Synthesis, photoluminescence, and theoretical studies of novel Cu(I) complex

A novel diimine Cu(I)complex [Cu(ABPQ)(DPEphos)]BF4 [ABPQ and DPEphos are acenaphtho[1,2-b]bipyrido[2,3-h:3,2-f]quinoxaline and bis(2-(diphenylphosphanyl)phenyl) ether, respectively] is synthesized, and its photophysical properties are experimentally and theoretically characterized. The emission bands centered at ca. 400/470 and 550 nm of [Cu(ABPQ)(DPEphos)]BF4 are attributed to the ligand-centered pi -> pi* transition and the metal-to-ligand charge transfer d pi(Cu) -> pi*(N-N) transition, respectively. The luminescence quantum yield of [Cu(ABPQ)(DPEphos)]BF4 in CHCl3 is found to be about five times higher than that of [Cu(Phen)(DPEphos)]BF4.

The Reasons for Ligand-Dependent Quantum Yields and Absorption Spectrum of Four Polypyridylruthenium(II) Complexes with a Tetrazolate-Based Ligand: TDDFT Study

The quantum yield, lifetime, and absorption spectrum of four [Ru(bpy)(2)L](+) [where bpy is 2,2'-bipyridyl; L is represented by the deprotonated form of 2-(1H-tetrazol-5-yl)pyridine (L1) or 2-(1H-tetrazol-5-yl)pyrazine (L2)], as well as their methylated complexes [Ru(bpy)(2)LMe](2+) (RuL1Me and RuL2Me) are closely ligand dependent. In this paper, density functional theory (DFT) and time-dependent DFT (TDDFT) were performed to compare the above properties among these complexes. The calculated results reveal that the replacement of pyridine by pyrazine or the attachment of a CH3 group to the tetrazolate ring greatly increases the pi-accepting ability of the ancillary ligands.

Synthesis, characterization, photophysics and electrophosphorescent applications of phosphorescent platinum cyclometalated complexes with 9-arylcarbazole moieties

A series of cyclometalating platinum(II) complexes with substituted 9-arylcarbazolyl chromophores have been synthesized and characterized. These complexes are thermally stable and most of them have been characterized by X-ray crystallography. The phosphorescence emissions of the complexes are dominated by (MLCT)-M-3 excited states. The excited state properties of these complexes can be modulated by varying the electronic characteristics of the cyclometalating ligands via substituent effects, thus allowing the emission to be tuned from bright green to yellow, orange and red light. The correlation between the functional properties of these metallophosphors and the results of density functional theory calculations was made. Because of the propensity of the electron-rich carbazolyl group to facilitate hole injection/transport, the presence of such moiety can increase the highest occupied molecular orbital levels and improve the charge balance in the resulting complexes relative to the parent platinum(II) phosphor with 2-phenylpyridine ligand.

Electronic structures and chemical bonding in 4d transition metal monohalides

Bond distances, vibrational frequencies, dipole moments, dissociation energies, electron affinities, and ionization potentials of NIX (XM = Y-Cd, X = F, Cl, Br, I) molecules in neutral, positively, and negatively charged ions were studied by density functional method, B3LYP. The bonding patterns were analyzed and compared with both the available data and across the series. It was found that besides ionic component, covalent bonds are formed between the 4d transition metal s, d orbitals, and the p orbital of halogen. For both neutral and charged molecules, the fluorides have the shortest bond distance, iodides the longest. Although the opposite situation is observed for vibrational frequency, that is, fluorides have the largest value, iodides the smallest. For neutral and anionic species, the dissociation energy tends to decrease with the increasing atomic number from Y to Cd, suggesting the decreasing or weakening of the bond strength. For cationic species, the trend is observed from Y to Ag.

Theoretical investigation of 5D-metal monocarbide

Bond distances, vibrational frequencies, electron affinities, ionization potentials and dissociation energies of the title molecules in neutral, positively and negatively charged ions were studied by use of density functional method. The calculated results were compared with previous theoretical and experimental studies. Ground states for each molecule were assigned. It was found that for some molecules, low-lying state, in which the energy is much close to the ground state, was obtained. In this case, further studies both experimentally and theoretically are necessary in order to find the true global minimum.

