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.     

A new particle-hole approach to collective states

The relevance of the particle-hole space is demonstrated by showing that in some commonly used formalisms the first excited state lies entirely within the particle-hole space generated from the correlated ground state. This property is proved for several cases of angularmomentum projection — projected Hartree-Fock method (PHF) — and for the generator coordinate method in the Gaussian overlap approximation, while in other cases it has been verified only numerically. A new method is presented for the approximate calculation of energies and transition amplitudes of particle-hole excited states. Only hermitian one-body operators are used to generate the excited states. The two-body density matrix of a correlated state approximating the ground state is required as input data. The formula is tested on the 2⁺ and 3^? states of ⁸Be and ¹²C by using the PHF ground state. Where comparison is possible the method gives better agreement with PHF and experiment than the extended random-phase approximation.     

壳模型对13N Gamow-Teller跃迁的研究

最近的研究表明¹³N的beta衰变对于Ia型超新星爆炸前的电子丰度有着重要的影响.本文在壳模型的基础上,首先计算¹³N基态到基态以及基态到不同激发态的Gamow-Teller(GT)跃迁强度,并将其与实验数据进行了比较.在理论计算的GT强度基础上,对不同温度和密度天体环境下¹³N的电子俘获率进行了细致的计算,并重点讨论基态到激发态的GT跃迁对电子俘获率变化的影响.结果表明,考虑基态到激发态的跃迁后,超新星的电子丰度下降,中微子能量损失增大.基态到激发态跃迁对电子俘获率的影响主要由低激发能级贡献. 关键词： Gamow-Teller跃迁 壳模型 电子俘获 激发态     

Investigation of the electronic structure of Be2+He and Be+He,and static dipole polarisabilities of the helium atom

The potential energy and spectroscopic constants of the ground and many excited states of the Be⁺He van der Waals system have been investigated using a one-electron pseudo-potential approach, which is used to replace the effect of the Be²⁺ core and the electron-He interactions by effective potentials. Furthermore, the core–core interactions are incorporated. This permits the reduction of the number of active electrons of the Be⁺He van der Waals system to only one electron. Therefore, the potential energy of the ground state as well as the excited states is performed at the SCF level and considering the spin–orbit interaction. The core–core interaction for Be²⁺He ground state is included using accurate CCSD (T) calculations. Then, the spectroscopic properties of the Be⁺He electronic states are extracted and compared with the previous theoretical and experimental studies. This comparison has shown a very good agreement for the ground and the first excited states. Moreover, the transition dipole moment has been determined for a large and dense grid of internuclear distances including the spin orbit effect. In addition, a vibrational spacing analysis for the Be²⁺He and Be⁺He ground states is performed to extract the He atomic polarisability.     

Microscopic multi-channel calculations for the10Li system

A microscopic multichannel calculation for the¹⁰Li system has been performed in the framework of the Refined Resonating Group Method. Elastic neutron scattering off the⁹Li ground state and transitions into four excited states were considered. The energy spectrum of¹⁰Li is deduced from a phase shift analysis. Besides theJ ^π = 1⁺ ground state, five excited states are identified.     

Configurational coordinate diagram of Ni2+ doped silver halide crystals,as determined by optical and luminescence measurements

Optical and luminescence measurements were carried out on Ni²⁺ doped silver halide crystals. The configurational coordinates of the ground and the first excited states made it possible to explain the important optical properties, such as the Stokes shift between the ground and excited states, the broadening of the bands with temperature and the thermal quenching. Determining the configurational coordinate diagram of the ground and first excited states is the first step for the design and fabrication of solid state and fiber lasers which are based on Ni²⁺ doped silver halides and which operate in the middle infrared.     

An angular momentum projected particle-hole theory for deformed nuclei and its application to theT=1 negative parity states of20Ne

An angular momentum projected particle-hole theory is proposed as an approach to describe excited states of deformed nuclei. Both for the ground and the excited states, angular momentum projections are done before variation. This allows one to look for the effect, with an appropriate constraint, of the difference in the deformations of these states. The theory is applied to the case of Ne²⁰ where the splitting of the giant resonance is observed. Other negative parity states are also studied and their transitions to the 2⁺ member of the ground state band show interesting features which may have experimental implications. On the other hand, the change in the deformation of the excited states has only a small effect on the transition probabilities.     

The low-lying level structure of87Rb

The low-lying states of⁸⁷Rb are studied in the framework of a quasiparticle-core coupling model. The agreement between the calculated and experimental level spectra, stripping strength, ground state static electromagnetic moments and theE2 transition rate of the first excited state is good. Electromagnetic moments and transition rates for other excited states are predicted.     

