铯原子里德堡态Stark能量及电偶极矩的测量和理论计算

里德堡原子由于具有体积大、寿命长、易极化及在外电场中能级易于操控等特点, 已经成为了目前物理学领域研究的热点之一. 本文在磁光阱中实验测量了铯原子15P_3/2和16P_3/2态的Stark光谱,根据光谱给出了15P_3/2和16P_3/2|m|=1/2 Stark态在0-1400 V/cm场强范围适用的Stark 能量和偶极矩的经验性解析表达式; 用数值方法求解薛定谔方程获得了这些态的Stark能量、偶极矩和电子几率密度分布. 电子几率密度分布定性说明了计算的偶极矩矢量的方向是正确的. 计算的Stark能量、偶极矩与实验结果相一致.     

Electric dipole moments of acrylonitrile and of propionitrile measured in supersonic expansion

New determinations of the ground-state electric dipole moments of acrylonitrile and propionitrile have been made from Stark effect measurements at conditions of supersonic expansion. The measurements were made on selected Stark lobes of fully resolved hyperfine components of several lowest-J rotational transitions. The results are μ_a = 3.821(3) D, μ_b = 0.687(8) D, μ_tot = 3.882(3) D for acrylonitrile, and μ_a = 3.816(3) D, μ_b = 1.235(1) D, μ_tot = 4.011(3) D for propionitrile. The new value of μ_b for acrylonitrile is appreciably different from those reported previously and it has been substantiated by both ab initio calculations and relative intensity measurements. The new dipole moment implies a considerable revision in the calculated intensities of the strongest THz-region rotational transitions of acrylonitrile, to 59% of previous values.     

Static electric dipole polarizability of lithium atoms in Debye plasmas

<正>The static electric dipole polarizabilities of the ground state and n≤3 excited states of a lithium atom embedded in a weekly coupled plasma environment are investigated as a function of the plasma screening radium.The plasma screening of the Coulomb interaction is described by the Debye-H（u|¨）ckel potential and the interaction between the valence electron and the atomic core is described by a model potential.The electron energies and wave functions for both the bound and continuum states are calculated by solving the Schrodinger equation numerically using the symplectic integrator.The oscillator strengths,partial-wave,and total static dipole polarizabilities of the ground state and n≤3 excited states of the lithium atom are calculated.Comparison of present results with those of other authors, when available,is made.The results for the 2s ground state demonstrated that the oscillator strengths and the static dipole polarizabilities from np orbitals do not always increase or decrease with the plasma screening effect increasing, unlike that for hydrogen-like ions,especially for 2s→3p transition there is a zero value for both the oscillator strength and the static dipole polarizability for screening length D = 10.3106a₀,which is associated with the Cooper minima.     

Electric dipole echoes in Rydberg atoms

We report the first observation of echoes in the electric dipole moment of an ensemble of Rydberg atoms precessing in an external electric field F. Rapid reversal of the field direction is shown to play a role similar to that of a pi pulse in NMR in rephasing a dephased ensemble of electric dipoles resulting in the buildup of an echo. The mechanisms responsible for this are discussed with the aid of classical trajectory Monte Carlo simulations.     

Matter-wave interferometry with atoms in high Rydberg states

Matter-wave interferometry has been performed with helium atoms in high Rydberg states. In the experiments the atoms were prepared in coherent superpositions of Rydberg states with different electric dipole moments. Upon the application of an inhomogeneous electric field, the different forces on these internal state components resulted in the generation of coherent superpositions of momentum states. Using a sequence of microwave and electric field gradient pulses the internal Rydberg states were entangled with the momentum states associated with the external motion of these matter waves. Under these conditions matter-wave interference was observed by monitoring the populations of the Rydberg states as the magnitudes and durations of the pulsed electric field gradients were adjusted. The results of the experiments have been compared to, and are in excellent quantitative agreement with, matter-wave interference patterns calculated for the corresponding pulse sequences. For the Rydberg states used, the spatial extent of the Rydberg electron wavefunction was ～320?nm. Matter-wave interferometry with such giant atoms is of interest in the exploration of the boundary between quantum and classical mechanics. The results presented also open new possibilities for measurements of the acceleration of Rydberg positronium or antihydrogen atoms in the Earth's gravitational field.     

New all-optical method for measuring molecular permanent dipole moment difference using two-photon absorption spectroscopy

Stark effect, in combination with spectral hole burning and single-molecule spectroscopy, has been a fruitful technique to study permanent electric dipole moment of molecules in condensed phase. However, because measuring Stark shifts relies on external fields and narrow line- or hole-widths, the applicability of this method at ambient conditions required by most biological systems has remained limited. Here we demonstrate a new all-optical method for measuring the molecular dipole moment difference between ground and excited states using two-photon absorption (2PA) spectroscopy. We show that the value and orientation of the static dipole moment difference can be determined from the corresponding absolute 2PA cross-section. We use this new method to determine for the first time the strength of local electric field E_loc=0.1-1.0×10⁸ V/cm inside beta-barrel of Fruit series of red fluorescent proteins. Because our method does not rely on external field and is applicable in liquid solutions, it is well suited for the study of biological systems.     

