电磁感应双光子光透明及共振吸收增强

研究了相干场控制下的电磁感应双光子光透明。讨论了外加相干场对双光子吸收特性的影响 ,分析了电磁感应双光子光透明及共振吸收增强的物理机制。应用密度矩阵方法推导出相干场作用下双光子吸收上能级粒子数的二阶近似表达式 ,同时利用微扰法在原子缀饰态表象中推导出双光子跃迁速率的解析表达式。并讨论了系统中多普勒效应的影响。     

单原子Al修饰空位缺陷V2C（MXene）对H2气体表面吸附的第一性原理研究

基于第一性原理计算方法,对含空位缺陷的V₂C(MXene)在不同位点修饰单原子Al的相关性能进行系统研究.研究表明,几何优化后得到含空位缺陷的V₂C稳定结构表面能为-3075.53 J/m²,单原子Al修饰本征V₂C单原子的吸附能为1.5511eV、单原子Al修饰空位缺陷V₂C的吸附能为-2.0763 eV,这表明含空位缺陷的V₂C,由于单原子Al的修饰可以明显改善晶体结构稳定性.进一步从态密度、分波态密度、吸氢能力研究发现,各体系态密度和分波态密度均出现分波越过费米能级的现象,表现出较强的金属性;V₂C吸附H₂气体分子吸附能为-7.5867 eV,而空位缺陷V₂C和单原子Al修饰空位缺陷V₂C两个体系对H₂气体分子的吸附能仅为-0.9851 eV、-2.7130 eV,均未能进一步改善V₂C对H₂气体分...     

NpFn分子结构与电子结构的理论研究

运用杂化密度泛函(B3LYP)方法,对NpFn(n=3~6)的分子结构特性进行了系统地研究.优化得到了各分子的平衡几何构型,计算了分子的振动频率,并进行了态密度和自然键价轨道(NBO)分析.讨论了不同芯电子相对论有效原子芯势(RECP)对计算结果的影响,分析了NpFn分子的成键,发现随着与Np结合的F原子数目增加,Np原子的5f与F原子的2p轨道能逐渐接近,成键依次增强,键长呈现出收缩的趋势.目前的计算结果与可行的理论和实验符合较好.     

Assessment of the coherent potential approximation for the absorption spectra of a one-dimensional Frenkel exciton system with a Gaussian distribution of fluctuations in the optical transition frequency

We investigate the accuracy of the coherent potential approximation (CPA) for the optical absorption spectra of a one-dimensional Frenkel exciton system with nearest-neighbor interactions and a Gaussian distribution of fluctuations in the optical transition frequency (diagonal Gaussian disorder). Our earlier studies have established that the CPA gives highly accurate results for the integral of the density of states of this system. In this paper we compare the CPA results for the normalized optical absorption with the finite-array calculations of Schreiber and Toyozawa and Schreiber for the same model. It is found that the CPA results for the absorption are in good agreement with their findings. It is pointed out that an expansion of the density of states in terms of the eigenstates of the ideal (no disorder) array contains a term proportional to the normalized absorption. Since the density of states is accurately approximated by the CPA, the presence of this term explains the success of the CPA in reproducing the absorption spectra. Our findings support the use of the Gaussian disorder model to interpret the absorption spectra of one and quasi-one dimensional exciton systems.     

溶剂密度对β胡萝卜素拉曼散射截面的影响

测量了含有9个CC共轭双键的链状多烯类生物分子β胡萝卜素在9种溶剂中的紫外—可见吸收和拉曼光谱.结果表明,β胡萝卜素C—C,CC键拉曼散射截面随溶剂体密度增加而线性增加,其机理是β胡萝卜素分子在体密度大的溶剂中受浮动干扰小,分子结构有序性高,π电子离域扩展,产生强的相干弱阻尼CC键振动,而产生大的拉曼散射截面.密度对分子拉曼散射截面影响研究还没见过报道,本文为多烯类链状分子的光散射理论研究提供了实验线索,也对多烯类链状分子性能研究及光电器件研制有参考价值. 关键词： 拉曼散射截面 多烯分子 吸收光谱 分子结构有序     

Time-dependent variational principle on the group SO(2r): Generalizations of time-dependent Hartree-Fock

