Lowest Absorption Band Research Articles

Elucidating the Photophysics and Nonlinear Optical Properties of a Novel Azo Prototype for Possible Photonic Applications: A Quantum Chemical Analysis.

The photophysics and nonlinear optical responses of a novel nitrothiazol-methoxyphenol molecule were investigated using density functional theory (DFT) and time-dependent density functional theory (TD-DFT) methods with the polarizable continuum model to take the solvent effect into account. Special attention is paid to the description of the lowest absorption band, characterized as a strong π → π* state in the visible region of the spectrum. The TD-DFT emission spectrum analysis reveals a significant Stokes shift of more than 120 nm for the π → π* state in gas phase condition. The results show a great influence of the solvent polarity on the nonlinear optical (NLO) response of the molecule. Specifically, the second harmonic generation hyperpolarizability β(-2ω; ω, ω) shows a large variation from gas to aqueous solvent (82 × 10-30 to 162 × 10-30 esu), exhibiting notably higher values than those reported for standard compounds such as urea (0.34 × 10-30 esu) and p-nitroaniline (6.42 × 10-30 esu). Furthermore, a two-photon absorption analysis indicates a large cross-section (δ2PA = 77 GM) with superior performance compared to several dyes. These results make the molecule quite interesting for nonlinear optics.

Dibenzothiophene Bridged Bis‐Bodipy and Bis‐Metal Dipyrrin Complexes

AbstractDibenzothiophene (DBT) bridged bis‐dipyrromethane was synthesized by treating readily available 4,6‐di(p‐formylphenyl) dibenzothophene with pyrrole under acid catalyzed conditions. The DBT bridged bis‐dipyrromethane was further oxidized with DDQ to afford the DBT bridged bis‐dipyrrin which was used as a ligand to prepare DBT bridged bis‐BODIPY, bis‐Ni(II) dipyrrin and bis‐Pd(II) dipyrrin complexes by treating the ligand with BF3 ⋅ Et2O, Ni(acac)2 and Pd(acac)2 respectively under mild reaction conditions. The DBT‐bridged bis‐BODIPY and bis‐metal dipyrrin complexes were thoroughly characterized and studied by HR‐MS, 1D & 2D NMR, absorption, fluorescence, cyclic voltammetry and DFT techniques. The bis‐BODIPY and bis‐Pd(II) dipyrrin showed highly intense absorption band at ~500 nm along with one low intense absorption band at 340 nm whereas the bis‐Ni(II) dipyrrin complex showed slightly broadened blue shifted high intense band at 490 nm along with one additional band at 426 nm. The bis‐BODIPY was fluorescent with fluorescence band at 524 nm and quantum yield of 0.031 whereas bis‐M(II) dipyrrin complexes were nonfluorescent. DFT optimized structures revealed that the BODIPY units are more planar with the dibenzophene moiety in bis‐BODIPY with an angle of ∼5.68°. However, in 3‐Pd and 3‐Ni, the M(II)‐dipyrrin units are much more deviated from the dibenzothiophene plane with an angle of 12.81°–14.23°.

Tuning the linear optical properties and two-photon absorption on the cinnamylideneacetophenone derivatives: The effect of methoxy group by a experimental and theoretical point of view

The present work studied the effect of the methoxy group position in two cinnamylideneacetophenone (CA) derivatives on both one-photon (1PA) and two-photon absorption (2PA) processes. Our outcomes exhibit a dependence on the methoxy group position spectrally and in magnitude for both. A decrease in the lower energy 1PA band of 0.23eV was observed when the methoxy group was moved to the more conjugated part of the cinnamaldehyde molecule. The opposite was also observed for the next higher absorption band. The Quantum Chemical Calculations (QCCs), besides a good agreement between the experimental and simulated 1PA spectra, except for the magnitude of the high energy absorption band, showed that the effect behind the observed experimental red-shift of the lower absorption band is caused by the higher charge transfer when the methoxy group is bounded to the longer conjugated part of the cinnamaldehyde derivative. For experimental 2PA spectra, the higher energy band is strongly affected by the presence of the methoxy group, pointing out an increase of about 56 % in the values of the two-photon absorption cross-section (2PACS). Furthermore, the phenomenological Sum-Over-Essential States (SOS) approach and QCCs were performed for further clarification in the 2PACS experimental results. Hence, our findings demonstrate that changing the methoxy position on opposite sides of the CA may open up a novel insight for designing new organic molecules, particularly when seeking to enhance the values of 2PACS significantly of CA derivatives.

