Selection rules for electric multipole transition of diatomic molecule in scattering experiments

The knowledge of the energy level structures of atoms and molecules is mainly obtained by spectroscopic experiments.Both photoabsorption and photoemission spectra are subject to the electric dipole selection rules(also known as optical selection rules). However, the selection rules for atoms and molecules in the scattering experiments are not identical to those in the optical experiments. In this paper, based on the theory of the molecular point group, the selection rules are derived and summarized for the electric monopole, electric dipole, electric quadrupole, and electric octupole transitions of diatomic molecules under the first Born approximation in scattering experiments. Then based on the derived selection rules, the electron scattering spectra and x-ray scattering spectra of H2, N2, and CO at different momentum transfers are explained, and the discrepancies between the previous experimental results measured by different groups are elucidated.     

X-ray emission spectra of small molecules

An instrument for X-ray emission studies of free molecules is described and electron and fluorescence excitations are discussed. The application of X-ray emission spectroscopy to free molecules is exemplified by the spectra of N₂, CO, NO and CO₂. From the spectra the core level binding energies of the molecules are deduced. For the diatomic molecules vibrational fine structure is resolved and analyzed in terms of different bond lengths in the initial and final states. The change in bond length, when the initial 1s vacancy is formed, is also discussed. The influence of the X-ray selection rules and molecular localization properties on the band intensities are discussed and exemplified by the O1s and C1s spectra of CO and CO₂. In the spectra about ten satellites are found.     

Automated Technique for Identifying Experimental Vibrational–Rotational Molecular Spectra Based on Variational Calculations

We describe a technique for automated identification of experimental vibrational–rotational molecular spectra, which is based on variational calculations. The proposed technique is used to analyze the experimental spectra of triatomic molecules H₂O and HDO. This technique significantly accelerates processing and analysis of experimental data and drastically improves accuracy and quality of the results obtained. The possibility of applying this technique for analyzing spectra of other polyatomic molecules is discussed.     

Orbital angular momentum exchange in the interaction of twisted light with molecules

In the interaction of molecules with light endowed with orbital angular momentum, an exchange of orbital angular momentum in an electric dipole transition occurs only between the light and the center of mass motion; i.e., internal "electronic-type" motion does not participate in any exchange of orbital angular momentum in a dipole transition. A quadrupole transition is the lowest electric multipolar process in which an exchange of orbital angular momentum can occur between the light, the internal motion, and the center of mass motion. This rules out experiments seeking to observe exchange of orbital angular momentum between light beams and the internal motion in electric dipole transitions.     

High-Resolution Infrared Spectrum of BrCN in the nu(2) and nu(1)/2nu(2) Regions

The vibrational excitations of bent triatomic molecules, including both bending and stretching vibrations, are studied in the framework of the U(4) algebra. For the bent triatomic molecules H(2)O and H(2)S, the highly excited vibrational levels (up to 14) are obtained using the U(4) algebraic approach. We have found that the spectra are made up of clustering structure. The number of levels in one cluster depends on the total quanta of stretching and bending. In addition, some other properties are also discussed. Copyright 2000 Academic Press.     

Molecular orbital momentum distributions and binding energies for H2O using an electron impact coincidence spectrometer

The construction and operation of an instrument which uses the techniques of coincidence counting and electron impact spectroscopy is reported for the study of molecular ionization at large momentum transfer in which the two outgoing electrons are detected at 45° to the incident beam. Variation of the incident energy provides binding-energy spectra for Xe, CH₄ and H₂O up to 45 eV. Alternatively variation of the azimuthal angle (symmetric, non-coplanar geometry) gives a measure of the electron momentum distribution for any selected orbital in the binding-energy spectrum. Momentum distributions for the four valence orbitals of H₂O are compared with various wavefunctions from the literature.     

Interband transitions in a narrow-band spherical InSb quantum layer in the presence of an electric field

The interband transitions in a narrow-band InSb quantum spherical layer are studied theoretically within the framework of the spherical rotator model. The electron and light-hole dispersions are described using the two-band Kane approximation, while for heavy holes the standard dispersion is considered. The absorption coefficients for transitions between conduction and lighthole, heavy-hole bands are calculated. The selection rules and threshold absorption frequencies are determined. It is shown that in the presence of a weak electric field the selection rules and threshold absorption frequencies for dipole transitions are modified.     

