Optically detected magnetic resonance from a complex donor in CdS

A new optically-detected magnetic resonance at g = 1.885 for H|c, associated with a broad emission band at 2.17 eV, has been observed. The 2.17 eV band is attributed to donor-acceptor recombination involving a complex double donor, and the optically-detected magnetic resonance effect to spin-dependent electron transfer from a shallow donor to the complex donor.     

Radiationless transitions in complexes

A theoretical study is presented for the possible changes in radiationless transition probability from the first excited states to the ground state when a molecule enters a complex. An expression is derived that incorporates the contribution from the totally symmetric intermolecular vibration of the donor relative to the acceptor. The bond-length change has been calculated for a molecule entering a complex and on excitation of the latter in the chargetransfer band and also in states localized in the donor. It is found that there should not be large changes in probability for transitions localized in the donor.     

Shallow donor state due to nitrogen-hydrogen complex in diamond

Based on an ab initio calculation, we propose a possible shallowing of a nitrogen (N) donor in diamond, in contrast to the traditional thinking that it is very deep. A complex defect of N and hydrogen (H), N-H-N, should be much shallower than an isolated N donor. A qualitative scenario for formation of the N-H-N defects is presented. The existence of this complex is strongly suggested by a recent discovery of a new muonium center in N-rich diamond.     

The effect of bromine substitution on the charge-transfer emission of the complex of phenanthrene and tetracyanobenzene

The absorption spectra of the charge-transfer complexes of sym-tetracyanobenzene (TCNB) with phenanthrene, 9-bromophenanthrene, and 9,10-dibromophenanthrene are measured in chloroform solutions at room temperature. The total emission and phosphorescence spectra of the donors and the complexes are measured at 77 K in rigid glasses. The phosphorescence decay lifetimes are determined for phenanthrene, TCNB, and for the phenanthrene-TCNB complex, and a decrease in the phenanthrene-TCNB complex lifetime relative to the lifetimes of the two components is observed. The luminescence spectra of the complexes exhibit both a red shift and a lack of structure as compared with the donor spectra. The results are interpreted, in agreement with the results of Iwata et al. for the phenanthrene-TCNB complex (1), as an indication that there is a considerable degree of charge-transfer character in the lowest triplet state (T₁). Bromine substitution leads to a decrease in the energy of the phenanthrene triplet state. As a result, the energy gap between the donor molecule triplet state and the complex charge-transfer triplet state decreases from phenanthrene, to 9-bromophenanthrene, to 9,10-dibromophenanthrene. The results suggest that the proximity of these two triplet states in 9,10-dibromophenanthrene and its charge-transfer complex leads to some local donor triplet state character in the emitting complex triplet state.     

The effect of donor self-association on EPR studies of transient complex formation between nitroxide radicals and solvent molecules

Nitroxide radical-hydrogen donor systems in which the donor can self-associate are examined by EPR techniques. Data for CH₃OH and CH₃COOH and the nitroxide radical TMPO are first fitted by using methods developed for transient complex formation between hydrogen donors and nitroxides. TheK _assoc and hyperfine coupling constants obtained are inconsistent with previous correlations with thepK _a of the hydrogen donor. An alternative method of analysis that incorporates donor self-association is developed and applied to the systems studied.     

硅中热施主的电子结构

利用20—300K的Hall系数测量和6-300K的红外光吸收,研究了含氧P型CZ硅单晶经450℃不同时间热处理后所产生的热施主问题。Hall系数测量表明:经100hr热处理的样品存在两个施主能级:E₁=58meV,E₂=110meV。对不同热处理时间的样品,从低温红外光吸收则可看见由于热施主所引起的复杂吸收光谱。这些吸收峰的数目随着热处理时间的加长而增加和加强。利用类氢模型和有效质量理论拟会和计算,可以证明与氧有关的热施主很可能是双重电荷施主。这些双重施主有多种组态,它与450℃热处理的时间有关。 关键词：     

Systematics of bound excitons and bound multiexciton complexes for shallow donors in silicon

We report luminescence measurements of transitions involving bound multiple exciton complexes in Si:Sb and Si:As. The systematics of the donor systems Si:P, Si:As and Si:Sb are examined. We find that the splittings between the two observed series of lines are independent of complex number and donor type.     

Single crystal conductivity of bipyridine-TCNQ salts

The sharp contrast between the conductivity of complex TCNQ salts with symmetric and asymmetric bipyridine donors reveals the role played by the asymmetric molecules in well conducting organic salts. A highly anisotropic strongly correlated semiconductor is obtained when the donor molecule is symmetric, a smeared out “metal insulator” transition is found with the asymmetric donor modification.     