Al, N Codoping and the Effect of O Vacancy in Photocatalyst SrTiO3

In light of the potential for enhancing SrTiO3 (STO)'s photocatalytic efficiency, particularly in the visible light region, a study is conducted on Al, N codoping in STO herein using first‐principles calculations. The effect of oxygen vacancy (VO) is also considered. It is found that AlSr, NO can significantly reduce the bandgap; however, their formation energies are rather high, and the defect levels they brought in may induce recombination centers. Under O‐deficient conditions, VO can facilitate Al, N doping in STO. When Al, N codope in STO, AlTi, NO, and VO would tend to combine, and formation of complex defect AlTi + NO + VO can further enhance N dopability in STO. Moreover, AlTi + NO + VO can simultaneously reduce the bandgap and eliminate the defect levels induced by NO. However, AlTi + NO + VO may not fully realize the potential for the photocatalytic activity due to the low optical absorption and unsuitable band alignment. The work provides a theoretical guidance for the photocatalytic performance of STO in the visible light region.

Two bits dual-band switchable terahertz absorber enabled by composite graphene and vanadium dioxide metamaterials

This article presents the design of a 2-bit dual-band switchable terahertz absorber using a stacked combination of graphene and vanadium dioxide (VO2) metamaterials. For the first time, the proposed absorber design offers four switchable states by controlling the conductivity of graphene and VO2 metamaterial layers. The lower absorption band is produced by the graphene metamaterial, whereas the upper band is implemented by the VO2 metamaterial pattern. The structure shows two absorption bands (State 11) at 0.745–0.775 THz and 2.3–5.63 THz, when the Fermi graphene level of graphene is 0.2 eV and the VO2 is in the metallic phase. The lower absorption band is turned off, while keeping the upper band (State 01), when the graphene Fermi level is 0 eV and the VO2 layer is in the metallic phase. The upper absorption band is turned off, while preserving the lower absorption band (State 10) by switching the VO2 into the insulator phase and keeping the graphene Fermi level at 0.2 eV. Finally, both of the absorption bands are turned off by setting the graphene Fermi level to 0 eV and switching the VO2 into the insulating phase. Equivalent circuit modelling analysis and full-wave electromagnetic simulations are used to explain the operation principle of the proposed absorber. Very good agreement is obtained between the theoretical analysis and the simulations confirming the presented design principle for the 2-bit switchable absorber.

Dissecting the Triplet-State Properties and Intersystem Crossing Mechanism of the Ligand-Protected Au13 Superatom.

Icosahedral Au13 nanoclusters are among the most typical superatoms and are of great interest as promising building blocks for nanocluster-assembled materials. Herein, the key parameters involved in the intersystem crossing (ISC) process of [Au13(dppe)5Cl2]3+ (Au13; dppe = 1,2-bis(diphenylphosphino)ethane) were characterized. Quenching experiments using aromatic compounds revealed that the T1 energy of Au13 is 1.63 eV. An integrative interpretation of our experimental results and the relevant literature uncovered important facts concerning the Au13 superatom: the ISC quantum yield is unity due to the ultrafast ISC (∼1012 s-1), the lowest absorption band includes contributions of direct singlet-triplet transitions, and there exists a large S1-T1 gap of 0.73 eV. To explain the efficient ISC, the El-Sayed rule was applied to the superatomic orbitals corresponding to the excited-state hole/electron distributions obtained from theoretical calculations. The strong spin-orbit coupling between the S1 and T2-T4 states offers a reasonable explanation for the ultrafast ISC.

Active electromagnetic absorption metasurface with a switchable reflection band

An active electromagnetic (EM) absorption metasurface is proposed to achieve a switchable reflection band between two absorption bands. The metasurface consists of one lossy layer and one active layer separated by an air gap. The top lossy layer is composed of periodic metallic unit cells, designed to absorb the incident EM wave at the lower and higher absorption bands. PIN diodes are embedded on the bottom periodic array to control the reflection coefficient. When the PIN diodes are turned off, the incident EM wave is absorbed at lower and higher bands while reflected at the intermediate band; when the PIN diodes are turned on, the reflection band is switched off and a wide absorption band is achieved. Experimental results verify the numerical simulations.

