Equation of state and Raman frequency of diamond from quantum Monte Carlo simulations

We report variational and diffusion quantum Monte Carlo (VMC and DMC) calculations of the equation of state and Raman frequency of diamond. The pressure derivative of the bulk modulus, which has not been accurately determined experimentally, is calculated to be 3.8 (VMC) and 3.7 (DMC). The values of the Raman frequency calculated at the experimental volume are 1373 cm-1(VMC) and 1359 cm-1 (DMC), in good agreement with the experimental value of 1333 cm-1.     

二氧四胺大环配合物光谱特性与其催化活性关系的研究

测量并研究了二氧四胺大环配体 1,4,7,10 四氮杂环十三烷 11,13 二酮及其Cu(Ⅱ )、Co(Ⅱ )、Ni(Ⅱ )配合物在不同 pH值下的常规荧光谱和激光诱导荧光谱 ,发现配合物的荧光量子产率满足 ΦCuL5<ΦCoL5<ΦNiL5的关系 ,并对其作了解释。与此同时 ,分析了其作为模拟超氧歧化酶的催化活性和荧光光谱特性的关系 ,由三种配合物的荧光量子产率 ,推测出其催化活性的关系可能是CuL5>CoL5>NiL5。     

Quantum Monte Carlo study of the optical and diffusive properties of the vacancy defect in diamond

Fixed-node diffusion quantum Monte Carlo (DMC) calculations of the ground and excited state energetics of the neutral vacancy defect in diamond are reported. The multiplet structure of the defect is modeled using guiding wave functions of the Slater-Jastrow type with symmetrized multideterminant Slater parts. For the ground state we obtain the 1E state in agreement with experiment. The calculated energy of the lowest dipole allowed transition is consistent with the experimentally observed GR1 band, which has long been identified with the neutral vacancy in diamond, although no previous first-principles ab initio calculation of this transition exists. The calculated multiplet splitting of over 2 eV indicates the importance of a proper treatment of electron exchange and correlation in this system. DMC calculations of the formation and migration energy of the vacancy defect are presented.     

First-principles studies of the metallization and the equation of state of solid helium

The insulator-to-metal transition in hcp solid helium at high pressure is studied with first-principles simulations. Diffusion quantum Monte Carlo (DMC) calculations predict that the band gap closes at a density of 21.3 g/cm;{3} and a pressure of 25.7 terapascals, which is 20% higher in density and 40% higher in pressure than predicted by density functional calculations based on the generalized gradient approximation (GGA). The metallization density derived from GW calculations is found to be in very close agreement with DMC predictions. The zero point motion of the nuclei had no effect on the metallization density within the accuracy of the calculation. Finally, fit functions for the equation of state are presented, and the magnitude of the electronic correlation effects left out of the GGA approximation are discussed.     

High-pressure phases of calcium: density-functional theory and diffusion quantum Monte Carlo approach

The phase diagram of Ca is examined using a combination of density-functional theory (DFT) and diffusion quantum Monte Carlo (DMC) calculations. Gibbs free energies of several competing structures are computed at pressures near 50 GPa. Existing disagreements for the stability of Ca both at low and room temperature are resolved with input from DMC. Furthermore, DMC calculations are performed on 0 K crystalline structures up to 150 GPa and it is demonstrated that the widely used generalized gradient approximation of DFT is insufficient to accurately account for the relative stability of the high-pressure phases of Ca. The results indicate that the theoretical phase diagram of Ca needs a revision.     

Photophysical properties, laser activity and photoreactivity of a heteroaryl chalcone: A model of solvatochromic fluorophore

The absorption and fluorescence characteristics of 3-(4′-dimethylaminophenyl)-1-(2-thienyl)prop-2-en-1-one (DMATP) have been investigated in different solvents. DMATP dye exhibits a large red shift in both absorption and emission spectra as solvent polarity increases, indicating a large change in the dipole moment of molecules upon excitation due to an intramolecular charge transfer interaction. The fluorescence quantum yield depends strongly on the properties of the solvents, which was attributed to positive and negative solvatokinetic effects. A crystalline solid of DMATP gave an excimer like emission at 570 nm due to the excitation of molecular aggregates. This is expected from the idealized crystal structure of the dye that belongs to the B-type class of Steven's classification. A dye solution ca. 10⁻³ mol dm⁻³ in CHCl₃ gave a good laser emission in the range 480–560 nm with emission maximum at 530 nm upon pumping by nitrogen laser (λ_ex=337.1 nm). The excitation energy transfer from 7-dimethylamino-4-methyl coumarine (DMC) to DMATP has been also studied in CHCl₃ and the values of energy transfer rate constant and critical transfer distance indicate a Főrster-type mechanism. The photoreactivity and net photochemical quantum yield of DMATP in chloromethane solvents are also determined. We applied semiempirical MO calculation using AMI and ZINO/S calculation to understand the geometric and electronic structure of DMATP molecule in both ground and excited states.     