Pd（Ⅱ）苊醌缩氨基硫脲配合物的合成、表征及其与DNA的相互作用

合成了新型配合物Pd（Ⅱ）苊醌缩氨基硫脲,用元素分析、红外光谱、紫外光谱、核磁共振光谱和热分析对配合物进行了表征,并用荧光光谱研究了配体和配合物与DNA的相互作用。结果表明,配合物中配体以氧、氮和硫（ON S）三齿鳌合形式与金属离子配位,配合物与DNA的结合能力远大于配体。     

Mutual passivation of donors and isovalent nitrogen in GaAs

We study the mutual passivation of shallow donor and isovalent N in GaAs. We find that all the donor impurities, SiGa, GeGa, SAs, and SeAs, bind to N in GaAs:N, which has a large N-induced band-gap reduction relative to GaAs. For a group-IV impurity such as Si, the formation of the nearest-neighbor SiGa-NAs defect complex creates a deep donor level below the conduction band minimum (CBM). The coupling between this defect level with the CBM pushes the CBM upwards, thus restoring the GaAs band gap; the lowering of the defect level relative to the isolated SiGa shallow donor level is responsible for the increased electrical resistivity. Therefore, Si and N mutually passivate each other's electrical and optical activities in GaAs. For a group-VI shallow donor such as S, the binding between SAs and NAsdoes not form a direct bond; therefore, no mutual passivation exists in the GaAs:(S+N) system.     

Enhanced Emission Induced by FRET from a Long-Lifetime, Low Quantum Yield Donor to a Long-Wavelength, High Quantum Yield Acceptor

We report observation of high quantum yield, long-lifetime fluorescence from a red dye BO-PRO-3 excited by resonance energy transfer (RET). The acceptor fluorescence was highly enhanced upon binding to the donor-labeled DNA. A ruthenium complex (Ru) was chosen as a donor in this system because of its long fluorescence lifetime. Both donor and acceptor were non-covalently bound to DNA. Emission from the donor-acceptor system (DA) at wavelengths exceeding 600 nm still preserves the long-lifetime component of the Ru donor, retaining average fluorescence lifetimes in the range of 30–50 ns. Despite the low quantum yield of the Ru donor in the absence of acceptor, its overall quantum yield of the DA pair was increased by energy transfer to the higher quantum yield acceptor BO-PRO-3. The wavelength-integrated intensity of donor and acceptor bound to DNA was many-fold greater than the intensity of the donor and acceptor separately bound to DNA. The origin of this effect is due to an efficient energy transfer from the donor, competing with non-radiative depopulation of the donor excited state. The distinctive features of DA complexes can be used in the development of a new class of engineered luminophores that display both long lifetime and long-wavelength emission. Similar DA complexes can be applied as proximity indicators, exhibiting strong fluorescence of adjacently located donors and acceptors over the relatively weak fluorescence of separated donors and acceptors.     

End-to-end diffusion coefficients and distance distributions from fluorescence energy transfer measurements: Enhanced resolution by using multiple donors with different lifetimes

We describe a method to improve the resolution of donor-to-acceptor distance distributions in molecules which are flexing on the timescale of the fluorescence lifetime. We measured the timedependent donor decays of two donor (D)-acceptor (A) pairs, where the donor lifetimes were substantially different. The donors were an indole residue (5.7 ns) and a naphthalene residue (24.4 ns). The same dansyl acceptor was used for both D-A pairs. The donor decays are complex due to both a distribution of D-A distances and D-A diffusion. Using the donor decay data for each D-A pair alone, it is difficult to resolve both the distance distribution and the D-to-A diffusion coefficient. However, these values are unambiguously recovered from global analysis of the data from both D-A pairs. The increased resolution from the global analysis is apparently the result of the complementary information content of the data for each D-A pair. The shorter-lived indole donor provides more information on the time-zero distance distribution because there is less time for D-A diffusion, and the longer-lived naphthyl donor is quenched to a greater extent than indole due to the longer time for diffusion-enhanced energy transfer. Simulations were also used to demonstrate the increased resolution of global analysis with different lifetime donors to obtain distance distribution parameters in the presence of D-A diffusion.     

Spectral intensities of lanthanide complexes

The effects of solvents and complex formation with nitrogen donor ligands on the spectral intensities of the f→f transitions in Nd(III) ion have been reported. The intensity parameters T_λ have been calculated for 14 systems and are compared with oxygen donor ligands.     

