One-photon Absorption Wavelengths Research Articles

Optical and morphological properties of DCM thin films co-doped of Znq2 by PVD: Theoretical and experimental investigations

In this article, new experimental results of the morphological and optical properties of thin films of 4-(dicyanomethylene)-2-methyl-6-(4-dimethylaminostyryl)-4H-pyran co-doped by 8-hydroxyquinoline zinc (Znq2) for different concentrations were presented. The physical vapor deposition in a high vacuum was used to create the thin films on glass substrates with a thickness of 100 nm. The morphological properties of the samples were identified using the Atomic Force Microscopy (AFM) apparatus in tapping mode. TEM images show amorphous structures. The phase composition of the samples was assessed using FTIR methods. The Tauc plot approach was used to examine the measured transmittance spectra in order to estimate the energy gap. Analysis of the results showed that the co-doping of DCM thin film by Znq2 influenced the structural and optical properties of the samples. To evaluate the experimental results found, theoretical calculations based on the maximum one-photon absorption (OPA) wavelengths of DCM and Znq2 have been first measured through the UV–Vis spectral technique. Then, the experimental conclusions on values for DCM and Znq2 have been compared with their corresponding simulation data procured from the time-dependent self-consistent-field (TD-SCF) computation utilizing the density functional theory (DFT) at B3LYP/6-311G(d,p) level. Besides, we have explored the first and second frontier molecular orbitals (MOs) for title compounds and their energy gaps via the DFT procedure. The calculations of maximum OPA wavelengths and the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) contributions on both molecules have also been crosschecked with the results of already published data in the literature.

Responsive mechanism and coordination mode effect of a bipyridine-based two-photon fluorescent probe for zinc ion**Project supported by the Natural Science Foundation of Shandong Province, China (Grant No. ZR2014AM026).

The properties of one-photon absorption (OPA), emission and two-photon absorption (TPA) of a bipyridine-based zinc ion probe are investigated employing the density functional theory in combination with response functions. The responsive mechanism and coordination mode effect are explored. The structural fluctuation is illustrated by molecular dynamics simulation. The calculated OPA and emission wavelengths of the probe are consistent with the experimental data. It is found that the red-shift of OPA wavelength and the enhancement of TPA intensity are induced by the increased intra-molecular charge transfer mechanism upon metal binding. The structural fluctuation could result in the blue-shift of TPA wavelength and the decrease of the TPA cross section. The TPA properties are quite different among the zinc complexes with different coordination modes. The TPA wavelength of the complexes with two ligands is close to that of the probe, which is in agreement with the experimental observation.

Second-order Nonlinearities of Anionic 3-dicyanomethylen-5,5-dimethyle-1-[2-(4-hydroxyphenyl)ethenyl)]-cyclohexene

Due to the connecting one π-conjugated group with the two backside donor and acceptor groups, anionic 3-dicyanomethylen-5,5-dimethyle-1-[2-(4-hydroxyphenyl)ethenyl)]-cyclohexene (1) might possess nonlinear optical (NLO) properties. To estimate the potential for second-order NLO behaviour; the electric dipole moments and dispersion-free dipole polarizabilities and first hyperpolarizabilities have been determined by density functional theory (DFT) at B3LYP/6-31++G(d, p) level. Quantum mechanical calculations using time-dependent Hartree-Fock (TDHF) procedure have been utilized to evaluate frequency-dependent second-order nonlinearities of 1. The one-photon absorption (OPA) characterization of 1 has been theoretically obtained by means of configuration interaction (CI) with 6-31G basis set. Our theoretical results on the maximum OPA wavelength, second-order susceptibilities and corresponding microscopic NLO responses are accorded with the previous experimental observations of the investigated compound. The highest occupied molecular orbitals, the lowest unoccupied molecular orbitals and the HOMO-LUMO band gaps for 1 have been also examined by DFT/B3LYP method.