动力学对称群方法对三原子分子高激发振动态的理论研究

利用动力学对称群方法研究了弯曲三原子分子的振动高激发态能谱-该方法显示：三原子分子的动力学对称性为U₁(4)U₂(4),则三原子分子的Hamiltonian量可写成代数的各元素之和,通过李代数处理而求得分子代数Hamiltonian量的本征值,进而得到分子的振动能谱-并具体计算了O₃分子- 关键词：     

Wave-particle duality of solitons and solitonic analog of the Ramsauer-Townsend effect

We study the interaction of light beams carrying angular momentum with a single, trapped and well localized ion. We provide a detailed calculation of selection rules and excitation probabilities for quadrupole transitions. The results show the dependencies on the angular momentum and polarization of the laser beam as well as the direction of the quantization magnetic field. In order to optimally observe the specific effects, focusing the angular momentum beam close to the diffraction limit is required. We discuss a protocol for examining experimentally the effects on the S_1/2 to D_5/2 transition using a ⁴⁰Ca⁺ ion. Various applications and advantages are expected when using light carrying angular momentum: in quantum information processing, where qubit states of ion crystals are controlled, parasitic light shifts could be avoided as the ion is excited in the dark zone of the beam at zero electric field amplitude. Such interactions also open the door to high dimensional entanglement between light and matter. In spectroscopy one might access transitions which have escaped excitation so far due to vanishing transition dipole moments.     

Angular distribution of the photoelectron spectrum of CO2, COS,CS2, N2O,H2O,and H2S

The photoelectron spectra of the triatomic molecules CO₂, COS, CS₂, N₂O, H₂O, and H₂S have been measured as a function of the angle θ between the direction of the incoming photon and outgoing photoelectron. The photoelectron spectra have been measured with a double-focusing electrostatic electron spectrometer to which has been attached a chamber containing a gas discharge lamp that can be freely rotated. (The photon source used was the 21.22 eV He I resonance line). From the dependence of intensity as a function of θ the angular parameter β was determined for each ionization band observed in the photoelectron spectra. A correlation was noted between the values of β and the molecular orbitals relative to the contributions of oxygen and sulfur atomic orbitals. Individual β values were also obtained for most of the vibrational bands seen in the photoelectron spectra. In most cases the vibrational structure showed little or no change in the angular parameter for a given electronic state. In certain cases, however, such as the fourth ionization band in CS₂, CO₂, and COS, rather sizeable changes in β were observed for the different vibrational bands.     

Selection rules for rovibronic transitions in symmetric top molecules

A simple diagrammatic rule is presented for determining the rotational selection rules governing transitions between any pair of vibronic states in electric dipole spectra of symmetric top molecules. The rule is useful in cases where degenerate vibronic levels with first-order Coriolis splittings occur, because it gives immediately the selection rule for the (+l) and (-l) components in any degenerate state. The rule is also helpful in determining the symmetry species and the effective zeta constants in overtone and combination levels involving degenerate vibrations. Particular attention is devoted to the conventions concerning the signs of zeta constants.     

Electron spectroscopy using excited atoms and photons IX. Penning ionization of CO2, CS2, COS,N2O,H2S,SO2, and NO2

The electron spectra resulting from thermal collisions of He* (predominantly 2³S) metastable atoms with the seven triatomic molecules, CO₂, COS, CS², N₂O H₂S, SO₂ and NO₂, are compared with their respective 584-Å photoelectron spectra using a transmission-corrected electron spectrometer. The normalised relative electronic-state transition probabilities for production of ionic states in Penning ionization and photoionization are reported together with energy shifts (ΔE values) for He*(2³S) Penning ionization. The cross-section for Penning ionization to lower states of NO₂⁺ is extremely low as has been observed in other open shell molecules such as NO and O₂.     

