- 标题
- 摘要
- 关键词
- 实验方案
- 产品
-
Application of polar solvent effects in absorption spectra for determination of lowest electron-excited states of phthalide
摘要： The optical absorption spectra of phthalide in polar (methanol) and nonpolar (n-hexane) solvents are recorded. The electronic phthalide spectrum was calculated by TDDFT B3LYP/6-311+G(d, p) using the polarisable continuum model. Based on an analysis of calculation data and the displacement of absorption bands in a polar solvent, it was established that the absorption bands of phthalide at energies of 3.51 and 3.96 eV correspond to singlet-triplet transitions to the T1 and T2 states, respectively.
关键词： Triplet excited states,Electronic absorption spectra,PCM TDDFT,Solvent effect,Phthalide
更新于2025-09-23 15:23:52
-
Theoretical study of photoreactions between oxidized pterins and molecular oxygen
摘要： Pterins are low molecular weight heterocyclic compounds that are widely distributed in living organisms, primarily in the form of reduced coenzyme forms. Oxidized pterins are present in the cells for the most part as oxidation products of tetrahydropterins and dihydropterins. Oxidized pterins are known to cause DNA photodamage under UV-irradiation. Photosensitization of oxidized pterins may cause oxidative stress in the human skin depigmentation disorder vitiligo. There have been made attempts to use oxidized pterins as sensitizers in photodynamic therapy (PDT) of cancer. The photoreactions between a set of six pterin compounds and molecular oxygen were explored using density functional theory, a time-dependent formalism for excited states (TD-DFT) and a continuum COSMO model to include the effects of H2O solvation. Both acid and base forms of pterins were taken into consideration. The computed singlet and triplet excitation energies are in agreement with the experimental data. We showed that compounds with the most electronegative lateral substituent (formyl, carboxyl) at C6 position have the highest value of both S0 and T1 state ionization potential. We conclude that pterin molecules do participate in photoreactions with molecular oxygen. Oxidized pterins are able to generate singlet oxygen and may also produce superoxide-anion radicals indirectly through autoionization reactions. Direct electron transfer reactions between pterins and oxygen were also studied.
关键词： TDDFT,DFT,Pterins,Singlet oxygen,Triplet states
更新于2025-09-23 15:23:52
-
Graphdiyne: A promising nonlinear optical material modulated by tetrahedral alkali-metal nitrides
摘要： A new series of the functionalized graphdiyne (GDY) material was designed by adsorbing the tetrahedral Li3NM molecules on the largely delocalized π-conjugated GDY surface, namely Li3NM@GDY (M = Li, Na, K), and its structure, chemical stability, electronic property, and the first hyperpolarizability were investigated by using the density functional theory computations. Our results reveal that the Li3NM molecules can interact with three triangular holes on the GDY surface, in which the van der Waals interactions play a crucial role in enhancing the structural stability. Meanwhile, the total NPA charges on the Li3NM molecules are gradually increased from Li to K, and the Li3NM molecules can transfer an electron to GDY, forming intramolecular electron donor and acceptor pairs. All of studied complexes exhibit the giant static first hyperpolarizabilities (βtot), up to ~2.88 × 105 a.u. for Li3NK@GDY, which can be explained by two-level expression from the TDDFT calculations. This study will inevitably stimulate further synthesis of the novel graphdiyne-based nonlinear optical materials.
关键词： Graphdiyne,Electronic structure,TDDFT,Charge transfer,Nonlinear optical property
更新于2025-09-23 15:23:52
-
Structural, energetic and spectroscopic studies of new luminescent complexes based on 2-(2′-hydroxyphenyl)imidazo[1,2- <i>a</i> ]pyridines and 1,2-phenylenediboronic acid
摘要： Three new blue-luminescent complexes of selected imidazo[1,2-a]pyridine derivatives and 1,2-phenylenediboronic acid have been synthesized and structurally characterized using single-crystal X-ray diffraction. Additionally, the crystal structures of two of the (N,O)-donor compounds have been evaluated for the first time. The crystal packing and molecular motifs observed in the studied crystals have been thoroughly analysed, including computational studies, and are also discussed within the context of analogous systems reported in the literature. It appears that the new compounds form different crystal networks with regard to the asymmetric unit content and packing, although some similarities can be found. In all cases a typical centrosymmetric dimer bound via boronic acid groups is formed, characterized by an interaction energy of about -80 kJ mol-1, while the 2-(2'-hydroxyphenyl)imidazo[1,2-a]pyridine complex and its methoxy derivative form solvate structures, somewhat resembling the previously studied 8-oxyquinolinate analogues. As far as the spectroscopic properties are concerned, the lowest energy excitation observed in the studied complexes is based on the highest occupied molecular orbital–lowest unoccupied molecular orbital transition, and both these molecular orbitals are centred predominantly on the (N,O)-donor species according to the results of time-dependent density functional theory. Thus, the charge transfer observed for the 8-oxyquinolinate equivalents does not occur in these cases. Consequently, the spectroscopic behaviour of the series is very much comparable with that of the parent imidazo[1,2-a]pyridine derivatives, if the excited-state intramolecular proton-transfer process does not take place, as shown by the absorption and emission spectra collected in toluene and acetone solutions. Complexation causes a reduction in the Stokes shift compared with the respective (N,O)-donor molecules.