Rhenium(I) Complexes with Sulfur-Bridged Dipyridyl Ligands: Structural, Photophysical, and Computational Studies.

A series of six new rhenium(I) tricarbonyl complexes [Re(CO)3(N-N)Br] bearing sulfur-bridged dipyridyl (N-N) ligands with three different oxidation states (sulfide (S), sulfoxide (SO), and sulfone (SO2)) are described. Spectroscopic studies show that changing the oxidation state of the ligands influences the photophysical properties of the complexes, with complexes 3 and 6 containing the sulfone ligand exhibiting a lower energy MLCT absorption band tailing into the visible region. Solution-state emission measurements show that these complexes exhibit readily tunable emission energies from 480 to 610 nm, depending on the oxidation state of the sulfur bridge and the presence of substituents on the pyridyl rings. Solid-state emission measurements show that the emission is significantly red-shifted upon oxidation of the sulfur bridge to sulfone with enhanced photoluminescence quantum yield.

Solvent Effects on the Photoinduced [6π]-Electrocyclization Reactions of Mono-, Di-, and Trisubstituted Arylamines: Photophysical, Preparative Photochemistry, and Mechanistic Investigations

The substituent and solvent effects on the spectroscopic behavior and on the photoinduced [6π]-electrocyclization reaction of substituted triphenylamine derivatives have been investigated. Direct irradiation of triphenylamines bearing electron-donor substituents in different solvents has provided for the first time the substituted exo/endo carbazole derivatives from modest to good yields, whereas triphenylamines bearing electron-withdrawing substituents did not provide the carbazoles due to the formation of charge transfer complexes (CTCs). A corollary of the experiments purports that the photoreaction is favored with weak electron-acceptor groups in polar solvents. The lowest-frequency absorption bands of the triarylamines (π,π* electronic transitions) displayed bathochromic shifts as the solvent polarity is increased. The fluorescence emission spectra of triarylamines bearing electron-donor substituents behave as mirror images of the lowest absorption bands, showing dependence on the solvent polarity. Conversely, triarylamines bearing formyl, acetyl, and nitro groups formed CTCs behaving as good fluorescence chromophores in polar solvents. Hammett correlations on the ΔE(0,0) energies of monosubstituted amines showed a bell-shape behavior where the ρ values depended on the solvent polarity. The physical quenching of the photoreaction of triarylamines has demonstrated for the first time that the triplet excited state is univocally the photoreactive state leading to exo/endo carbazole derivatives.

Molecular level solvent interaction (microscopic), electronic, covalent assembly (RDG, AIM & ELF), ADMET prediction and anti-cancer activity of 1-(4-Fluorophenyl)-1-propanone): Cytotoxic agent

1-(4-Fluorophenyl)-1-propanone) has been extensively investigated in this work due to its significant theoretical and experimental interest and potential pharmacological implications in the evaluation of cytotoxicity. To rationalize compound structure in solution phases through potential energy scan (PES) with optimization of the compound and its stable structure was validated with spectral analysis. Further structural characteristics of weak interactions with chemical functionalities are obtained by topological studies of the AIM and RDG parameters. In LOL and EFL studies, the strongest delocalized zones were found to occur at the locations C7-C10-C11 and C8-C4-C5 of the molecule. When the electronic properties of the title chemical were studied in solutions, the FMOs energies and MEP analysis showed that the compound was more reactive in the aqueous phase and the lower electronic absorption band gap was given by the ethanol solvent. Moreover, variations in the hyperpolarizability (α) and NBO characteristics of the compound were observed in different media. The efficiency of the title compound’s anti-cancer activity was evaluated using molecular docking studies, and drug affinity & toxicity of the compound were also anticipated by SwissADME.

Excited-state resonance Raman spectroscopy probes the sequential two-photon excitation mechanism of a photochromic molecular switch.