Theoretical study of the electronic states and transition dipole moments of the LiK molecule

The adiabatic potential energy, the spectroscopic constants and the transition dipole moments of the lowest electronic states of the LiK⁺ molecule, dissociating into Li(2s, 2p, 3s, 3p, 3d, 4s, and 4p) + K⁺ and Li⁺ + K(4s, 4p, 5s, 3d, 5p, 4d, and 6s), have been investigated. We have used an ab initio approach involving a non-empirical pseudopotential for the Li (1s²) and K (1s²2s²2p⁶3s²3p⁶) cores and core valence correlation correction. A very good agreement has been obtained for the ground state for the spectroscopic constants with the available theoretical works. The transition dipole moment from X²Σ, 2²Σ, 3²Σ, and 4²Σ states to higher excited states have been determined. Numerous avoided crossing between electronic states of ²Σ and ²Π symmetries, have been localised and analysed. Their existences are related to the charge transfer process between the two ionic systems Li⁺K and LiK⁺.     

The theoretical and experimental investigations of Stark structure in sodium Rydberg states atoms

The experimental results of the Stark structure of Na in the vicinity of n~*=21-23 with the external electric field from 0 to 380V/cm are reported. The theoretical calculation of the stark levels of Na based on the atomic potential model are in good agreement with experiment. The limiting error between the theory and experiment turns out to be due to experimental uncertainty.     

Fully conjugated push–pull dendrons with high dipole moments in excited state; synthesis and theoretical rationalization

Novel fully conjugated push–pull dendrons were synthesized by a divergent approach to evaluate the performance of non‐conventional architectures like dendritic one in charge separation processes associated with photovoltaic events. The dipole moments in excited state were estimated by the solvatochromic method, to be related to the charge separation efficiency. A 1:2 ratio of donor–acceptor groups (methoxy and nitro groups respectively) promotes the largest dipole moment in both ground and excited state (up to 17 D), due to the efficient electron density transfer over the entire molecule, through the π‐electron system. The synthesized dendrons induce charge transfer on excitation as follows from UV–vis absorption–emission analysis and theoretical calculations. Copyright © 2015 John Wiley & Sons, Ltd.     

Potential energy curves,transition dipole moments,and radiative lifetimes of KBe molecule

An ab initio calculations on the ground and low-lying excited states(X~2Σ+, 2~2Σ+, 3~2Σ+, 1~4Π, 2~4Π, 1~4Σ~+, 2~4Σ~+,and 3~4Σ~+) of KBe molecule have been performed using multireference configuration interaction(MRCI) plus Davidson corrections(MRCI+Q) approach with all electron basis set aug-cc-p CV5Z-DK for Be and def2-AQZVPP-JKFI for K.The 3~2Σ+, 1~4Π, 2~4Π, 1~4Σ~+, 2~4Σ~+, and 3~4Σ~+states are investigated for the first time. Inner shell electron correlations are computed on the potential energy curves(PECs) calculations. The spectroscopic and molecular parameters are also predicted. In addition, The transition properties including transition dipole moment, Franck–Condon factors qv'v', Einstein coefficients Av'v', and the radiative lifetimes τυ for the 2~2Σ~+–X~2Σ~+, 3~2Σ~+–X~2Σ~+, and 2~4Π–1~4Π transitions are predicted at the same time.     

CASPT2 and CCSD(T) calculations of dipole moments and polarizabilities of acetone in excited states

The acetone molecule is investigated in its ground state and valence ^1,3n-π*, ^1,3π-π*, and ^1,3σ-π* excited states and Rydberg ^1,3n-3s, ^1,3π-3?, ^1,3n-3p_y and ^1,3π-3p_y states using the CASSCF, CASPT2, and CCSD(T) methods. Equilibrium geometries of excited states are obtained and their changes with respect to the ground state are discussed. For most excited states the C_2v symmetry of the ground state is lowered to the C_s symmetry. A series of valence vertical and adiabatic excitation energies is presented along with excitation energies for Rydberg states. The main body of the paper contains Finite-Field Perturbation Theory (FFPT) calculations of electric properties of the vertically as well as geometry relaxed excited states. Dipole moments of valence excited states decrease significantly upon excitation, being about one half of the ground state dipole moment. Polarizabilities usually change upon excitation much less (increase by about 30%) but hyperpolarizabilities are enhanced up to one or two orders of magnitude. The orientation of the dipole moment is reversed in some vertically excited Rydberg states. Properties of the ground and excited states are discussed considering alterations of the electronic structure and shifts in the geometry.     

