The theoretical studies on the two-photon absorption properties of symmetric l,4-bis{2-[4-(2-aryl)phenyl]vinyl}-2,5-bisdialkoxybenzenes

<正>On the level of the time-dependent hybrid density functional theory,the one- and two-photon absorption properties of a series of symmetric 4-bis{2-[4-(2-aryl) phenyl]vinyl}-2,5-bisdialkoxybenzenes are studied respectively utilizing the analytic response theory and the few-state model methods.The calculated results show that the planarity of the geometrical structure plays a great role in enhancing the linear and nonlinear optical abilities of the molecule.However the effect of the length of the chain linked to theπ-centre on the optical property is very little.For the investigated compounds,the A-π-A type charge-transfer molecules display more superior one- and two-photon absorption characteristics than the D-π-D type ones.Furthermore,the two-photon absorption results by use of few-state model are generally consistent with those by analytic response theory,demonstrating the reliability of the few-state model for evaluating the two-photon absorption cross section.The numerical simulations are in good agreement in tendency with the available experimental measurements.     

Solvent effects on optical properties of a newly synthesized two-photon polymerization initiator： BPYPA

Time-dependent hybrid density functional theory in combination with polarized continuum model is applied to study the solvent effects on the geometrical and electronic structures as well as one- and two-photon absorption processes, of a newly synthesized asymmetrical charge-transfer organic molecule bis-（4-bromo-phenyl）-[4-（2-pyridin-4-yl-vinyl）phenyl]-amine （BPYPA）. There exist two charge-transfer states for the compound in visible region. The two-photon absorption cross section calculated by a three-state model and solvatochromic shift of the charge-transfer states are found to be solvent-dependent, where a nonmonotonic behaviour with respect to the polarity of the solvents is observed. The numerical results show that the organic molecule exhibits a rather large two-photon absorption cross section as compared with the compound 4-trans-[p-（N, N-Di-n-butylamino）-p-stilbenyl vinyl] pyridine （DBASVP） reported previously, and is predicted to be a good two-photon polymerization initiator. The hydrogen-bond effect is analysed. The computational results are in good agreement with the measurements.     

First-principles calculations for electronic and optical properties of the zinc-blende structured BeS compound under pressure

The electronic and the optical properties of the cubic zinc-blende (ZB) BeS under high pressure have been investigated by using \it ab initio plane-wave pseudopotential density functional theory method in the generalised gradient approximation (GGA) for exchange-correlation interaction. The electronic band structure and the pressure dependence of the total and partial densities of state under pressure are successfully described. Our calculations show that the ZB BeS has large and indirect band gaps associated with (Γ → X) transitions in ambient conditions. The results obtained are consistent with the experimental data available and other calculations. The optical properties, including dielectric function, energy-loss function, complex refractive index, reflection and absorption spectra, are investigated and analysed at different external pressures. The results suggest that the optical absorption appears mostly in the ultra-violet region and the curve of refractive index shift toward high energies (blue shift) with pressure increasing.     

Nonlinear Optical Properties and Ultrafast Dynamics of Undoped and Doped Bulk SiC

Ultrafast third-order nonlinear optical response of bulk 6H-SiC undoped and doped with different nitrogen concentrations are investigated utilizing femtosecond Z-scan and optical Kerr effect （OKE） techniques at the wavelength of 800hm. The Z-scan measurement shows that the third-order nonlinear optical susceptibilities of the doped samples are improved in comparison to the intrinsic sample. The OKE results additionally reveal that the instantaneous nonlinear optical response of the samples can be ascribed to the distortion of the electron cloud. The ultrafast transient spectroscopic measurements with the one-color and two-color pump-probe techniques demonstrate that the ultrafast recovery process in subpicosecond domain is induced by two-photon absorption process, while the slow relaxation component reflects the carrier dynamics of the excited electrons.     