The family of all Hartree-Fock-Bogoliubov (HFB) states for a given set of r isosopin-spin orbitals form a set of coherent states. The set of antisymmetrized geminal power (AGP) states for a given set of r isospin-spin orbitals form a set of charge-projected coherent states, with the number of particles n as the “charge” and the HFB coherent state as the generating function. Both these coherent states are associated with the group SO(2r). The approximate time evolution of the system generated by restricting the quantum mechanical evolution to the family of HFB and AGP coherent states is described as a classical dynamics with the energy of the coherent state as hamiltonian function. The phase space is isomorphic to the coset space SO(2r)/U(r). The random phase approximation based on HFB and AGP states is derived by considering the harmonic approximation to the hamiltonian function. This work generalizes the group theoretical approaches to Hartree-Fock, and time-dependent Hartree-Fock theory by the use of non-number-conserving (HFB) and correlated (AGP) states.     

Collective spin tunneling in spinor Bose-Einstein condensates

We investigate a novel aspect of rotational tunneling of the macroscopic spin for multicomponent spinor Bose-Einstein condensate (BEC). The Lagrangian is deduced from the multi-component BEC system formalism, and is written in terms of spin coherent states. From the effective Hamiltonian for the collective spin, the tunneling rate is obtained through a functional integral of the spin variable. It is pointed out that the cooperative effect between the Zeeman energy and the anisotropic nature of the spin-dependent inter-atomic interaction plays a key role for occurrence of collective spin tunneling.     

基于密度泛函理论的肾上腺素分子的光谱分析

肾上腺素是一种神经和激素的传送体,研究肾上腺素分子的光谱和能级有助于了解其化学稳定性和药理作用。基于密度泛函理论（DFT）,利用Gaussian 09软件在B3LYP/6-311G（d,p）基组水平上对肾上腺素分子进行结构优化,采用含时密度泛函理论（TD-DFT）的PBE方法在def2tzvp基组水平上计算肾上腺素分子在气相中的前20个激发态,利用Multiwfn3.7（dev）软件绘制出其紫外光谱图并对激发性质进行分析。肾上腺素分子紫外光谱对应的主要跃迁是从基态分别到第1,2,4,8,15和16激发态的跃迁,其他的激发态的振子强度低于阈值0.03。理论计算得出肾上腺素的紫外光谱有两个吸收峰,分别位于206.23和273.92 nm,206.23 nm峰主要由基态跃迁到第16激发态形成,273.92 nm峰主要是基态跃迁到第2、4激发态形成,主要是由苯环上π→π*跃迁所产生,并与实验光谱吻合较好。对肾上腺素分子的激发态性质分析可知,上述吸收峰都是在最高占据轨道和最低空轨道的临近轨道跃迁产生的。利用密度泛函的PBE方法在6-311G（d, p）的基组水平上计算肾上腺素分子频率并绘制红外光谱,由振动分析可知,3 738和3 662 cm-1峰是由酚羟基O-H伸缩振动产生的特征吸收峰,3 715 cm-1峰是由醇羟基O-H伸缩振动产生的特征吸收峰,2 854 cm-1峰是由甲基的C18-H20键的伸缩振动产生的特征吸收峰,1 516和1 439 cm-1峰是苯环骨架的伸缩振动的特征吸收峰,1 279与1 057 cm-1峰分别是由C6-O10和C12-O23键伸缩振动产生的特征吸收峰,620 cm-1峰是N22-H17键摇摆振动的特征吸收峰。对比肾上腺素的实验红外光谱,发现理论光谱与实验光谱中各基团的特征吸收峰都较为明显且总体吻合较好。由于肾上腺素分子二聚体和多聚体之间形成氢键,分子间氢键的形成削弱了O-H键的强度,降低了能形成分子间氢键的羟基O-H的伸缩振动频率,从而导致实验光谱在3 500～2 500 cm-1之间呈现出一个宽峰。     

Theoretical investigation of photoprocesses in complex organic compounds upon high-power laser excitation

A procedure of theoretical investigations into the dynamics of energy level populations of organic molecules upon high-power laser excitation is developed that allows information on stimulated emission of molecules, gain and lasing spectra, dynamics of lasing pulses, populations of the ground and excited states, and influence of the induced absorption on lasing of the organic molecules to be obtained. Laws of changing of the above-indicated processes are established for two pyran substitutes. Results of theoretical and experimental investigations are well correlated. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 3, pp. 51–60, March, 2009.     