运动介质的电偶极矩与磁矩

在推导出介质的极化强度与磁化强度的坐标变换公式的基础上,分析导出了运动介质的电偶极矩与磁矩.     

PbnSn(n=1-19)合金团簇电偶极矩和极化率的研究

利用基于密度泛函理论的有限电场方法对PbnSn(n=1-19)团簇的电偶极矩和极化率进行研究。PbnSn(n=1-19)合金团簇的高对称性抑制其电偶极矩的产生。在团簇原子总数N＜14时,团簇的电偶极矩与能隙表现出相反的变化趋势（同一尺寸下,高能隙与低电偶极矩相对应）,然而在14≤N≤19范围内,由于构型生长方式的转变,能隙与电偶极矩展现出相同的演化趋势。研究所得的极化率与实验值在部分尺寸相符合较好,但总体上与实验值还有一定的差别,这可能是实验中包含混合态或激发态的缘故。     

PbnSn(n=1-19)合金团簇电偶极矩和极化率的研究

利用基于密度泛函理论的有限电场方法对PbnSn(n=1-19)团簇的电偶极矩和极化率进行研究。PbnSn(n=1-19)合金团簇的高对称性抑制其电偶极矩的产生。在团簇原子总数N＜14时,团簇的电偶极矩与能隙表现出相反的变化趋势（同一尺寸下,高能隙与低电偶极矩相对应）,然而在14≤N≤19范围内,由于构型生长方式的转变,能隙与电偶极矩展现出相同的演化趋势。研究所得的极化率与实验值在部分尺寸相符合较好,但总体上与实验值还有一定的差别,这可能是实验中包含混合态或激发态的缘故。     

Theoretical investigation of the molecular structure and transition dipole moments of the NaK low lying electronic states

The electronic structure and the spectroscopic constants of the low lying electronic states of the NaK⁺ ionic molecule have been determined through using an ab initio approach involving a non-empirical pseudopotential for the Na and K cores and core valence correlation correction. The potential energy of nearly 26 electronic states of ²Σ⁺, ²Π, and ²Δ symmetries has been calculated up to their dissociation limit Na(4d) + K⁺ and Na⁺ + K(6s). Their spectroscopic constants (R_e, D_e, T_e, ω_e, ω_eχ_e, and B_e) are derived and compared with the few available theoretical studies. A good agreement has been found for the ground state and few excited states with previous works. New potential energy curves were presented, for the first time, for the higher excited states. Numerous avoided crossing between electronic states of ²Σ⁺, ²Π symmetries have been localized and analyzed. Their existences are related to the charge transfer between the two ionic molecules Na⁺K and NaK⁺. Furthermore, we have determined the transition dipole moments for several states and analyzed the avoided crossings related to charge transfer between alkaline atoms.     

New measurements and global analysis of rotational spectra of Cl-, Br-, and I-benzene: Spectroscopic constants and electric dipole moments

The data available from rotational spectroscopy for chlorobenzene, bromobenzene, and iodobenzene have been extended by new measurements in the mm-wave region and in supersonic expansion in the cm-wave region. All available ground state measurements have been combined in global fits to derive precise rotational, centrifugal, and nuclear quadrupole coupling constants for the molecules. Rotational transitions in first excited states of the lowest frequency normal modes in bromobenzene and iodobenzene have been assigned and fitted. The values of electric dipole moments for ³⁵Cl-, ⁷⁹Br-, ⁸¹Br-, and I-benzene have been determined from Stark effect measurements on selected hyperfine components in the supersonic expansion spectrum, and are compared with values for several other series of monohalogen molecules.     

Coherent excitons at different orientation arrangements of local transition dipole moments in circular light-harvesting complexes

The coherent exciton plays an important role in the photosynthetic primary process, and its functions are deeply dependent on the orientation arrangements of local transition dipole moments (TDMs). We theoretically and systematically study the physical property of the coherent exciton at different orientation arrangements of the local TDMs in circular light-harvesting (LH) complexes. Especially, if the orientation arrangements are different, the delocalized TDMs of the coherent excitons and the energy locations of the optically active coherent excitons (OACEs) can be obviously different, and then there are more manners to capture, store and transfer light energy in and between LH complexes. Similarly, if the orientation arrangements are altered, light absorption and radiative intensities can be converted fully between the OACEs in the upper and lower coherent exciton bands, and then the blue and red shifts of the absorption and radiative bands of the pigment molecules can occur simultaneously at some orientation arrangements. If the systems are in the vicinities of the critical orientation arrangements, the weak static disorder or small thermal excitation can destroy the coherent electronic excitations, and then the coherent exciton cannot exist any more.