Solvent effects on structure and optical properties of a D- π-A azobenzene dye

Time-dependent hybrid density functional theory in combination with Onsager reaction field model and super-molecular model has been applied to study solvent effects on the geometrical and electronic structures, as well as one/two-photon absorption properties, of 4-（N-（2-hydroxyethyl）-N-methyl）-amino-4＇-nitroazobenzene. It is found that the short-range interaction has a large effect on the electronic structure of the solute molecule, namely, large red-shift of the maximum one-photon absorption is induced by hydrogen bonding. The solute molecule has a large two-photon absorption cross section, which is enhanced by the solvent effect. The computational results are in good agreement with measurements.[第一段]     

Optical fiber temperature sensor based on wavelength-dependent detection

Semiconductor fiber temperature sensors have been used widely in many fields, but most of them pick up temperature by measuring the optical intensity of certain fixed narrow-band in absorption spectrum. Furthermore,they are sensitive to the loss of optical intensity and the fluctuation of light source power. The novel temperature measurement system proposed in this paper is based on the semiconductor absorption theory and the spectral analysis of method.To measure temperature,the sensor model detects not the certain narrow-band spectrum but the most spectra of the optical absorption edge.Therefore the measurement accuracy and the stability can be improved greatly.Experimental results are in agreement with theoretical analysis results perfectly.     

Quantum logic operations on two distant atoms trapped in two optical-fibre-connected cavities

Based on the coupling of two distant three-level atoms in two separate optical cavities connected with two optical fibres, schemes on the generation of several two-qubit logic gates are discussed under the conditions of Δ = δ - 2ν cos πk/2 >> g/2 and ν ~ g. Discussion and analysis of the fidelity, gate time and experimental setups show that our schemes are feasible with current optical cavity, atomic trap and optical fibre techniques. Moreover, the atom-cavity- fibre coupling can be used to generate an N-qubit nonlocal entanglement and transfer quantum information among N distant atoms by arranging N atom-cavity assemblages in a line and connecting each two adjacent cavities with two optical fibres.     

Responsive mechanism of 2-(2'-hydroxyphenyl)benzoxazole-based two-photon fluorescent probes for zinc and hydroxide ions

Response theory is used to investigate one- and two-photon absorption(TPA) as well as the emission properties of a series of potential zinc ion and pH sensitive materials containing 2-(2’-hydroxyphenyl)benzoxazole(HPBO) end groups.Special emphasis is placed on the evolution of their optical properties upon combining with zinc ions or deprotonation.Our calculated results indicate that upon combining with zinc ions or deprotonation,these HPBO derivatives show drastic changes in their one-photon absorption(OPA),emission,and TPA properties.Moreover,the mechanisms of the probes are analyzed and found to be an intramolecular charge transfer.These compounds are thus proved to be excellent candidates for two-photon fluorescent zinc and pH probes.     

Microstructural and Optical Absorption Properties of Cu—MgF2 Nanoparticle Cermet Film

We examine the microstructural and optical absorption spectra of 10-30vol% Cu-MgF2 nanoparticle cermet films prepared by co-evaporation in vacuum.The results show that the Cu-MgF2 cermet films are mainly composed of the amorphous MgF2 matrix with embedded fcc Cu nanoparticles of average size 12-24nm.The results also show that the optical absorption of the films decreases as the wavelength increases in the range of 200-800nm.The surface plasmon resonance absorption peaks of Cu nanoparticles in 10,20 and 30vol% Cu-MgF2 films appear at 578,588 and 606 nm,respectively.The interband transition absorption of Cu starts from 590nm downwards.Based on the Maxwell-Garnett theory,the experimental optical absorption properties of the films have been quantitatively evaluated.     

Spatially nonlocal effects on optical absorption properties in coupled quantum wells with an applied electric field

Based on the microscopic nonlocal optical response theory, the intersubband optical absorption properties in AlGa As/Ga As couple quantum wells（CQWs） are investigated for p-polarized states. The numerical results show that spatial nonlocality of optical responses can induce a radiation shift on optical absorption spectra due to nonlocal effects. The dependence of the radiation shift on the CQW structure and the applied electric field is clarified. It is also demonstrated that the maximal radiation shift and the least optical absorbance can be obtained by adopting an appropriate CQW structure and a suitable applied electric field. This work may provide some methods of designing the nanomaterials with controllable nonlocality and observing the spatial nonlocal effects in experiment.     