Quantum chemical calculations and experimental studies of third-order nonlinear optical properties of conjugated TTF–quinones

To investigate microscopic third-order nonlinear optical (NLO) behaviour of two tetrathiafulvalene (TTF) derivatives, TTF–diquinone triad (1) and TTF–monoquinone dyad (2), we have computed both dispersion-free and also dispersion of dipole polarizabilities (α) and third-order hyperpolarizabilities (γ) at 532nm wavelength using time-dependent Hartree–Fock (TDHF) method. The one-photon absorption (OPA) characterizations of the title molecules have been theoretically obtained by means of configuration interaction (CI) method with all doubly occupied molecular orbitals. We have also calculated the dynamic third-order susceptibilities (χ(3)) using the TDHF method. Our theoretical results on the maximum OPA wavelengths, third-order susceptibilities and corresponding microscopic NLO responses are in good agreement with the previous experimental observations of the examined TTF-based molecules. The highest occupied molecular orbitals (HOMO), the lowest unoccupied molecular orbitals (LUMO) and the HOMO–LUMO band gaps for 1 and 2 have been evaluated by density functional theory (DFT) quantum mechanical calculations at B3LYP/6–31G(d,p) level.

Molecular design and theoretical investigation into one- and two-photon absorption properties of two series of cyclometalated platinum (II) complexes

We have theoretically investigated two series of cyclometalated Pt(II) complexes, a series [Pt (C, N, N) Cl] and b series [Pt (C, N, Npyrazolyl) Cl]. The geometrical and electronic structures are calculated at the ECP60MWB//6-31G*(H, C, Cl, N, S) basis set level using DFT method; one-photon absorption (OPA) properties are calculated by using both TDDFT and ZINDO methods and two-photon absorption (TPA) properties are obtained with the ZINDO/SOS method. The resonance integrals parameters ( β sp and β d) for Pt are adjusted to -1 and -28.5 eV, respectively, to make max OPA wavelength calculated by ZINDO closest to the experimental data and TDDFT results. The calculated results indicate the molecule 2b ([Pt (Cnaphthyl, N, Npyrazolyl) Cl]) has the biggest potential as outstanding TPA materials because (i) the TPA properties of b series are more outstanding in IR wavelength range, the molecules in b series have good transparencies and possess 1-pyrazolyl-NH that is also available for another metal coordination (e.g., dimerization) and chemical interactions; (ii) when C is Cnaphthyl in the C, N, N ligand of cyclometalated Pt(II) complexes, the molecules have the best conjugation effect and the best TPA properties.

Theoretical study of one‐ and two‐photon absorption properties of expanded donor–acceptor calix[4]arenes

AbstractTwo types of donor(D)–acceptor(A) calix[4]arenes have been theoretically studied using DFT//B3LYP/6‐31G(d) method and ZINDO/CISD method. The calculations show that the substitution of CC by the conjugation bridge CC and NN plays an important part in altering one‐photon absorption (OPA) and two‐photon absorption (TPA) properties. The maximum OPA wavelengths of all studied compounds are less than 400 nm, which means high transparency. The geometry of the calixarenes strongly influences the TPA properties of the studied compounds. In addition, the nitro derivatives have a wider TPA response range than other non‐nitro derivatives. The tetrasubstituted calix[4]arenes (type B calixarenes) have a larger TPA cross‐section values than the bisubstituted calix[4]arenes (type A calixarenes). Copyright © 2009 John Wiley & Sons, Ltd.

Theoretical studies on the one- and two-photon absorption properties of azulenylporphyrins and azulene-fused porphyrins

The electronic structures, one-photon absorption (OPA) and two-photon absorption (TPA) properties of the azulenylporphyrins and azulene-fused porphyrins have been comparatively studied by using DFT/B3LYP/6–31G(d) and the ZINDO/SDCI method. With the number of azulenyl groups increasing, the OPA wavelengths of all molecules are red-shifted in 400–600 nm and the two-photon absorption cross section is gradually enlarged. The azulene-fused structures facilitate an expanding conjugated area and increasing TPA cross section. The origin of TPA properties of studied compounds is studied with a two-level model. In summary, the azulene-fused porphyrins exhibit strong two-photon absorption.

THIRD-ORDER NONLINEAR OPTIC AND OPTICAL LIMITING PROPERTIES OF A MN(III) TRANSITION METAL COMPLEX

N,N′-bis(5-bromosalicylidene)propane-1,2-diamine-O,O′,N,N′)-manganese(III) chloride transition metal complex has been synthesized and characterized by elemental analysis and UV-vis spectroscopy. Its crystal structure has been determined using X-ray diffraction analysis. To provide an insight into the optical limiting (OL) behavior of the title compound, the third-order nonlinear optical (NLO) properties, one-photon absorption (OPA) and two-photon absorption (TPA) characterizations have been theoretically investigated by means of the time-dependent Hartree–Fock (TDHF), AM1 and configuration interaction (CI) methods, respectively. According to ab initio calculation results, the examined molecule exhibits second hyperpolarizabilities (γ) with non-zero values at the positions of TPA peaks, implying microscopic third-order optical nonlinearity. The maximum OPA wavelengths recorded by linear optical experiment and quantum mechanical computations are estimated in the UV region to be shorter than 400 nm, showing good optical transparency to the visible light. The TPA cross-sections (δ(ω)) at [Formula: see text] values indicate that the synthesized compound might possess OL phenomena, which are in accord with the experimental observations on the manganese complexes in the literature.

