An experimental and computational study of the valence photoelectron spectra of halogenated pyrimidines

The electronic structures of pyrimidine and a selection of its halogen-substituted derivatives have been investigated using ultraviolet photoelectron spectroscopy and ab initio quantum chemical methods. Assignments are proposed for all of the features in the PES spectra by comparison with the vertical ionization energies of the molecular orbitals calculated using the partial third-order quasiparticle approximation as applied to electron propagator theory and a corrected density functional method based on the B3LYP functional. The shifts of the outermost five molecular orbitals of the pyrimidine ring structure in the halogen-substituted derivatives with respect to the binding energies of the equivalent orbitals in the parent pyrimidine molecule are discussed as a function of the identity and ring position of the halogen atom.     

Universality in the Four-Body System in an EFT Framework

We extend previous calculations by Platter et al. to include higher partial waves using the same effective quantum mechanics approach for a non-relativistic four-boson system. The Yakubovsky equations are reduced to a simple eigenvalue problem, which is then solved numerically. Instead of introducing a three-body force, we fix the cutoff so that the three-body system is reproduced correctly. The thus obtained results show good agreement with Platter’s. Preliminary results for higher partial waves are shown as well.     

Magnetic-field-dependent excitation transfer in quantum wells of diluted magnetic semiconductor

We studied the excitation transfer in double quantum wells of a diluted magnetic semiconductor using a scanning near-field optical microscope at 7 K in external magnetic fields up to 9 T. In each quantum well, local energy minima are generated by local fluctuation of layer thickness and doping concentration of magnetic components. Excitons relax into the local energy minima and transfer between the minima via near-field optical interactions even across quantum wells toward stable sites at which to localize. We measured the intensity maps of near-field photoluminescence with spatial resolution estimated to be 30 nm under varying external magnetic fields. The measurement position reproducibility was confirmed by scanning tunneling microscope images. Analysis of the maps derived the magnetic-field dependence of the typical size of exciton-localization sites for each quantum well. Based on these results, we investigated the excitation transfer between the two quantum wells lying in different layers of the double quantum well system, and showed that the exciton transfer takes place at the two specific applied magnetic-field intensities that result in the crossing of Zeeman-split energy levels of the two different wells. We concluded that both the localization and the inter-quantum-well transfer of excitons are able to be controlled by an external magnetic field. This provides the basis for functional devices operating without any wiring.     

拉曼光活性(ROA)经典理论模型研究

拉曼光活性（ＲＯＡ）经典理论模型研究马树国吴国祯（清华大学物理系北京１０００８４）ＡＣｌａｓｉｃａｌＴｈｅｏｒｙｆｏｒｔｈｅＲａｍａｎＯｐｔｉｃａｌＡｃｔｉｖｉｔｙＭａＳｈｕｇｕｏ，ＷｕＧｕｏｚｈｅｎ（ＤｅｐａｒｔｍｅｎｔｏｆＰｈｙｓｉｃｓ，Ｔｓｉｎ...     

Ag/ZnO纳米结构的荧光增强效应

利用化学合成方法制备了Ag纳米线和ZnO量子点。对这两种纳米结构的表面形貌、晶体结构和光学性质分别进行了研究。结果表明：Ag纳米线和ZnO量子点均为单晶结构,平均直径分别为160 nm和5 nm左右。将Ag纳米线混入ZnO量子点可以使其紫外荧光显著增强,其中位于345 nm和383 nm 的荧光分别增强30倍和12倍。这与Ag纳米线和ZnO量子点混合体系的局域表面等离子体共振耦合吸收峰位相一致,说明该体系存在两种共振耦合模式。该研究结果为将来开发ZnO基纳米发光器件提供了一条新的途径。     

An Inverse Problem in Quantum Statistical Physics

We address the following inverse problem in quantum statistical physics: does the quantum free energy (von Neumann entropy + kinetic energy) admit a unique minimizer among the density operators having a given local density n(x)? We give a positive answer to that question, in dimension one. This enables to define rigourously the notion of local quantum equilibrium, or quantum Maxwellian, which is at the basis of recently derived quantum hydrodynamic models and quantum drift-diffusion models. We also characterize this unique minimizer, which takes the form of a global thermodynamic equilibrium (canonical ensemble) with a quantum chemical potential.     

Quantum logical solution to the measurement problem of quantum mechanics

In this paper I propose a reformulation and solution of the measurement problem of quantum mechanics. The reformulation depends on a quantum logical interpretation of quantum mechanics, broadly construed. The solution depends on a theorem about partial Boolean algebras which is proved here.     