Some diarylethene molecular switches have a low quantum yield for cycloreversion when excited by a single photon, but react more efficiently following sequential two-photon excitation. The increase in reaction efficiency depends on both the relative time delay and the wavelength of the second photon. This paper examines the wavelength-dependent mechanism for sequential excitation using excited-state resonance Raman spectroscopy to probe the ultrafast (sub-30fs) dynamics on the upper electronic state following secondary excitation. The approach uses femtosecond stimulated Raman scattering (FSRS) to measure the time-gated, excited-state resonance Raman spectrum in resonance with two different excited-state absorption bands. The relative intensities of the Raman bands reveal the initial dynamics in the higher-lying states, Sn, by providing information on the relative gradients of the potential energy surfaces that are accessed via secondary excitation. The excited-state resonance Raman spectra reveal specific modes that become enhanced depending on the Raman excitation wavelength, 750 or 400nm. Many of the modes that become enhanced in the 750nm FSRS spectrum are assigned as vibrational motions localized on the central cyclohexadiene ring. Many of the modes that become enhanced in the 400nm FSRS spectrum are assigned as motions along the conjugated backbone and peripheral phenyl rings. These observations are consistent with earlier measurements that showed higher efficiency following secondary excitation into the lower excited-state absorption band and illustrate a powerful new way to probe the ultrafast dynamics of higher-lying excited states immediately following sequential two-photon excitation.

Push-Pull Effect of Terpyridine Substituted by Triphenylamine Motive-Impact of Viscosity, Polarity and Protonation on Molecular Optical Properties.

The introduction of an electron-donating triphenylamine motive into a 2,2′,6′,2′′-terpyridine (terpy) moiety, a cornerstone molecular unit in coordination chemistry, opens new ways for a rational design of photophysical properties of organic and inorganic compounds. A push-pull compound, 4′-(4-(di(4-tert-butylphenyl)amine)phenyl)-2,2′,6′,2′′-terpyridine (tBuTPAterpy), was thoroughly investigated with the use of steady-state and time-resolved spectroscopies and Density Functional Theory (DFT) calculations. Our results demonstrate that solvent parameters have an enormous influence on the optical properties of this molecule, acting as knobs for external control of its photophysics. The Intramolecular Charge Transfer (ICT) process introduces a remarkable solvent polarity effect on the emission spectra without affecting the lowest absorption band, as confirmed by DFT simulations, including solvation effects. The calculations ascribe the lowest absorption transitions to two singlet ICT excited states, S1 and S2, with S1 having several orders of magnitude higher oscillator strength than the “dark” S2 state. Temperature and viscosity investigations suggest the existence of two emitting excited states with different structural conformations. The phosphorescence emission band observed at 77 K is assigned to a localized 3terpy state. Finally, protonation studies show that tBuTPAterpy undergoes a reversible process, making it a promising probe of the pH level in the context of acidity determination.

Frequency-Selective Rasorber Based on High-Q Minkowski Fractal-Shaped Resonator for Realizing a Low Radar Cross-Section Radiating System

In this article, a novel design of compact frequency-selective rasorber exhibiting absorption–transmission–absorption characteristics and having high passband selectivity has been proposed. A square-loop resonator with mounted lossy elements serves as the elemental broadband absorber from 4 to 12 GHz. The transmission frequency at 8.4 GHz is realized by printing a Minkowski fractal-shaped resonator with a high-Q factor on the resistive layer, which provides a transmission pole at the frequency corresponding to the passband of a double-cross-slot-shaped bandpass layer. The functioning of the proposed frequency-selective rasorbers (FSR) is explained by a corresponding equivalent circuit model. The proposed FSR exhibits higher selectivity at the passband, thus making it a suitable candidate for shielding the narrowband radiating system. Measurements performed on the fabricated prototype of a 17 × 17 unit cell array provides experimental validation. Further, a low radar cross-section antenna is realized by integrating a patch antenna with the proposed FSR, which achieves an average out-of-band monostatic radar cross-section (RCS) reduction of 11.92 and 5.04 dB in the lower (4–7.5 GHz) and upper (9.2–10.8 GHz) absorption bands, respectively, while maintaining the other antenna parameters. Furthermore, the bistatic total RCS reduction of 77% and 60% are achieved in the lower and upper frequency bands, respectively.

Facile synthesis of an ambient stable pyreno[4,5-b]pyrrole monoanion and pyreno[4,5-b:9,10-b']dipyrrole dianion: from serendipity to design.