Effect of the Semiconductor Quantum Dot Shell Structure on Fluorescence Quenching by Acridine Ligand

The main line of research in cancer treatment is the development of methods for early diagnosis and targeted drug delivery to cancer cells. Fluorescent semiconductor core/shell nanocrystals of quantum dots (e.g., CdSe/ZnS) conjugated with an anticancer drug, e.g., an acridine derivative, allow real-time tracking and control of the process of the drug delivery to tumors. However, linking of acridine derivatives to a quantum dot can be accompanied by quantum dot fluorescence quenching caused by electron transfer from the quantum dot to the organic molecule. In this work, it has been shown that the structure of the shell of the quantum dot plays the decisive role in the process of photoinduced charge transfer from the quantum dot to the acridine ligand, which is responsible for fluorescence quenching. It has been shown that multicomponent ZnS/CdS/ZnS shells of CdSe cores of quantum dots, which have a relatively small thickness, make it possible to significantly suppress a decrease in the quantum yield of fluorescence of quantum dots as compared to both the classical ZnS thin shell and superthick shells of the same composition. Thus, core/multicomponent shell CdSe/ZnS/CdS/ZnS quantum dots can be used as optimal fluorescent probes for the development of systems for diagnosis and treatment of cancer with the use of anticancer compounds based on acridine derivatives.     

Influence of solvent polarity and temperature on dual fluorescence of 10,10′-dibromo, 9,9′-bianthryl

Fluorescence of 10,10′-dibromo, 9,9′-bianthryl (DBrBA) in solvents of different polarities (n-hexane, dibutyl ether, tetrahydrofuran, and acetone) has been investigated as a function of temperature. Changing of the solvent and variation of temperature modifies the ratio of local (LE) and charge transfer (CT) fluorescence quantum yields. From the basic fluorescence data (quantum yields, lifetimes, ratio of CT to LE fluorescence quantum yields) the temperature-dependent equilibrium constants for the charge transfer process in the excited singlet state were calculated and discussed on the basis of the modern electron transfer theories. It has been found that the intersystem crossing in DBrBA in nonpolar n-hexane, leading to the population of the lowest triplet state, proceeds via the third triplet state. It has been confirmed by the fluorescence measurements and quantum mechanical calculations. Surprisingly, the experimentally obtained intersystem crossing rate constants are very weakly dependent on temperature. Thus, the electron transfer reaction leading to the population of the molecular triplet state is probably an adiabatic reaction with a rate constant controlled by the dielectric relaxation of the solvent.     

Diffusivity in water and fluorescence properties of?organic nanoparticles produced in?flames

Rotational and translational diffusion properties in water of nano organic carbon (NOC) particles collected from premixed laminar ethylene/air flames have been investigated using both time resolved fluorescence polarisation anisotropy (TRFPA) and fluorescence correlation spectroscopy (FCS). Insight into the NOC sizes, structures and rigidity has been gained through diffusion properties exploiting their fluorescence in different spectral ranges. The TRFPA measurements revealed the presence of two classes of particles. The first composed of particles with a mean size of 1.5?nm which absorb and fluoresce in the UV, and a second class composed of slightly larger particles, about 2.2?nm, which absorb and fluoresce in the visible and were also detected by FCS. From FCS measurements particle concentration and fluorescence quantum yield have been evaluated.     

Photophysical properties of the Corrole photosensitizers

The photophysical properties of a series of hydroxyl Corroles, Corrole-F, Corrole-Cl, Corrole-Br, Corrole-I and Corrole-2I, have been investigated by steady-state and time-resolved transient spectroscopy. The absorption spectra show a strong peak around 420 nm corresponding to B band and several weak Q absorption bands between 450 nm and 650 nm, exhibiting much stronger Q band absorption than that of porphyrin. The absorptions of these Corroles increase with the atom weight and the number of halogen atoms. All samples show similar fluorescence characteristics of an emission peak at 650 nm. The fluorescence intensities significantly decrease with the atom weight and the number of halogen atoms. The fluorescence quantum yield of Corrole-I is 0.947%, which is larger than that of Corrole-2I (0.381%). The fluorescence dynamics of the hydroxyl Corroles shows that both the fluorescence lifetime and the intersystem-crossing transition time of these Corroles decrease sharply with the increase of the atom weight and the number of halogen atoms, which may lead to the increase of the triplet state quantum yield. The heavy-atom effect on active oxygen of PDT has also been discussed by the end of this paper.     

