped KDP crystals: Effect of thermal treatment

Potassium dihydrogen phosphate crystals (KDP, KH₂PO₄) doped with the organic xylenol orange (XO) dye are grown, the XO concentration in the crystal matrix is about 10 ppm. The spectral and luminescent properties of nominally pure, dye-doped and dye-doped/annealed at 150 °C crystals (KDP, KDP:XO and KDP:XO_an) were measured. The annealing temperature effect on the degree of dye protonation in the crystal matrix is established. Analysis of the IR-absorption spectra reveals a strong interaction between the incorporated dye molecules and the hydrogen subsystem of the matrix. The nonlinear optical (NLO) properties of KDP, KDP:XO and KDP:XO_an crystals are studied within the self-action effect of picosecond laser pulses at 532 nm. The mechanism of photoinduced bleaching and the effects of laser beam self-focusing (in KDP) and self-defocusing (in KDP:XO and KDP:XO_an) are supposed to be due to resonance excitation of the subsystems of intrinsic defects and dye molecules, correspondingly. For KDP:XO_an it is shown that thermal annealing of intrinsic crystal defects leads to domination of more effective NLO response of the subsystem of dye molecules that is correlated with photoluminescence data.