两个新合成化合物EPVPC和OPVPC非线性光学特性的理论研究

在杂化密度泛函理论（DFT/B3LYP）的水平上，研究了最新实验室合成的两个化合物分子9-乙烷基-3-{2-[4-2-吡啶-4-乙烯基苯]-乙烯基}-9氢咔唑（EPVPC）和9-十八烷基-3-{2-[4-2-吡啶-4-乙烯基苯]-乙烯基}-9氢咔唑（OPVPC）的非线性光学特性。理论结果与现有的实验测量结果符合得的较好。利用扩展的少态模型方法计算了分子的双光子吸收截面，结果表明三态模型可以很好地描述它们的最大双光子吸收截面。数值模拟显示这两个化合物都具有较大的双光子吸收截面，并且，在低频范围内，OPVPC分子比EPVPC分子显示出较强的双光子吸收特性。     

One- and two-photon absorption properties of two metalloporphyrin complexes

The linear and nonlinear optical properties of two metalloporphyrin complexes formed by the complementary coordination of central zinc or magnesium ions to the ligand 5, 10, 15-tri-(p-tolyl)-20-phenylethynylporphyrin are theoretically investigated by using the analytic response theory at the density functional theory level. The results indicate that the studied complexes present more symmetric geometry structures than the ligand. The charge-transfer states of the two complexes in the lower energy region are all almost degenerate but those of the ligand are well separated. The ratio of the two-photon absorption cross sections of the ligand, zinc-porphyrin and magnesium-porphyrin complexes is 1.0:1.5:1.8, demonstrating that the two-photon absorption capability can be greatly increased when the ligand is coordinated with a metal ion. Moreover, several physical micro-mechanisms including electron transitions and intramolecular charge-transfer processes are discussed to explore the differences in optical property between the ligand and two complexes.     

Tuning the absorption spectra and nonlinear optical properties of D‐π‐A azobenzene derivatives by changing the dipole moment and conjugation length: a theoretical study

The optical properties of several azobenzene derivatives were modulated by varying the dipole moments and conjugation lengths of the D‐π‐A systems. The relationship between the structure and absorption spectrum and polarizability was studied in the gas phase, THF and MeOH solutions, respectively, by using the density functional theory. The calculated absorption spectra and second‐order polarizabilities are in good agreement with the available experimental observations. In comparison with the D‐π‐A monomer, the H‐shaped D‐π‐A dimer almost doubles the dipole moments and hence increases the second‐order polarizabilities, without a significant shift in the maximum absorption bands. The addition of another azobenzol group between electron‐donating and ‐accepting groups increases the second‐order polarizabilities by 4–6 times, but leads to an evident red‐shift of about 65–80 nm in spectra. The relative second‐order polarizability of the halogen‐substituted derivatives is in the sequence of ? CF₃ > ? F > ? Cl > ? Br, without obvious substituent effects on the optical transparency. The D‐π‐A chromophores with the strong electron‐donating (amino) and ‐accepting (acetyl) substituent present the larger second‐order polarizabilities, at the cost of about 20 nm red‐shift of the maximum absorption lengths relative to the halogen‐substituted species. It is also demonstrated that both the linear and nonlinear optical properties augment with the increase in solvent polarity, accompanied by a red‐shift in the wavelengths of maximum absorption by about 18 and 23 nm, respectively, in THF and MeOH solutions. The changes in optical properties upon the structural modifications are further rationalized by the electronic structures of various H‐shaped dimers. Copyright © 2010 John Wiley & Sons, Ltd.     

Two-photon absorption properties of D-A-D type chromophores containing tetraphenylethylene and triphenylamine moieties: a close look at the effects of the strength,position and number of donors

The two-photon absorption (TPA) properties of a series of D-A-D type chromophores containing tetraphenylethylene (TPE) and triphenylamine moieties have been investigated employing the density functional response theory in combination with the polarisable continuum model. Special emphases are placed on the effects of the strength, position and number of donors on TPA. Our calculations demonstrate that the TPA intensity enhances with the increase of the electron-donating ability of the substituents on the triphenylamine unit, which is consistent with experimental observations. It is shown that the position of donors has an important effect on TPA. The donor on the side position of TPE unit decreases the TPA cross section, thereby more donors could not necessarily produce stronger TPA. The cis-trans isomerism effect is also explored and it is found that all the cis structures have lower TPA intensities than those of corresponding trans forms. By considering a different number of donors on TPE and triphenylamine unit respectively, it is interesting to find that the structure with one terminal donor on TPE and two donors on triphenylamine unit has the largest TPA cross section. The few-state model and the natural bond orbital charge analysis are used to explore the reason behind it.     