(n,t) and (n, α) reactions on 9Be

A metallic ⁹Be target was bombarded with 13.99 MeV neutrons; α-particles, tritons and ⁶He recoil nuclei were detected and identified with a telescope consisting of two proportional counters and a solid state detector. Absolute differential cross sections were measured for the (n, t) reactions leading to the ground state and first excited state of ⁷Li and for the (n, α) reactions leading to the ground state and first excited state of ⁶He. No evidence for higher excited states in ⁶He has been found. An attempt has been made to interpret the observed (n, α) angular distributions in terms of the direct reaction model.     

Theoretical investigations of the SH and LiS cations

Reliable theoretical data on spectroscopy and spin-orbit matrix elements are computed for the lowest electronic states of SH⁺ and LiS⁺ ions. Accurate spectroscopic predictions for their excited electronic states are given. For SH⁺, polarization minima at large internuclear distances are located in addition to the strongly bound electronic states already known. For LiS⁺, our calculations confirm that the electronic ground state of this ion is of ³Σ⁻ species and reveal the existence of a ¹Δ state presenting a potential well as deep as the potential of the ground state. Moreover, the LiS⁺ electronic excited states potential energy curves possess shallow potential minima in the molecular region and at long-internuclear distances. Generally, these shallow minima may be populated during low energy collisions between the corresponding atomic fragments. Finally, spin-orbit calculations have allowed giving accurate determinations of the spin-orbit splittings for these cations and elucidation of the predissociation mechanisms of SH⁺ leading to the formation of the S⁺ and H species in their electronic ground states. Accordingly, long-lived SH⁺ ions can be found in the X³Σ⁻, a¹Δ and b¹Σ⁺ electronic states and the rovibrational levels of LiS⁺ in its electronically excited and ground states should be weakly perturbed.     

甲基乙烯基硅酮在外场作用下的光激发特性研究

采用密度泛函B3P86和组态相互作用方法在6-311++G^**基组水平上计算了甲基乙烯基硅酮分子从基态到前10个激发态的跃迁波长，振子强度，自发辐射系数A_n0和吸收系数B_0n(n＝1—10).同时研究了外电场对甲基乙烯基硅酮分子激发态的影响规律.结果表明，随外电场强度增大，最高占据轨道与最低空轨道能隙变小，激发能随电场增加而急剧减小.因而表明在外电场作用下，分子易于激发和 关键词： 甲基乙烯基硅酮 激发态 外电场     

Effect of lattice relaxation on spin density of nitrogen-vacancy centers in diamond and oscillator strength calculations

Using a generalized Hubbard Hamiltonian, many-electron wavefunctions of negatively charged (NV⁻) and neutral nitrogen-vacancy (NV⁰) centers in diamond were calculated. We report the effect of symmetric relaxation of surrounding atoms on the spin density, calculated from the many electron wavefunctions in the ground and excited states. We evaluated the error, that, arises in estimation of spin density when lattice relaxation effect is neglected in Electron Paramagnetic Resonance experiment and showed that the ground state spin density distribution is accessible in outward relaxations. The computed oscillator strengths give a higher efficiency for the 1.945 eV photoluminescence (PL) line of NV⁻ with respect to 2.156 eV PL line of NV⁰ which agrees well with experiment. This result is explained based on the largest the ground state spin among available values for the NV⁻ with respect to NV⁰. The transition probability between degenerate ground and excited states slightly depends on the S _z value. Finally, we report on the electronic configurations which contribute to the ground and excited states and discuss the population variation of electronic configurations with relaxation.     

Microwave spectrum of 3-bromopropene in the excited torsional states

The microwave spectra in the excited states of the CC torsion for the ⁷⁹Br and ⁸¹Br isotopic species of 3-bromopropene were measured in the frequency region 15.3–23.7 GHz. The a-type R-branch and b-type Q-branch rotational transitions in the first and second excited states of one conformer, skew, have been assigned and analyzed. Analysis of the spectrum yields the rotational constants and the nuclear quadrupole coupling constants. From relative intensity measurements the energy differences associated with the CC torsion, between the ground and first excited state, the ground and second excited state have been found to lie 109 and 206 cm^?1, respectively.     

Excited state spin waves in ErFe2

Neutron inelastic scattering measurements on ErFe₂ reveal an unusual doubling of the two lowest energy spin wave branches over a wide temperature range. Crystal field calculations suggest that one member of each doublet is associated with transitions from the ground state of Er³⁺ to the first excited state, while the other is associated with transitions between excited states. The gapless acoustic mode appearing at high temperatures is identified as a propagating excited state spin wave.     