Interaction of Twisted Light with Electrons in Two-Dimensional Quantum Rings

We investigate the dynamics of charge carriers propagating in a ring being induced by twisted light: The exciting laser beam is assumed to have nonzero orbital angular momentum. The selection rules for the transitions between the eigenstates of the two-dimensional ring are determined with the aid of analytic and numerical methods. Using these results, we gain an insight into the physical process that leads to the transfer of the angular momentum of the laser beam to the electrons in the quantum ring.     

Birefringence and absorption of infrared radiation in tunnel-coupled GaAs/AlGaAs quantum wells in a longitudinal electric field

Birefringence and absorption modulation under electron heating in a longitudinal electric field in the tunnel-coupled GaAs/AlGaAs quantum wells have been found and investigated in the spectral region corresponding to intersubband electron transitions. The observed phenomena are explained by electron heating in electric field and electron transfer in real space. The equilibrium absorption spectra at different lattice temperatures are analyzed.     

Spectroscopic evidence for the effect of the ortho H<Subscript>2</Subscript>O spin on the electron transfer in photosynthesis

A spin mechanism for electron transfer control in the reaction center of purple bacteria in photosynthesis is proposed. Rotation and conversion of the ortho/para spin isomers of two H₂O molecules located near the special pair of the reaction center are treated as the sources of the coherent modulations of transient kinetics. Modulation of the collective wave function of the reaction center electrons by the total proton spin of ortho H₂O is a key feature allowing the molecule to play the role of a gate controlling the electron transfer. The iron atom in the reaction center with the gradient magnetic field is treated as a catalyst removing the strict forbiddenness of H₂O ortho/para conversion. It is shown that the modulation of the reaction center stimulated emission kinetics observed in the field of femtosecond pulses coincides with the rotational transitions of ortho/para H₂O. Influence of the effect of the electric field (Stark effect) on the level displacement and ortho/para conversion rate is discussed.     

Quantized orbital angular momentum transfer and magnetic dichroism in the interaction of electron vortices with matter

Following the very recent experimental realization of electron vortices, we consider their interaction with matter, in particular, the transfer of orbital angular momentum in the context of electron energy-loss spectroscopy, and the recently observed dichroism in thin film magnetized iron samples. We show here that orbital angular momentum exchange does indeed occur between electron vortices and the internal electronic-type motion, as well as center-of-mass motion of atoms in the electric dipole approximation. This contrasts with the case of optical vortices where such transfer only occurs in transitions involving multipoles higher than the dipole. The physical basis of the observed dichroism is explained.     

Charge transfer-transitions and X-ray photoelectron spectroscopy of copper(II) complexes

Satellite structure in the X-ray photoelectron (Cu 2p) spectra of some squareplanar cupric complexes has been compared to electron paramagnetic resonance and electronic spectra results on the electronic structure of these complexes. It is shown that these satellites can be assigned to various ligand → metal 3d or ligand → ligand* transitions within the monopole selection rules of the sudden approximation.     

Signatures of short-range many-body effects in the dielectric function of silicon for finite momentum transfer

We present an investigation of the dynamic structure factor and of the dielectric function epsilonM(Q,omega) of the prototypical semiconductor silicon for finite momentum transfer, combining inelastic x-ray scattering experiments and ab initio calculations. In contrast with optical spectra, for finite momentum transfer time-dependent density-functional theory in the adiabatic local-density approximation together with lifetime broadening describes the physics of valence excitations correctly. Major structures in the spectra, governed by short-range crystal and exchange-correlation local-field effects, are strongly influenced by a mixing of transitions of positive and negative energies, in striking difference to spectra for vanishing momentum transfer. This mixing gives rise to a pronounced Fano asymmetry.     

Selection rules in DWBA theory of (p,t) reactions

Angular momentum selection rules for (p, t) reactions within the framework of DWBA formalism are given for the particular case where the triton wavefunction is classified according to its orbital permutation symmetry. The selection rules demonstrate that certain previous calculations of unnatural parity transitions should exactly vanish, and suggest the important result that “weak” unnatural parity transitions can occur as direct one step reactions via the mixed symmetry S and D state components of the triton wavefunction.