Temperature, pressure, and bath gas composition dependence of fluorescence spectra and fluorescence lifetimes of toluene and naphthalene

Time-resolved fluorescence spectra of gas-phase toluene and naphthalene were investigated upon picosecond laser excitation at 266 nm as a function of temperature (toluene 296–1,025 K, naphthalene 374–1,123 K), pressure (1–10 bar), and bath gas composition (varying concentrations of N₂, O₂, and CO₂) with a temporal resolution of 50 ps. In the investigated temperature range, the fluorescence spectra of both toluene and naphthalene show a significant red-shift, whereas the fluorescence lifetime decreases with increasing temperature, more pronounced for toluene than for naphthalene. Increasing the total pressure of either N₂ or CO₂ from atmospheric to 10 bar leads to an increase by about 20 % (naphthalene at 373 K) and a decrease by 60 % (toluene at 575 K) in fluorescence lifetimes, respectively. As expected, at atmospheric pressure collisions with O₂ shorten the fluorescence lifetime of both toluene and naphthalene significantly, e.g., by a factor of 30 and 90 when changing O₂ partial pressure at 373 K from 0 to 0.21 bar, respectively. The fluorescence model of Koban et al. (Appl Phys B 80: 777, 2005) for the dependence of the toluene quantum yield on temperature and O₂ partial pressure at atmospheric pressure describes toluene fluorescence lifetimes well within its range of validity. The model is modified to satisfactorily predict effective toluene fluorescence lifetimes in N₂ at pressures up to 10 bar. However, it still fails to predict the dependence at simultaneously elevated temperatures and pressures in air as bath gas. Similarly, an empirical model is presented for predicting (relative) fluorescence quantum yields and lifetimes of naphthalene. Although the fitting models have their shortcomings this publication presents a data set of great importance for practical LIF applications, e.g., in-cylinder mixture formation diagnostics in internal combustion engines.     

Effects of increasing number of rings on the ion sensing ability of CdSe quantum dots: a theoretical study

A computational study on the structural and electronic properties of a special class of artificial atoms, known as quantum dots, has been carried out. These are semiconductors with unique optical and electronic properties and have been widely used in various applications, such as bio-sensing, bio-imaging, and so on. We have considered quantum dots belonging to II–VI types of semiconductors, due to their wide band gap, possession of large exciton binding energies and unique optical and electronic properties. We have studied their applications as chemical ion sensors by beginning with the study of the ion sensing ability of (CdSe) _n (n?=?3, 6, 9 which are in the size range of ~?0.24, 0.49, 0.74 nm, respectively) quantum dots for cations of the zinc triad, namely Zn²⁺, Cd²⁺, Hg²⁺, and various anions of biological and environmental importance, and studied the effect of increasing number of rings on their ion sensing ability. The various structural, electronic, and optical properties, their interaction energies, and charge transfer on interaction with metal ions and anions have been calculated and reported. Our studies indicate that the CdSe quantum dots can be employed as sensors for both divalent cations and anions, but they can sense cations better than anions.     

Fundamental Problems in the Unification of Physics

We discuss the following problems, plaguing the present search for the “final theory”: (1) How to find a mathematical structure rich enough to be suitably approximated by the mathematical structures of general relativity and quantum mechanics? (2) How to reconcile nonlocal phenomena of quantum mechanics with time honored causality and reality postulates? (3) Does the collapse of the wave function contain some hints concerning the future quantum gravity theory? (4) It seems that the final theory cannot avoid the problem of dynamics, and consequently the problem of time. What kind of time, if this theory is supposed to be background free? (5) Will the dynamics of the “final theory” be probabilistic? Quantum probability exhibits some essential differences as compared with classical probability; are they but variations of some more general probabilistic measure theory? (6) Do we need a radically new interpretation of quantum mechanics, or rather an entirely new theory of which the present quantum mechanics is an approximation? (7) If the final theory is to be background free, it should provide a mechanism of space-time generation. Should we try to explain not only the generation of space-time, but also the generation of its material content? (8) As far as the existence of the initial singularity is concerned, one usually expects either “yes” or “not” answers from the final theory. However, if the mathematical structure of the future theory is supposed to be truly more general that the mathematical structures of the present general relativity and quantum mechanics, is a “third answer“ possible? Could this third answer be related to the probabilistic character of the final theory? We discuss these questions in the framework of a working model unifying gravity and quanta. The analysis reveals unexpected aspects of these rather wildly discussed issues.     

Geometry and ground-state electronic structure of neutral ruthenium metal complexes of potential relevance to metal-based drugs for cancer control

There is considerable current interest in some Ru metal complexes in relation to the general area of metal-based drugs for cancer control. Therefore, we stress here the potential role of quantum chemical modelling as an aid to cancer technology in the above area. Prompted by earlier experience on the role of a Ru metal surface in influencing the geometry of small adsorbed molecules (e.g. H₂O outside metallic Ru) we here consider models of specific neutral metal complexes with a single Ru atom which are relevant in this area of cancer control using metal-based drugs. In particular, geometries plus some ground-state electronic structure properties are presented using quantum chemical methods.     