基于谷胱甘肽配体的ZnSe量子点对pH响应的时间分辨荧光光谱特性

当前,有关量子点pH响应方面的研究主要集中在含Cd（镉）类量子点,且都是研究其稳态荧光光谱对pH值的响应。然而,Cd类量子点对生物体系具有一定的毒性,且稳态荧光光谱法由于受浓度等因素的影响具有一定的不稳定性,因此应用于生物体系中作为pH探针具有明显的缺点。基于以上分析,通过水相合成法,我们制备出了基于谷胱甘肽配体的水溶性ZnSe量子点,该量子点具有毒性小,生物兼容性好等特点,适合被应用于生物体系中。利用所制备的ZnSe量子点,采用时间相关单光子计数技术,结合紫外可见吸收光谱和稳态荧光光谱,对pH值在5~11不同环境下的ZnSe量子点荧光动力学进行了系统性的研究。ZnSe量子点荧光衰减具有两个寿命组分,拟合得到分别为4和24 ns。通过采集不同探测波长下ZnSe量子点荧光衰减曲线,发现其长寿命组分随探测波长的增加而增加,而短寿命组分基本不随探测波长的改变而改变,结合有关报道分析判断,短寿命和长寿命组分分别来源于核内非局域载流子复合和表面态局域载流子复合。实验发现,处于不同pH值的环境下的ZnSe量子点具有不同的荧光寿命,其荧光寿命与pH值的变化呈负相关。通过比较ZnSe量子点两种荧光寿命组分随pH值的变化关系,发现ZnSe量子点的荧光寿命对pH值的响应主要来源于长寿命组分即表面态寿命,且在不同pH值范围内响应的灵敏度不同,在6~8的pH值范围内响应最为显著,表现为长寿命组分随pH值的增加出现一个较大幅度的衰减。实验进一步发现,ZnSe量子点两个寿命组分的比值在不同pH值范围内具有较好的线性相关性,但在不同pH值范围内斜率不同,通过比较,最大值在pH值为6~8的范围内。另外,与金属钠离子相互作用实验及相关报道表明,金属离子对ZnSe量子点荧光寿命的影响较小。以上研究表明,ZnSe量子点在生物体系pH值检测中具有良好的应用前景。     

On the Fluorescence of Luminol in a Silver Nanoparticles Complex

The photophysical properties of luminol in a silver nanoparticles complex have been studied by steady-state and time resolved fluorescence spectroscopy. The effect of the serum albumin on the luminol fluorescence in the silver nanoparticles has been also investigated. It was found that the fluorescence quantum yield value of luminol in a silver nanoparticles complex is ??=?0.00407. The decrease of the average fluorescence lifetime value of the luminol in the silver nanoparticles complex was found to be low, <τ>?=?1.712 ns. The luminol does not bind to the serum albumins in the presence of silver nanoparticles. The formation of a new species of luminol on silver nanoparticles is discussed. The results have influence regarding the use of luminol as an assay for bio-analytical applications.     

Influence of interaction of chromophores, linked by the unconjugated chain, on the luminescence properties of biscyanine dyes

Deactivation of electronically excited state of chemically bound dimers – biscyanines with two chromophores linked by unconjugated chains and corresponding monomer dye was investigated. It was found that the quantum yield of dimer fluorescence is lower than that of a monomer dye. The amount of quantum yield of fluorescence decreases with the increase of chromophores interaction degree (the decrease of the isolating polymethylene bridge length). It is shown on the basis of the external heavy-atom effect studies that the decrease of biscyanines fluorescence ability is connected with the enhancment of singlet–triplet intersystem crossing (S₁T₁). It has been established that the probability of the triplet states population in biscyanines with chromophores in parallel arrangement is considerably higher than that in similar compounds with an angular arrangement of chromophores. The delayed fluorescence was observed in the case of dyes with parallel arrangment of chromophores.     