Excitons in molecular J-aggregates of cyanine dyes: Simulation of trapping and energy transfer

A theoretical model is provided to simulate the energy transfer and trapping of excitons in cyanine J-aggregates for various geometrical configurations. Intermolecular interactions are calculated using the extended dipole method. Frenkel exciton states are obtained by a numerical diagonalization of the aggregate Hamiltonian taking into account the static disorder. A model of exciton–phonon coupling is used to describe the trapping and the energy transfer processes among the exciton states. Scattering rates are calculated and used in a Master Equation to obtain the time evolution of the excitonic populations after initial excitation. Configurationally averaged absorption lineshapes and time-resolved fluorescence decays are obtained. Our simulation model is applied to describe the excitation energy transfer between two closely spaced linear chains of pseudoisocyanine (PIC) molecules and to a two-dimensional monolayer composed of a mixing of oxacyanine and thiacyanine molecules.     

Formation of nonclassical states of light in media with a three-photon resonance

The process of simultaneous absorption of three photons in a medium subjected to a three-photon parametric perturbation is considered. It is shown that in such a medium one can observe the formation of the radiation field states, which are the quantum superposition of three coherent components. One-photon and twophoton absorption processes in the medium also destroy the interference between the components of the superposition state. The states being formed are investigated in both the temporal development (numerically) and the stationary limit (numerically and analytically); the Wigner functions, as well as the quantum entropy, are calculated for a whole series of initial states. It is shown that depending on the initial state of the radiation field, the interference between the three-component superposition states being formed can lead, for example, to the almost total localization of the system in a two-component state or to the destruction of the interference between different coherent components.     

Rotational spectroscopy and dynamics of carbonyl sulphide studied by terahertz free induction decays signals

A terahertz time domain spectroscopy experiment is used to study the coherent re-emission after exciting more than 60 energy rotational states of OCS molecules in gas phase. Due to the regular structure of the absorption spectrum of such linear molecules, a set of subsequent pulses separated by 82.6 ps is re-radiated from the vapour and recorded up to 450 ps. A model based on a linear response of the gas and by use of “Maxwell-Bloch” equations has permitted the re-emitted free induced decay to be investigated. Spectroscopic parameters, such as rotational constant, centrifugal distortion coefficient and relaxation times are responsible for the temporal shape and so can be evaluated. The influence of the optical thickness to access the relaxation times is discussed.     

Transient grating experiments on supercooled molecular liquids II: microscopic derivation of the phenomenological equations

The constitutive equations including the energy conservation aspect, for the long-wavelength dynamics of a liquid comprised of identical, axially symmetric, rigid molecules are microscopically derived. These equations are extended to the case where the dynamics is generated by the interactions of two coherent lasers (the pumps) with the liquid. This interaction corresponds to a weak energy absorption and also to the coupling of the pumps with fluctuations in the mass density, the molecular orientation density and the temperature of the liquid. The microscopic equations generalise those phenomenologically derived in Pick et al. [1] where the role of the temperature fluctuations was ignored. Constraints on the relaxation functions related to the temperature fluctuations and to their coupling with density are derived.     

Bulk- and surface-sensitive high-resolution photoemission study of two mott-hubbard systems: SrVO3 and CaVO3

We study the electronic structure of Mott-Hubbard systems SrVO3 and CaVO3 with bulk and surface-sensitive high-resolution photoemission spectroscopy, using a vacuum ultraviolet laser, synchrotron radiation, and a discharge lamp (hv = 7-21 eV). A systematic suppression of the density of states (DOS) within approximately 0.2 eV of the Fermi level (EF) is found on decreasing photon energy, i.e., on increasing bulk sensitivity. The coherent band in SrVO3 and CaVO3 is shown to consist of surface and bulk-derived features, separated in energy. The stronger distortion on surface of CaVO3 compared to SrVO3 leads to a higher surface metallicity in the coherent DOS at EF, consistent with recent theory.     