Study on stimulated emission of Eu2+ in crystal KMgF3 : Eu2+

The line emission peak of Eu2+ ion in crystal KMgF3 is at 360 nm. The probability of stimulated emission on 4f(7) (P-6(7/2))-> 4f(7)(S-8(7/2)) transition was predicted with a four-level decay model of Eu2+6P7/2 excited states proposed by the authors. Optic gain and net gain coefficient (g = 11.4 +/- 3.2)cm(-1) of 360 nm emission in crystal KMgF3 : Eu2+ were measured by ASE method, and the predication was proved by experiment. The net gain coefficient can be increased by annealing or doping crystal KMgF3 : Eu2+ with Gd3+ or Ce3+.

Sequential deprotonation of meso-(p-hydroxyphenyl)porphyrins in DMF: From hyperporphyrins to sodium porphyrin complexes

Sequential deprotonations of meso-(p-hydroxyphenyl)porphyrins (p-OHTPPH2) in DMF + H2O (V/V = 1:1) mixture have been verified to result in the appearance of hyperporphyrin spectra. However, when the deprotonations of these p-OHTPPH2 are carried out in DMF, the spectral changes differ considerably from those in the mixture mentioned above. At low [OH-], the optical spectra in the visible region are still considered to have characteristics of hyperporphyrin spectra. Further deprotonation at much higher basicity makes the optical spectra form three-banded spectra similar to those in the acidic solution. To clarify the molecular origins of these changes, UV-vis, resonance Raman (RR), proton nuclear magnetic resonance (H-1 NMR) experiments are carried out. Our data give evidence that p-OHTPPH2 in DMF can be further deprotonated of pyrrolic-H by higher concentrated NaOH, due to an aprotic medium like DMF effectively weakening the basicity of the porphyrin relative to that of the NaOH, and coordinates with two sodium ions (except the sodium ions that interact with the peripherial phenoxide anions) to form the sodium complexes of p-OHTPPH2 (Na2P, to lay a strong emphasis on the sodium ions that coordinate with the central nitrogen atom), which can be regarded as the porphyrin anions being perturbed by the sodium cations due to their highly ionic character.

Synthesis of Sr2CeO4: Eu-3 by citrate-gel method and its luminescence properties

A novel phosphor Sr2CeO4 was synthesized by the citrate-gel method. The results of XRD show that the temperature at which the crystallization starting is lowered and the soak time for complete crystallization is decreased. The values of pH of the precursor and the ratio( R) between the citrate and cation ions have an effect on the crystallization process. The host can transfer its exciting energy to rare earth ion Eu3+. The doped compound emits strong white light when the concentration of the doped Eu3+ is low. When that of Eu3+ is increased, it emits strong red light. The fluorescence from the higher excited states can be observed because the multiphonon relaxation probability between Eu3+ ions is low.

The multicolour three-photon resonant ionization spectrum studies in uranium atom

The multicolour three-photon resonant ionization spectra of U-238 were measured by using the pulsed dye lasers system synchronously pumped by a frequency doubled Nd:YAG-laser 532 nm output(operated at 10 Hz),a device for atomic beam of U, time-of-flight mass spectrometer and boxcar integrator. The dye laser pulses have a 6 ns duration. Beams from the dye lasers, which have the same polarization direction and are focused by lenses, entered an interaction chamber through opposite windows on a common axis and spatialy overlapped the U atomic beam. The optical pulse from dye laser DL2 was delayed to arrive at the interaction region 8 ns after the pulse from dye laser DL1; in the same way,the pulse from DL3 was delayed 8 ns after from DL2. The atomic beam device was made from stainless steel. We generated the U vapor by heating solid U in a graphite crucible by e-type electron -field on first excited states were studied in uranium atom. The question how to determine single-colour, two-colour and three-colour three-photon resonant ionization peak in the three-colour three-photon resonant ionization spectra diagram were solved.

