Modeling of the vibrational structure of the vibronic spectrum and an excited state of the dinaphthylethylene molecule

The vibrational structure of the fluorescence spectrum and the structure of a dinaphthylethylene molecule in an excited state are calculated in the first and second approximations of the parametric method employed in the theory of vibronic spectra. The calculated spectra are in quantitative agreement with experimental data. The role of the angular parameters of the parametric method in the quantitative prediction of the vibrational structure of the fluorescence spectrum and changes observed in the geometry of the dinaphthylethylene molecule under excitation is determined. It is demonstrated that the polyene and acene parameters of the parametric method possess a high degree of transferability and that the models obtained are quite adequate to the real structures of the molecules under investigation. The proposed approach permits qualitative predictions and quantitative predictive calculations of the spectra of the studied molecules, as well as the spectral characteristics necessary for simulation of photochemical molecular transformations.     

电子的交换作用对激发态能量的影响

根据作者提出的物理模型和简洁有效的计算方法,考虑电子交换应对于激发态的影响,计算了激发态Ｌｉ原子（１ｓ＾２４ｓ）＾２Ｓ１／２的能量。计算结果表明：电子的交换能对低激发态的贡献较大,而对较高激发态（５ｓ、６ｓ…以上）在计算过程中可以忽略不计。     

Vibrational resonances of non-rotating HCN in the excited electronic state

A multi reference internally contracted configuration interaction (MRCI) method is used to generate the potential energy function (PEF) of the excited electronic state of HCN molecule. The analytic representation of the PEF is employed to calculate complex eigenvalues (resonance positions and widths) by a discrete variable representation (DVR) of the Hamiltonian for the non-rotating (J =0) molecule. The computational method used is a variant of the filter-diagonalization technique based on a recursive polynomial expansion of the absorbing-boundary-conditions (ABC) Green operator. Reasonable agreement with existing experimental data is found. Received 27 July 1999 and Received in final form 18 October 1999     

Multipole corrections to the electronic terms of a highly excited molecule

The properties are investigated of the electronic terms of a molecule with one of its electrons highly excited. These terms have a form similar to the ground electronic term of the corresponding molecular ion (core), and are obtained in the zeroth approximation by a parallel downward shift equal to Ry/n₂ and independent of the internuclear distances (symbasis property). The main causes of the deviation from this property are discussed. The nonsymbatic corrections, necessitated by the multipole interaction of the Rydberg electron with the ion core, are discussed. The possibility of using the results to detect new exciplexes is indicated.Translated from Trudy Fizicheskogo Instituta im. P. N. Lebedeva, Vol. 120, pp. 107–119, 1980.     

The electronic structure of the S8 molecule

The UV and X-ray photoelectron spectra of the S₈ molecule are presented together with an SCF-Xα-SW calculation of the electronic structure. The calculated optical transition energies are also presented and compared with the experimental UV absorption spectrum.     

The KrXe molecule: Modification of potential curves of the ground and first excited electronic states

Potential curves of the ground state of the KrXe molecule and its excited states that converge to the Kr(4p ^{6 1} S ₀) + Xe(5p ⁵6s ³ P ₁) atomic states are corrected and tested using the results of modeling published vacuum ultraviolet spectra of a gas-discharge plasma of a krypton/xenon mixture.     

Vibronic state specific predissociation rates from excited electronic states

It is shown that predissociation can be perceived as a primary process due to the continuum part of a Morse oscillator potential. In the model proposed here internal conversion to the ground state is thus not necessarily the primary process of a consecutive dissociation but may be a simultaneous decay. As a consequence, dissociation rates should show strong variations from specific (ro-) vibrational states of the first excited electronic states that are similar to those known from “pure” internal conversion rates. This behaviour is demonstrated by calculating predissociation rates for the process. Especially the out-of-plane modes seem to play an extraordinary role in the excess energy behaviour of the predissociation rate. At lower excess energies, rates from single vibronic levels with out-of-plane mode characteristics may show an increase by several orders of magnitude. Received: 13 November 1998     

Determination of dunham coefficients and calculation of the energies of highly excited vibrational-rotational levels of the carbon monoxide molecule in the electronic ground state

The values of Dunham constants are calculated for the electronic ground state of the carbon monoxide molecule on the basis of new values of the effective rotational and centrifugal constants and the energies of the high vibrational-rotational states are predicted. The peculiarity of the approach consists in the use of vibrational-rotational levels computed according to the traditional polynomial equation of energy values as the initial data for the procedure of Dunham coefficients determination. The role of the maximum degree of the Dunham polynom in determining its coefficients is analyzed, and the energy levels up to ν = 40 and J = 60 are calculated. A comparison with the literature data is made.     