Synthesis, structure, linear and third-order nonlinear optical behavior of N-(3-hydroxybenzalidene)4-bromoaniline

N-(3-Hydroxybenzalidene)4-bromoaniline has been synthesized. Its crystal structure has been determined by X-ray diffraction analysis. To investigate microscopic third-order nonlinear optical (NLO) behavior of the title compound, we have computed both dispersion-free (static) and also frequency-dependent (dynamic) linear polarizabilities ( α) and second hyperpolarizabilities ( γ) at λ = 825–1125 nm and 1050–1600 nm wavelength areas using time-dependent Hartree–Fock (TDHF) method. The one-photon absorption (OPA) characterization has been theoretically obtained by means of configuration interaction (CI) method. The maximum OPA wavelengths are estimated in the UV region to be shorter than 450 nm, showing good optical transparency to the visible light. According to ab-initio calculation results on (hyper)polarizabilities, the synthesized molecule exhibits second hyperpolarizabilities with non-zero values, and it might have microscopic third-order NLO behavior.

Calculation on the one- and two-photon absorptions properties for two series of dimethylfluorene core derivatives

Two series of dimethylfluorene core derivatives, which have different conjugation length or different peripheral substituted groups, are theoretically investigated in the paper. Using the density functional theory B3LYP with 6-31G basis set, we have obtained the equilibrium geometries and electronic structures for all the studied molecules. On the basis of the geometrical and electronic structures, the one- and two-photon absorptions properties are studied theoretically with ZINDO-SOS method in detail. The computational results are in good agreement with the available experimental values. According to our calculations, from the series I molecule to the series II counterparts, the maximum one-photon absorption (OPA) intensities and the maximum two-photon absorption (TPA) cross sections values δ max are obviously increased as the conjugation length increases. And for both series the maximum OPA wavelength λ max ( 1 ) and δ max values are increased with the stronger electron-donating or electron-accepting capability. This demonstrates that the conjugation length and the different substituent groups play important roles in the OPA and the TPA cross section.

Wavelength dependence and figures of merit of ultrafast third-order optical nonlinearity of a conjugated 3,3'-bipyridine derivative.

The wavelength dependence and figures of merit of the third-order optical nonlinearity of a conjugated 3,3'-bipyridine derivative, a designed nondipolar structure of the donor-acceptor-acceptor-donor type, are reported. Z scans reveal positive nonlinear refractive-index changes for wavelengths longer than the one-photon absorption wavelength. Although the value of nonlinear Kerr coefficient n2 decreases from 6.0(+/- 0.2) x 10(-6) cm2/GW at 750 nm to 4.6(+/- 0.7) x 10(-6) cm2/GW at 1550 nm, the value of nonlinear absorption beta decreases from 0.084 cm/GW at 750 nm to a negligible value at 1550 nm, giving rise to excellent nonlinearity-to-loss figures of merit at telecommunications wavelengths.

Two-photon fluorescence excitation cross sections of biomolecular probes from 690 to 960 nm

We report on two-photon fluorescence excitation (TPE) action cross sections for five widely used molecular fluorophores. Measurements were performed by use of ultrashort (~100-fs) Ti:sapphire pulsed excitation over the range 690-960 nm. TPE spectra were obtained by comparison with a fluorescein calibration standard. Large cross sections were found for the cyanine reagent Cy 3 (~140 GM) and for Rhodamine 6G (~150 GM), both at 700 nm [1 GM = 10(-50) (cm(4) s)/photon]. Several fluorophores show interesting and desirable blue shifts with respect to twice the one-photon absorption wavelength. Fluorophore fluorescence intensities showed no significant departure (?4%) from quadratic illumination power dependence, indicating genuine two-photon processes. Implications of these measurements for two-photon laser-scanning microscopy are discussed.