CALCULATIONS OF THE EIGENVALUES OF PURE QUADRUPOLE INTERACTION IN MOSSBAUER-EFFECT STUDIES

Two approximate formulae to calculate the eigenvalues of pure quadrupole interaction in Mossbauer effect studies have been proposed and the eigenvalue coefficients in the formulae have been given for various excited states and ground states of the nucleus with different spin. All the eigenvalues of pure quadrupole interaction between both excited state and ground state of nucleus with spin I = 3/2 divided-by 9/2 and the electric-field gradient with different asymmetry parameter (eta = 0 divided-by 1.0) have been calculated by these formulae. The results show that the accuracies in all the calculations are more satisfactory or same in comparison with those obtained by the formula of Shenoy and Dunlap, especially when the asymmetry parameter of electric-field gradient is larger than 0.8 for the nucleus with spin I = 5/2.

Photodissociation of o-dichlorobenzene at 266 nm

The photodissociation o-dichlorobenzene at 266 nm has been investigated using the universal crossed molecular beam technique. Photofragment translational energy distribution P(E-t) and angular distribution of photofragments have been obtained and it is estimated that 23% of the available energy is assigned to translational energy. The anisotropy parameter is determined to be 0.4. From P(E-t) and beta we deduce that o-C6H4Cl2 photodissociation is a slow process. Ab initio calculation has been performed and it shows that the parent molecule has a larger geometry deformation in its excited states comparing with that of the ground state. The possible dissociation mechanism has also been proposed. (C) 1999 Elsevier Science B.V. All rights reserved.

Three-photon-excited upconversion luminescence of Ce3+: YAP crystal by femtosecond laser irradiation

Infrared to ultraviolet and visible upconversion luminescence was demonstrated in trivalent cerium doped YAlO3 crystal (Ce3+: YAP) under focused infrared femtosecond laser irradiation. The fluorescence spectra show that the upconverted luminescence comes from the 5d-4f transitions of trivalent cerium ions. The dependence of luminescence intensity of trivalent cerium on infrared pumping power reveals that the conversion of infrared radiation is dominated by three-photon excitation process. It is suggested that the simultaneous absorption of three infrared photons pumps the Ce3+ ion into upper 5d level, which quickly nonradiatively relax to lowest 5d level. Thereafter, the ions radiatively return to the ground states, leading to the characteristic emission of Ce3+. (c) 2005 Optical Society of America.

Selectively excited photoluminescence of GaAs1-xNx single quantum wells

GaAsN bulk and GaAsN/GaAs single quantum wells grown by molecular beam epitaxy are studied by selectively excited photoluminescence (PL) measurements. A significant difference is observed in the PL spectra when the excitation energy is set below or above the band gap of GaAs for the GaAsN/GaAs quantum well samples, while the spectral features of GaAsN bulk are not sensitive to the excitation energy. The observed difference in PL of the GaAsN/GaAs quantum well samples is attributed to the exciton localization effect at the GaAsN/GaAs interfaces, which is directly correlated with the transfer and trap processes of the photogenerated carriers from GaAs into GaAsN through the heterointerfaces. This interface-related exciton localization effect can be greatly reduced by a rapid thermal annealing process, making the PL be dominated by the intrinsic delocalized transition in GaAsN/GaAs. (C) 2003 American Institute of Physics.

Doubly excited 2s2p P-1,3(1) resonances in photoionization of helium

The multi-configuration Dirac Fock (MCDF) method is implemented to study doubly excited 2s2p P-1,3(1) resonances of the helium atom and the interference between photoionization and photo excitation autoionization processes. In order to reproduce the total photoionization sprectra, the excited energies from the ground 1s(2) S-1(0) state to the doubly excited 2s2p P-1,3(1) states and the relevant Auger decay rates and widths are calculated in detail. Further more, the interference profile determined by the so-called Fano parameters q and rho(2) is also reproduced. Good agreement is found between the present results and other available theoretical and experimental results. This indeed shows a promising way to investigate the Fano resonances in photoionization of atoms within the MCDF scheme, although there are some discrepancies in the present calculations of the 2s2p P-3(1) state.