Design of shallow donor levels in diamond by isovalent-donor coupling

Using the first-principles pseudopotential method, we have studied simultaneous isovalent and n-type doping in diamond. We show that Si induces fully occupied isovalent levels near the valence band maximum. The Si levels interact with N donor levels, making them much shallower. The donor transition energy level of the N + 4Si defect complexes is found to be 0.09 eV below the conduction band minimum, which is the shallowest level found thus far for this system. The binding energy of the N + 4Si complex is also large enough to insure its stability.     

Ultrasonic and optical studies on charge transfer complexes of p-chloranil with certain aromatic hydrocarbons in DMSO at 303.15 K

Ultrasonic investigation has been carried out on six ternary systems to establish the complex formation between p-chloranil (acceptor) and six aromatic hydrocarbons (donors), namely, benzene, toluene, o-xylene, m-xylene, p-xylene and mesitylene in DMSO medium at 303.15 K and at atmospheric pressure. Studies were carried out in the concentration range of 0.002 to 0.02 M of acceptor and donor with equimolar concentration of the two components in solution. The trend in the acoustical parameters and magnitude of excess thermo acoustical parameters has been used to identify the existence of strong intermolecular interaction through charge transfer complex formation. The formation of 1:1 complex was also confirmed by UV-Visible spectroscopic method at 303.15 K in these systems. It may be pointed out that the formation constants of the charge transfer complexes determined by Benesi-Hildebrand (spectroscopic) and Kannappan (ultrasonic) methods show similar trend and well establish the influence of structural aspect of the donor aromatic compounds on the stability of charge transfer complexes.     

Metal-insulator electronic phase transitions in wide-gap ZnO semiconductors

Metal-insulator electronic phase transitions in wide-gap ZnO semiconductors have been studied. The influence of defect complex caused by oxygen vacancy and interstitial zinc atom on the metal-insulator transition is considered. The peculiarities of this transition in ZnO films doped with donor or acceptor impurity and the influence of mentioned defect complex on the charge carrier transfer mechanism were investigated.     

A Quantitative Study of Effects of Rare Earth Chelates on NMR Chemical Shifts: I. Treatment of 1:1 Complexes and Chemical Shifts of the Pure Complexes

Recently several rare earth chelates have been found that induce large and dramatic chemical shifts when complexed with a ligand.¹ This is due to paramagnetic shielding, the mechanism of which is observed to be a pseudo-contact shift. In cases such as this involving dynamic equilibria where exchange of protons is rapid compared to observation time, the observed chemical shift represents an average environment determined by the time the proton nuclei spend at each site. The effective site of the complex is a lone pair donor such as the oxygen of a carbonyl group, alcohol, or ether, or the nitrogen of various nitrogen containing groups. The oxygen bearing compounds could theoretically form strong complexes with the added possibility of multiple complexes with chelates. The nitrogen bearing compounds of weak donor strength and containing only a lone pair would presumably form only the 1:1 complex.     

Spectrophotometric and E.P.R. study of TCNE charge-transfer complexes

Liquid state charge-transfer complexes formed from the strong acceptor tetracyanoethylene (TCNE) and four donors of like donor properties are studied by spectrophotometric and E.P.R. techniques. If the enthalpy of complex formation ΔH is sufficiently large, the triplet state of the complex ³C will be appreciably populated thermally during complex formation. The E.P.R. signal of the TCNE anion promptly arises because of a dissociation of ³C, reaches a maximum, and then follows second-order decay kinetics. The higher the dielectric constant of the donor, the slower the decay rate. The initial intensity of the E.P.R. signal is proportional to the original TCNE concentration in the donor-solvent. Reversible photoinduced TCNE anions are formed by irradiating the complexes in the charge-transfer band. The relationship between the prompt and photoinduced E.P.R. signals is shown. Singlet-triplet separation energies are estimated.     

Excited states of the donor-exciton complex in CdS

The excitation spectrum of the I₂ recombination line of the donor-exciton complex (D⁰, X) in CdS exhibits a set of nine distinct resonances. They represent transitions into excited (D⁰, X) states as shown by polarization, temperature, and magnetic field dependent measurements. The investigation of several sample series involving chemically different donor centers indicates that each donor center is responsible for a shift of the whole set of (D⁰, X) states but its influence is weakened for higher excited states. The analysis of the resonances reported requires an extended (D⁰, X) term scheme and a renewed assignment of the optical transitions to the possible electronic excited states of this complex.