关键词： periodic calculations,TDDFT,UV–Vis spectroscopy,X-ray diffraction,time-dependent density functional theory,spectroscopic properties,luminescent boron complexes,transferred aspherical atom model (TAAM) refinement
更新于2025-09-23 15:22:29
-
Resonance Raman Spectro-Electrochemistry to Illuminate Photo-Induced Molecular Reaction Pathways
摘要： Electron transfer reactions play a key role for artificial solar energy conversion, however, the underlying reaction mechanisms and the interplay with the molecular structure are still poorly understood due to the complexity of the reaction pathways and ultrafast timescales. In order to investigate such light-induced reaction pathways, a new spectroscopic tool has been applied, which combines UV-vis and resonance Raman spectroscopy at multiple excitation wavelengths with electrochemistry in a thin-layer electrochemical cell to study [RuII(tbtpy)2]2+ (tbtpy = tri-tert-butyl-2,2′:6′,2′′-terpyridine) as a model compound for the photo-activated electron donor in structurally related molecular and supramolecular assemblies. The new spectroscopic method substantiates previous suggestions regarding the reduction mechanism of this complex by localizing photo-electrons and identifying structural changes of metastable intermediates along the reaction cascade. This has been realized by monitoring selective enhancement of Raman-active vibrations associated with structural changes upon electronic absorption when tuning the excitation wavelength into new UV-vis absorption bands of intermediate structures. Additional interpretation of shifts in Raman band positions upon reduction with the help of quantum chemical calculations provides a consistent picture of the sequential reduction of the individual terpyridine ligands, i.e., the first reduction results in the monocation [(tbtpy)Ru(tbtpy?)]+, while the second reduction generates [(tbtpy?)Ru(tbtpy?)]0 of triplet multiplicity. Therefore, the combination of this versatile spectro-electrochemical tool allows us to deepen the fundamental understanding of light-induced charge transfer processes in more relevant and complex systems.
关键词： ruthenium bis-terpyridine complex,resonance Raman,in situ spectro-electrochemistry,TDDFT,UV-vis
更新于2025-09-23 15:22:29
-
Effect of Fluorination on Bandgap, First and Second order Hyperpolarizabilities in Lithium Substituted Adamantane: A Time Dependent Density Functional Theory
摘要： Time dependent density functional theory is used to systematically examine the band gap variation of Li-substituted adamantanes upon fluorination. It is realized that the absorption wavelength of Li-Adamantane can be fine tuned within UV-Visible region by changing the degree of fluorination. The static and dynamic hyperpolarizabilities of fluorinated Li-Adamantane derivatives were computed using coupled perturbed Kohn Sham theory. In this article, we report Pockel, dc-Kerr, ESHG, degenerate four wave mixing coefficients and nonlinear refractive indices from the first and second order hyperpolarizability calculations. A high positive nonlinear refractive index and significant second harmonic generation efficiency at Nd:YAG Laser wavelength are observed in F3Li-Adm derivative.