The stability of singly or multiply negatively charged π-conjugated organic compounds is greatly influenced by their electronic delocalization. Herein, we report a strategic methodology for isolation of a mysterious compound. The isolated compounds, a pyreno[4,5-b]pyrrole monoanion and pyreno[4,5-b:9,10-b′]dipyrrole dianion, were highly stable under ambient conditions due to high delocalization of the negative charge over multiple electron deficient C Created by potrace 1.16, written by Peter Selinger 2001-2019 ]]> N groups and pyrene π-scaffolds and allowed purification by column chromatography. To our knowledge, this is the first report on TCNE type reductive condensation of malononitrile involving pyrene di- and tetraone and formation of pyrenopyrrole. All compounds were characterized by spectroscopic methods and X-ray crystallography. A UV-vis spectroscopic study shows an intense low energy absorption band with a large absorption coefficient (ε).

Absorption/transmission integrated frequency selective surface with low profile and ultra-wide absorption band

ABSTRACT In this paper, an integrated low-profile frequency selective surface (FSS) is proposed, which has an ultra-wide absorption band in low band and a low loss transmission in passband. It consists of a bandpass metasurface (MS) and an absorptive MS loaded with resistors. Through coupling of the two metasurfaces, the perfect absorption in UWB is realized. Also, the equivalent circuit model of integrated FSS is deduced and its impedance is calculated. Furthermore, the mechanism of UWB absorption is provided. In addition, the integrated FSS with a central symmetrical unit is polarization-independent. The experimental results show that the absorptivity of the integrated FSS is larger than 89.8% in the range of 4–8.7 GHz except for some frequency points. The insertion loss at 12.64 GHz is only 0.4 dB. The experimental results are in good agreement with the simulation ones.

Switchable Polarization-Insensitive Frequency-Selective Surface Reflector/Absorber With Low Profile by Using Magnetic Material

A multifunctional frequency-selective surface reflector (FSSR) is found to be an applicable candidate for the realization of an antenna's radar cross-section reduction in or out of its operating frequency. In this letter, a polarization-selectable in-band switchable FSSR/absorber based on diodes is designed and experimentally demonstrated, which comprises a layer of active frequency-selective surface and a layer of metal-backed frequency-dispersive magnetic material (FDMM). The design realizes the switching functions of broadband absorption band from 3.5 to 12.0 GHz (110% bandwidth) with at least −10 dB reflectivity and a reflection band at 6.2 GHz with two-sided absorption bands (2.2–4.8 GHz, 74.3% bandwidth for the lower absorption band and 7.1–12.9 GHz, 58% bandwidth for the upper absorption band) by manipulating the <sc xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">on</small> and <sc xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">off</small> states of PIN diodes. Besides, due to the use of FDMM, the thickness of the FSSR is only 0.074 <italic xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">λ_L</i> , making it easy to design the reflective surface of the antenna. A prototype of the proposed FSSR/absorber is fabricated and measured, where reasonable agreement is observed.

Energy Tuning of Electronic Spin Coherent Evolution in Methylammonium Lead Iodide Perovskites.

We investigated the coherent evolution of the electronic spin at low temperature in high-quality CH3NH3PbI3 polycrystalline films by picosecond-resolved photoinduced Faraday rotation. We show that this coherent evolution can be tuned by choosing the pump-probe energy within the lowest optical-absorption band, and we explain it as the result of two main contributions: the localized electron and the localized hole. Their corresponding amplitude ratios are not constant across the lowest absorption band-an observation which disqualifies a free exciton from being at the origin of the electronic spin coherent evolution. We measured a spin coherence time of localized electrons (holes) of 4.4 ns (3.7 ns) at 1.635 eV, which evolves to about 7 ns at 1.612 eV (the hole coherence time remains almost constant at lower energies). Finally, we provide a global image of the spin coherent evolution in bulk metal halide perovskite, which overcomes recent controversies.