Facile synthesis, optical properties and theoretical calculation of two novel two-photon absorption chromophores

Two heterocycle-based derivatives that can be used as two-photon absorption chromophore, 9-butyl-3-(2, 6-diphenylpyridin-4-yl)-9H-carbazole (BDPYC) and 9-butyl-3-(4-(2, 6-diphenylpyridin-4-yl)styryl)-9H-carbazole (BDPSC) have been successfully synthesized and fully characterized by elemental analysis, IR, ¹H NMR, ¹³C NMR and MS. The molecules possess D-π-A structures, but have different π bridge. The 9-butylcarbazole is used as a donor (D), and the pyridine ring is used as an acceptor (A). One- and two-photon absorption and excited fluorescence properties in various solvents were experimentally investigated. Two-photon initiated optical data recording experiments have been carried out under 740 nm laser radiation, and the possible mechanism of optical data storage is discussed based on theoretical calculations.     

Au纳米颗粒阵列中双光子吸收的饱和过程

采用纳米球蚀刻法制备了Au纳米颗粒阵列.并通过扫描电子显微镜观测了其表面形貌,表明三角形的Au纳米颗粒呈阵列状分布.采用Z扫描方法(800 nm, 50 fs)测量了Au纳米颗粒阵列的三阶非线性光学特性.在较小的激发功率下,结果呈现出双光子吸收效应,随着激发功率不断增加,出现了双光子吸收饱和的过程;非线性折射则呈现出自散焦效应.这种高效率的非线性响应机理使得该种Au纳米颗粒阵列在高速全光开关中有潜在的应用价值. 关键词： 纳米球蚀刻技术 Au纳米颗粒 三阶光学非线性     

Shift photocurrent induced by two-quantum transitions

A theory of the shift current induced by direct two-photon and indirect one-photon absorption is developed for noncentrosymmetric crystals. A formula is derived for the microscopic shifts of Bloch electrons induced by two-quantum processes. It is shown that the ratio of the two-photon photocurrent at the photon frequency ω to the photocurrent induced by direct one-photon transitions at the photon frequency 2ω, as compared to the corresponding absorption-rate ratio, contains a large factor {ie152-1}ω/(2{ie152-2}ω − E _g), where E _g is the bandgap; i.e., these photocurrent can be comparable in order of magnitude. For crystals of T _d symmetry, the photocurrents induced by one- and two-photon absorption are compared in terms of polarization dependence.     

三苯胺衍生物分子非线性光学性质的理论研究

在密度泛函理论水平上,利用响应函数方法,研究了1-{(1E)-2-[4-(二苯胺基)苯基]乙烯基}-4-[4-N,N-二甲胺]苯(PVMB)和1-[(1E)-2-(4-(1E)-2-{4-[4-N,N-二甲胺]苯基}乙烯基)苯基]苯胺}苯基)乙烯基]-4-[4-N,N-二甲胺]苯(DPVMB)两分子的双光子吸收特性.计算结果表明,这两个化合物都具有较好的双光子吸收特性,且具有两分支结构的DPVMB分子比具有单支结构的PVMB分子有更强的双光子吸收强度.计算数值结果和实验结果符合地较好.     

Functional polymers by two-photon 3D lithography

In the presented work, two-photon 3D lithography and selective single-photon photopolymerization in a prefabricated polydimethylsiloxane matrix is presented as an approach with potential applicability of waveguide writing in 3D by two-photon polymerization.Photopolymers based on acrylate chemistry were used in order to evaluate the optical capabilities of the available two-photon system. Several photoinitiators, tailored for two-photon absorption, were tested in a mixture of trimethylolpropane triacrylate and ethoxylated trimethylolpropane triacrylate. Best results were obtained with a recently synthesized diynone-based photoinitiator. Feature resolutions in the range of 300 nm were achieved. Due to the cross-conjugated nature of that donor-π-acceptor-π-donor system a high two-photon absorption activity was achieved. Therefore, a resin mixture containing only 0.025 wt% of photoinitiator was practical for structuring by two-photon polymerization. The required initiator content was therefore a factor of 100 lower than in traditional one-photon lithography.The aim of the second part of this work was to fabricate optical waveguides by selectively irradiating a polymer network, which was swollen by a monomer. The monomer was polymerized by conventional single-photon polymerization and the uncured monomer was removed by evaporation at elevated temperatures. This treatment leads to a local change in refractive index. Refractive index changes in the range of Δn = 0.01 (Δn/n = 0.7%) were achieved, which is sufficient for structuring waveguides for optoelectronic applications.