Convergent perturbation expansion for the anharmonic oscillator

We study the ground state as well as the first three excited states of the anharmonic oscillator with anharmonicity λx⁴ for a range of λ = (0, 10) with the first-order logarithmic perturbation iteration method (FOLPIM). This leads to convergent results. The initial choice of the wave function seems only to affect the rate of convergence in the case of the ground state but may critically affect the convergence for the excited states. For large values of λ, convergence is best obtained by choosing the asymptotic solution as the initial “unperturbed” wave function.     

Decay properties of the key resonant states in8Li(α, n)11B for primordial nucleosynthesis

The particle decay property of the key resonant states in the reaction⁸Li(,n)¹¹B for the inhomogeneous big bang models was studied experimentally. The sum of the branching ratios of the 10.572 MeV state for the neutron decays to the excited states in¹¹B is as large as for the ground state, indicating that the neutron decays to excited states are crucial and enhance the reaction rate for heavy element synthesis considerably.     

Microwave spectrum,dipole moment,and structure of 3-aminopropanol

The microwave spectra of 3-aminopropanol and three of its deuterium substituted isotopic species have been investigated in the 26.5 to 40 GHz frequency region. The rotational spectrum of only one conformer has been assigned in which presumably a hydrogen bond of the OH---N type exists. The rotational spectra of a number of excited vibrational states have been observed and assignments made for some of these excited states. The average intensity ratio for the rotational transitions between the ground and excited vibrational states indicates that the first excited state is about 120 cm^?1 above the ground state.and the next higher state is roughly 200 cm^?1 above the ground vibrational state. The dipole moment was determined from the Stark effect measurements to be 3.13 ± 0.04 D with its principal axes components as |μ_a| = 2.88 ± 0.03 D, |μ_b| = 1.23 ± 0.04 D and |μ_c| = 0.06 ± 0.01 D. The possibility of another conformer where the hydrogen bond could be of NH---O type was explored, but the spectra of such a conformer could not be identified.     

The structure of 16O; A review of the theory

The nucleus ¹⁶ ₈O₈ is the prototype for a large number of developments in nuclear structure theory. It is a doubly magic N=Z nucleus, light enough that an isotopic spin formalism should be a valid approximation. The Brueckner-Hartree-Fock procedure in a spherical basis should be capable of describing the gross properties of the ground state. The excited states of negative parity exhibit the characteristic low-lying ‘octupole vibrational state’ and there is a much studied ‘giant dipole region’ which should be amenable to the analysis of the ‘random phase approximation’. The first excited state is the ‘mysterious second zero’ par excellence and a great deal of work on describing it via the method of ‘deformed state admixtures’ has been carried out. The first excited state and a number of other excited states appear to support spectra reminiscent of rotational bands and the collective character of these states has been extensively studied in both the Bloch-Horowitz and α-cluster model schemes.     

Study of ground state and some low-lying excited states of formaldehyde molecule by CNDO/VN−1 method

The semiempirical CNDO/V^N–1 method presented for calculating the excited states of molecules permits both the ground state and excited states to be considered with one parametrization. The equilibrium geometry is calculated for the ground state¹A₁ and excited states³A₂,¹A₂, and³A₁ of the formaldehyde molecule. The results of calculation are in good agreement with experimental data. The frequencies of electronic transitions are calculated for radiation and absorption.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 6, pp. 43–48, June, 1978.     

Study of the diffraction scattering 12C + 12C with the excitation of the 12C exotic state 0 2 + (the Hoyle state)

New results from a series of experiments dedicated to the study of the ¹²C exotic state (the so-called Hoyle state) are presented. In spite of the many investigations that have been carried out, the structure of this state (which lies above the threshold for breaking up into three alpha particles) is still unknown. The different models assume that the nucleus has an abnormally large size in this excited state. However, until recently, methods for measuring the radii of unbound states have not been suggested. The best way to solve this problem seems to be by measuring the angular distributions of elastic and inelastic scattering of ¹²C on different target nuclei, and the determination of the radii is based on the fact that, at small scattering angles, the cross sections for direct reactions at high enough energies behave like Frauenhofer diffraction on a black ball. Accordingly, an experiment was performed aimed at measuring the elastic and inelastic angular distributions of ¹²C with an energy of (121.5 ± 0.5) MeV on a ¹²C target. The elastic scattering was measured in the angular range from 18° to 50° in the c.m. system with uncertainty in the angle of measurement equal to Δθ = ± 0.6°. The inelastic cross section was measured for the ¹²C excited state 2⁺ (4.44 MeV) and 0⁺ (7.65 MeV). Estimates were made for the diffraction radii for the ground and excited states. An increase was observed in the radius of the state at 7.65 MeV compared to those of the ground and first excited states.