Extending Fluorescence of meso-Aryldipyrrin Indium(III) Complexes to Near-Infrared Regions via Electron Withdrawing or π-Expansive Aryl Substituents

The absorption and fluorescence spectra of 14 In(III) dipyrrin-based complexes are studied using time-dependent density functional theory (TDDFT). Calculations confirm that both heteroatom substitution of oxygen (N2O2-type) by nitrogen (N4-type) in dipyrrin ligand and functionalization at the meso-position by aromatic rings with strong electron-withdrawing (EW) substituents or extended π-conjugation are efficient tools in extending the fluorescence spectra of In(III) complexes to the near-infrared (NIR) region of 750-960 nm and in red-shifting the lowest absorption band to 560-630 nm. For all complexes, the emissive singlet state has π-π* character with a small addition of intraligand charge transfer (ILCT) contributing from the meso-aryl substituents to the dipyrrin ligand. Stronger EW nitro group on the meso-phenyl or meso-aryl group with extended π-conjugation induces red-shifted electronic absorption and fluorescence. More tetrahedral geometry of the complexes with N4-type ligands leads to less intensive but more red-shifted fluorescence to NIR, compared to the corresponding complexes with N2O2-type ligands that have a more planar geometry.

Structural, cation distribution, thermal properties, and electrical resistivity of nano NiAlxFe2-xO4 synthesized by flash auto combustion method

This work reports the effect of Al substitution in Ni ferrite on the structural and electrical resistivity of NiAlxFe2-xO4 (where, x= 0.00, 0.20, 0.40, 0.60, 0.80, and 1.00) nanoparticles synthesized by the flash auto combustion method. The XRD results show the presence of single-phase spinel structure. The average particle size estimated using Debye–Scherer׳s equation and was found to be in the range of 14 – 23.9 nm. Lattice parameter a (Å), cell volume and density the studied ferrite NiAlxFe2-xO4 were decreased with increasing Al+3 content. Fe, Al and Ni ions dominantly occupy both tetrahedral (A) and octahedral (B) sites. Occupancy from x=0 to x=1, are changed in A site, from 25%, 8% and 0% to 16% 13% and 6% for Fe, Ni, and Al ions, respectively, and in B site, from 42%, 25% and 0%, to 17% Fe, 22% Ni, 26% for Fe, Ni, and Al ions, respectively. The formation of spinel ferrite confirmed by the two types of stretching vibrations of metal oxide (M-O) bonds. The lower absorption band ʋocta lies in the range of 399-462 cm−1 and the higher absorption band ʋtetra lies in the range of 590-624 cm−1. Mössbauer measurement showed three broad hyperfine magnetic sextets in addition to superparamagnetic doublet were observed in most the measured samples. the component with the higher field value is associated with Fe3+ ions at B- site, while that with smaller field is associated with Fe3+ ions at A-site. The third collapse sextet which have smallest field and very broad width represents an intermediate phase between magnetic and superparamagnetic states. From TGA results, the activation energy of two weight losses are 20.7, 40.6 KJ/mol for Ni-Al ferrite and 14.12, 26.08 KJ/mol for Ni ferrite. The increase of Al content lead to increase in the resistivity from 7.4 to 412 MΩ at room temperature. With increasing temperature, the resistivity of all samples decreased which is a typical semiconductor behavior of ferrites consistent with Verwey hopping model. Curie temperature also increase as Al content increased in range of 353-634 K and in range of 474-577 K for DC and AC respectively. The high electrical resistivity of Ni-Al ferrites makes it preferable to be used in data storage devices

Ultraviolet spectroscopy of pressurized and supercritical carbon dioxide

Carbon dioxide (CO2) is prevalent in planetary atmospheres and sees use in a variety of industrial applications. Despite its ubiquitous nature, its photochemistry remains poorly understood. In this work we explore the density dependence of pressurized and supercritical CO2 electronic absorption spectra by vacuum ultraviolet spectroscopy over the wavelength range 1455-2000 Å. We show that the lowest absorption band transition energy is unaffected by a density increase up to and beyond the thermodynamic critical point (137 bar, 308 K). However, the diffuse vibrational structure inherent to the spectrum gradually decreases in magnitude. This effect cannot be explained solely by collisional broadening and/or dimerization. We suggest that at high densities close proximity of neighboring CO2 molecules with a variety of orientations perturbs the multiple monomer electronic state potential energy surfaces, facilitating coupling between binding and dissociative states. We estimate a critical radius of ~4.1 Å necessary to cause such perturbations.