Doublet structure of the first excited state of 71As

The possible multiplet structure of the first-excited state of ⁷¹As has been investigated by the high resolution ⁷⁰Ge(³He, dγ) reaction and the γ-rays emitted in the decay of ⁷¹Se. Both studies reveal a doublet at 143.2 keV and 147.3 keV excitation energies. The existence of this doublet in ⁷¹As brings the low-lying level structure in better resemblance to the heavier odd-A arsenic isotopes.     

Polarization spectroscopy of an excited state transition

We demonstrate polarization spectroscopy of an excited state transition in room-temperature cesium vapor. An anisotropy induced by a circularly polarized pump beam on the D2 transition is observed using a weak probe on the 6P(3/2)→7S(1/2) transition. At high pump power, a subfeature due to Autler-Townes splitting is observed that theoretical modeling shows is enhanced by Doppler averaging. Polarization spectroscopy provides a simple modulation-free signal suitable for laser frequency stabilization to excited state transitions.     

Features of the electronic structure of the intermetallic Co3Ti in an atomically disordered state

Using a method based on incorporating statistics into the theory of multiple scattering via the distribution function of atoms on lattices, the electronic structure of the intermetallic Co₃Ti is calculated for both complete atomic order and complete disorder. An unusual feature of the electronic structure of this intermetallic when it is disordered in the solid state is identified. Possible consequences of this behavior are analyzed. Fiz. Tverd. Tela (St. Petersburg) 39, 809–810 (May 1996)     

Fine structure inversion of the 3d excited state of sodium

The observed inversion of the fine structure of the excited 3d state of the sodium atom explained as due to a second-order effect between the electrostatic dipole exchange interaction and the magnetic spin-orbit interaction acting on the core 2p electrons.     

Ionization of ytterbium atoms from an excited state

The cross sections of the photoionization and the electron impact-induced ionization of Yb atoms from the excited 6s6p(³ P ₁) state are numerically calculated. Matrix elements are computed in multielectron relativistic and nonrelativistic approximations with allowance for the superposition of configurations and a relaxation effect. The radial part of the electron wavefunction in a continuous spectrum is calculated using the solutions to one-configuration Hartree-Fock and Dirac-Fock equations. The cross sections calculated by a relativistic method are compared to those for a nonrelativistic approximation. The ratios of the radiation reduced matrix elements and the phase shifts of the wavefunctions of a continuous spectrum calculated for the 6p ɛs and 6p → ɛd transitions are compared to the values obtained by approximating the experimental dependences of the angular distribution of photoelectrons for the photoionization by ultraviolet radiation from an oriented excited state.     

The thermionic double-diode,an efficient detector in excited state laser spectroscopy

We are describing the thermionic double-diode which is a suitable instrument for excited state laser spectroscopy. In comparison to the optogalvanic technique the signal-to-noise ratio was found to be 10²?10³ times better, investigating transitions between excited Sr or Ba states. Combined with its high detection sensitivity the thermionic double-diode presents the possibility of investigating transitions between high angular momentum states. It is demonstrated by studying transitions between Rydberg levels and doubly-excited autoionizing states in Ba. Further advantages are (i) the small strength of the dc electric field and the low electron density in the laser excitation region of the double-diode commending itself for studies of Doppler-free transitions to highly excited states and (ii) the very stable working conditions allowing to vary the pressure and current conditions in the diode in a much wider range than in a discharge.     

Photoemission from laser excited semiconductors: Dynamic response of the electronic structure in Si

Using angle-resolved photoemission in coincidence with a pulsed Nd:Yag laser beam (hν_L = 2.33 eV), we have studied the dynamic rearrangement of the electronic states in Si in the presence of a large number of electron hole pairs created by laser photon excitation. We observed considerable changes in the valence band structure, a renormalization of the bandgap, and a satellite peak in the 2p core level emission due to more effective core hole screening.