非对称耦合量子阱ZnCdSe/ZnSe的荧光光谱与拉曼散射谱

本文研究了非对称Ⅱ -Ⅳ族耦合多量子阱Zn1-xCdxSe/ZnSe的荧光光谱和拉曼散射谱特性。实验中观察到了比较明显的量子阱荧光峰 ;在拉曼散射谱中观察到了分别对应于与ZnCdSe窄阱和宽阱的一级限制光学模LOL 和LOW 及对应于ZnSe/GaAs界面的声子和等离子体的耦合模 ,并对它们进行了简单分析。     

Quantum Monte Carlo study of small hydrocarbon atomization energies

A benchmark study of atomization energies is reported for 22 hydrocarbons using single determinant trial functions in the diffusion Monte Carlo (DMC) variant of the quantum Monte Carlo (QMC) method. The DMC atomization energies are compared to experiment, a complete basis set approach (CBS-Q), density functional theory with the B3LYP functional, and coupled-cluster singles, doubles and perturbative triples, CCSD(T), methods. Comparison of the DMC results to experiment yields a mean absolute deviation of 1.9kcalmol^?1, which is comparable to that of the B3LYP/cc-pVQZ (1.7kcalmol^?1) level of theory, but less accurate than that of CBS-Q (1.1kcalmol^?1). DMC performs similarly for both closed-shell and open-shell molecules with mean absolute deviations of 2.1kcalmol^?1 for the former and 1.7kcalmol^?1 for the latter systems. The use of experimental zero-point energies (ZPEs), rather than scaled B3LYP ZPEs, is found to have negligible effect on DMC atomization energies. The latter reported here provide a baseline from which further improvement in the calculation of DMC atomization energies, including the use of multi-determinant and other trial function improvements, can be measured.     

Quantum Monte Carlo study of the CO interaction with a dimer model surface for Cr(110)

The chemisorption of CO on a Cr (110) surface is investigated using the quantum Monte Carlo method in the diffusion Monte Carlo (DMC) variant and a model Cr₂CO cluster. The present results are consistent with the earlier ab initio HF study with this model that showed the tilted/near-parallel orientation as energetically favoured over the perpendicular arrangement. The DMC energy difference between the two orientations is larger (1.9 eV) than that computed in the previous study. The distribution and reorganization of electrons during CO adsorption on the model surface are analysed using the topological electron localization function method that yields electron populations, charge transfer and clear insight on the chemical bonding that occurs with CO adsorption and dissociation on the model surface.     

Time-resolved fluorescence of carbon nanotubes and its implication for radiative lifetimes

The temporal evolution of fluorescence from isolated single-wall carbon nanotubes (SWNTs) has been investigated using optical Kerr gating. The fluorescence emission is found to decay on a time scale of 10 ps. This fast relaxation arises from nonradiative processes, the existence of which explains the relatively low observed fluorescence efficiency in isolated SWNTs. From the measured decay rate and a determination of fluorescence quantum efficiency, we deduce a radiative lifetime of 110 ns.     

Fluorescence Quantum Yield Determination of Propylparaben Using Flow Injection Spectroscopy

The determination of the fluorescence quantum yield of Propylparaben is introduced and applied to L-tyrosine as a standard by a new approach that can be applied to the pharmaceutical compound utilised in this study. The quantum yield is a critical figure of quality for the optical nature of a fluorophore. Numerous investigations have considered the glitter in both pharmaceutical and nature compounds for its medical and industrial significance. A straightforward method is detailed here to decide the quantum yield of Propylparaben in solution as an element of the fluorescence concentration. For this reason, L-Tyrosine is chosen as a fluorescence standard perspective to gauge the Propylparaben fluorescence quantum yield. The impacts of pH, solvents and flow rate on the assessment of quantum yield and quantum efficiency, for the reference and the solutions of Propylparaben, have been investigated. The results indicated that these parameters significantly influence the accuracy of the method. Diverse methods are concentrated on to represent distinctive quantum yield advancements with the quantum efficiency. The impact of these parameters was likewise considered. In this study, the application of the single method may be taken into consideration to compute quantum yield of Propylparaben, which was 0.36, and this is an exceptionally basic and general technique to solve the imperative issue of luminescence quantum yield assurance of other fluorescence compounds.     

Influence of a Solvent on the Quantum Yield and Duration of the Fluorescence of Tetraazoporphin

In view of the discrepancies between the values available in the literature for the photophysical parameters of tetraazaporphin in solutions, we measured its quantum yield and duration of fluorescence in a number of solvents. It has been found that alcohols (isobutanol and isopropanol) quench the fluorescence appreciably. For a solution in toluene — a stable chemically inactive and low-polar solvent — the measured quantum yield of the fluorescence of tetraazaporphin is equal to 0.180 ± 0.015 and its duration is 3.4 ± 0.1 nsec. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 5, pp. 697–699, September–October, 2005.