Local density approximation in site-occupation embedding theory

ABSTRACT

Site-occupation embedding theory (SOET) is a density functional theory (DFT)-based method which aims at modelling strongly correlated electrons. It is in principle exact and applicable to model and quantum chemical Hamiltonians. The theory is presented here for the Hubbard Hamiltonian. In contrast to conventional DFT approaches, the site (or orbital) occupations are deduced in SOET from a partially interacting system consisting of one (or more) impurity site(s) and non-interacting bath sites. The correlation energy of the bath is then treated implicitly by means of a site-occupation functional. In this work, we propose a simple impurity-occupation functional approximation based on the two-level (2L) Hubbard model which is referred to as two-level impurity local density approximation (2L-ILDA). Results obtained on a prototypical uniform eight-site Hubbard ring are promising. The extension of the method to larger systems and more sophisticated model Hamiltonians is currently in progress.     

Kinetic Approach to Reaction and Diffusion in Many-Particle Systems

A derivation of hydrodynamic equations which describe diffusion in connection with reaction processes in many-particle systems is given on the basis of quantum kinetic theory. For this purpose kinetic equations are derived for a quantum gas with chemical reactions. Following Grad's method in a linear approximation reaction-diffusion equations can be obtained with explicite expressions for the diffusion and reaction rate coefficients. The influence of nonideality effects in reaction-diffusion equations is discussed.     

Partial Measurements and the Realization of Quantum-Mechanical Counterfactuals

We propose partial measurements as a conceptual tool to understand how to operate with counterfactual claims in quantum physics. Indeed, unlike standard von Neumann measurements, partial measurements can be reversed probabilistically. We first analyze the consequences of this rather unusual feature for the principle of superposition, for the complementarity principle, and for the issue of hidden variables. Then we move on to exploring non-local contexts, by reformulating the EPR paradox, the quantum teleportation experiment, and the entanglement-swapping protocol for the situation in which one uses partial measurements followed by their stochastic reversal. This leads to a number of counter-intuitive results, which are shown to be resolved if we give up the idea of attributing reality to the wavefunction of a single quantum system.     

Linear-scaling and parallelisable algorithms for stochastic quantum chemistry

For many decades, quantum chemical method development has been dominated by algorithms which involve increasingly complex series of tensor contractions over one-electron orbital spaces. Procedures for their derivation and implementation have evolved to require the minimum amount of logic and rely heavily on computationally efficient library-based matrix algebra and optimised paging schemes. In this regard, the recent development of exact stochastic quantum chemical algorithms to reduce computational scaling and memory overhead requires a contrasting algorithmic philosophy, but one which when implemented efficiently can achieve higher accuracy/cost ratios with small random errors. Additionally, they can exploit the continuing trend for massive parallelisation which hinders the progress of deterministic high-level quantum chemical algorithms. In the Quantum Monte Carlo community, stochastic algorithms are ubiquitous but the discrete Fock space of quantum chemical methods is often unfamiliar, and the methods introduce new concepts required for algorithmic efficiency. In this paper, we explore these concepts and detail an algorithm used for Full Configuration Interaction Quantum Monte Carlo (FCIQMC), which is implemented and available in MOLPRO and as a standalone code, and is designed for high-level parallelism and linear-scaling with walker number. Many of the algorithms are also in use in, or can be transferred to, other stochastic quantum chemical methods and implementations. We apply these algorithms to the strongly correlated chromium dimer to demonstrate their efficiency and parallelism.     

不同取代基对喹啉电子光谱影响的理论研究

不同取代基团会引起电子光谱发生不同的变化,为获得分子结构与电子光谱之间的关系,采用量子化学计算方法进行了理论分析。使用DFT、CIS分别对基态、激发态进行几何结构优化,再用TDDFT计算优化结果得出电子光谱。结果表明:不同取代基团都改变了碳氮环基态、激发态的几何构型,前线区域轨道能量,π电子共轭系统,这些变化都导致电子光谱发生相应变化。得出不同取代基对电子光谱的影响规律,为电子光谱分析鉴定衍生物提供了理论参考。     

Tuning the photoluminescence of graphene quantum dots by co-doping of nitrogen and sulfur

Nitrogen and sulfur co-doped graphene quantum dots (NS-GQDs) were successfully synthesized using a facile, inexpensive, and environmentally friendly hydrothermal reaction of aqueous ammonia, S powder, and graphene quantum dots. The NS-GQDs with oxygen-rich functional groups have a high quantum yield of 41% and a diameter of 1–5 nm. The photoluminescence (PL) properties of the nitrogen-doped graphene quantum dots (N-GQDs) and NS-GQD were investigated. The results showed that the PL emission of the NS-GQD exhibits a clear blue shift of 54 nm compared to that of the N-GQDs.