关键词： adamantane,non linear responses,hyperpolarizability,TDDFT
更新于2025-09-23 15:21:21
-
Assessment of functionals for TDDFT calculations of one- and two-photon absorption properties of neutral and anionic fluorescent proteins chromophores
摘要： Performance of DFT functionals with different percentage of exact Hartree-Fock exchange energy (EX) is assessed for recovery of the CC2 reference one- (OPA) and two-photon absorption (TPA) spectra of fluorescent proteins chromophores in vacuo. The investigated DFT functionals, together with their EX contributions are: BLYP (0%), B3LYP (20%), B1LYP (25%), BHandHLYP (50%) and CAM-B3LYP (19% at short range and 65% at long range). Our test set consists of anionic and neutral chromophores as naturally occuring in the fluorescent proteins. For the first time, we compare TDDFT and CC2 methods for higher excited states, than the S1 state, exhibiting relatively large TPA intensity. Our TDDFT results for neutral chromophores reveal an increase of excitation energies as well as TPA and OPA intensities errors, compared to CC2-derived results, as the DFT functional contains less exact exchange. The long-range-corrected CAM-B3LYP functional performs the best, closely followed by BHandHLYP, while BLYP usually significantly underestimates all investigated spectral properties, hence being the worst in reproducing the reference CC2 results. The hybrid B3LYP and B1LYP functionals can be roughly placed in between. We propose that TDDFT may underestimate the TPA intensities for neutral chromophores of fluorescent proteins due to underestimated oscillator strengths between some excited states. In case of anionic chromophores, we find that B3LYP and B1LYP functionals overcome others in terms of reproducing CC2 excitation energies. On the other hand, however, TPA intensity is usually significantly underestimated and in this respect CAM-B3LYP functional seems to be again superior. In contrast to the case of neutral chromophores, it seems that large magnitude of excited-state dipole moment or change in dipole moment upon excitation may be the driving force behind high TPA transition moments.
关键词： fluorescent proteins chromophores,one-photon absorption,DFT functionals,two-photon absorption,TDDFT,CC2
更新于2025-09-23 15:21:21
-
Osmium sensitizer with enhanced spin-orbit coupling for panchromatic dye-sensitized solar cells
摘要： Low-lying triplet metal-to-ligand charge transfer (3MLCT) transitions of osmium complexes induced by spin-orbit coupling (SOC) is promising to extend photocurrent response when applied to dye-sensitized solar cells. In this study, we present a newly designed osmium complex (coded CYC-33O), incorporating a 2-thiohexyl-3,4-ethylenedioxythiophene functionalized bipyridyl ancillary ligand to red-shift the absorption and enhance the absorbance of both singlet and triplet MLCT transitions. Time-dependent density functional theory (TDDFT) calculations clearly signify the reinforced 1MLCT and 3MLCT transitions of CYC-33O mainly originate from osmium to 4,4',4"-tricarboxy-2,2':6',2"-terpyridine anchoring ligand, advantaging the heterogeneous electron transfer between CYC-33O and TiO2. The device sensitized with CYC-33O exhibits the panchromatic conversion beyond 1000 nm, yielding the photocurrent density of 19.38 mA cm–2 which is much higher than those of the cells based on the ruthenium analogue (CYC-33R) and model osmium complex (Os-3) sensitizers.
关键词： dye-sensitized solar cell,triplet metal-to-ligand charge transfer (3MLCT),ruthenium complex,spin-orbit coupling (SOC),osmium complex,time-dependent density functional theory (TDDFT)
更新于2025-09-23 15:21:01
-
Significance of five membered heterocycles in fine tuning of HOMO-LUMO gap of simple donor-acceptor system as organic solar cell material: A DFT approach
摘要： The significance of five membered heterocycles in simple donor-acceptor system was elaboratively studied by density functional theory (DFT) and time dependent density functional theory (TDDFT). By effectively substituting eight different rings the HOMO-LUMO gap can be reduced considerably. The nuclear independent chemical shift (NICS) calculations help to predict the aromaticity of central heterocyclic systems. The natural bond orbital (NBO) analysis reveals the charge contribution. The close observation of frontier molecular orbitals (FMO) gives a detailed explanation of delocalization.
关键词： NICS,DFT,NBO,TDDFT,HOMO-LUMO
更新于2025-09-23 15:19:57
-
Effect of Electron Withdrawing/Donating Groups on the Sensitizing Action of the Novel Organic Dye a??3-(5-(4-(diphenylamino)styryl)thiophen-2-yl)-2-cyanoacrylic acida?? for N-type Dye Sensitized Solar Cells: A Theoretical Study
摘要： Computational studies using DFT and TDDFT approaches have been performed to study a series of metal free donor-π-acceptor (D-π-A) dyes. Taking the novel organic D5 dye (3-(5-(4-(diphenylamino)styryl)thiophen-2-yl)-2-cyanoacrylic acid) as the primary structure, with triphenylamine as the donor, cyanoacrylic acid as the acceptor and a thiophene group as the π-linker, we have studied the effect of the substitution of different electron withdrawing and electron donating groups at different positions on the dye efficiency, by analyzing the geometry, charge distribution, electron injection and absorbance spectra. Electron injection has also been addressed for the substituted dyes immobilized on TiO2. Our calculations show that adding electron withdrawing groups at specific positions will lead to a higher efficiency of the dye.
关键词： TDDFT,electron withdrawing groups,DFT,electron donating groups,dye sensitized solar cells,D5 dye
更新于2025-09-23 15:19:57