Electronic transitions of fluorene, dibenzofuran, carbazole, and dibenzothiophene: From the onset of absorption to the ionization threshold

A comparative study of the electronic transitions of fluorene and its hetero-analogues dibenzofuran, carbazole, and dibenzothiophene was performed in a wide energy range. Gas phase, crystal phase, and linear dichroism electronic transmittance spectra were measured with synchrotron radiation. Electronic transitions to excited singlet states were predicted with time-dependent density functional theory, TD-B3LYP/6-31+G(d,p). Based on the experimental and theoretical results, symmetry assignments of electronic transitions in the vacuum and near-UV region are suggested. The correspondence between excited states in these molecules, similarities, and differences between their electronic spectra are discussed.     

Ab initio study of water adsorption on TiO2-terminated (100) surface of SrTiO3 with and without Cr doping

Water molecule adsorption on TiO₂-terminated (100) surface of SrTiO₃ with and without Cr doping is investigated by first principle calculation based on density functional theory. The band gap is shrunk compared with that of bulk due to the existence of defect states on the surface and 3d states of dopants. As a result the absorption energy edge is reduced and locates in the visible region. When adsorbed on the surface, energy levels of water molecules as a whole are lowered with respect to the Fermi energy, but the higher levels are split and electrons are transferred from low levels to high levels due to the decrease of the density of states in low energy region. Weak bonding is formed between water hydrogen atoms and surface oxygen atoms. This bonding causes the electron transferring from substrate to molecule and the occupation of the corresponding states.     

Absorption characteristics of bacteriorhodopsin molecules

The bacteriorhodopsin molecule absorbs light and undergoes a series of structural transformation following a well-defined photocycle. The complex photocycle is transformed to an equivalent level diagram by considering the lifetime of the intermediate states. Assuming that only B and M states are appreciably populated at any instant of time, the level diagram is further simplified to two-level system. Based on the rate equations for two-level system, an analytic expression for the absorption coefficient of bacteriorhodopsin molecule is derived. It is applied to study the behaviour of absorption coefficient of bacteriorhodopsin film in the visible wavelength region of 514 nm. The dependence of absorption coefficient of bacteriorhodopsin film on the thickness of the film, total number density of active molecules and initial number density of molecules in B-state is presented in the graphical form.     

Plasmonic Dicke effect

We study cooperative emission by an ensemble of emitters, such as fluorescing molecules or semiconductor quantum dots, near a metal nanoparticle. The primary mechanism of cooperative emission is resonant energy transfer between emitters and plasmons rather than Dicke radiative coupling between emitters. The emission is dominated by three superradiant states with the same quantum yield as a single emitter, leading to a drastic reduction of ensemble radiated energy down to just thrice of that by a single emitter, the remaining energy being dissipated in the metal through subradiant states. We perform numerical calculations of system eigenstates and find that the plasmonic Dicke effect interactions affect is not impacted by the interactions between emitters or non-radiative losses in the metal.     

Self-consistent theory of pressure on doped Kondo insulators

The effects of pressure on doped Kondo insulators are studied in the framework of slave-boson mean-field theory under the coherent potential approximation. A unified picture is presented for both the h-type Kondo insulators (SmB₆ and YbB₁₂) and the e-type Kondo insulators (Ce₃Bi₄Pt₃). The f-electron's density of states within the whole range of the concentration of nonmagnetic atoms are calculated self-consistently under various pressures. The variation of the energy gap and the Kondo temperature with pressure are also obtained. These theoretical results can be considered as a possible approach to study systematically the development of the gap behavior by doping and by mechanical pressure.     

Density Operator in Terms of Coherent States Representation with the Applications in the Quantum Information

In the quantum information theory operates with qubits and N-qubits that can be express through coherent states. Density operator admits a representation in terms of coherent states formalism. Consequently, in this paper the notions of qubit and density operators are described in the framework of coherent states. We have expressed a qubit as a coherent state, and thus a sequence of qubits becomes the tensor product of the coherent states. For the ensembles of qubits, it could be used the density operator, in order to describe the informational content of the ensemble. The coherent states representation may play an important role in the quantum information theory and the use of this formalism is not only theoretical, but also, due to its applications, of some practical relevance.