Photoelectron spectroscopy of molecular systems and quantum-chemical calculations in terms of the density functional theory: Iron π complexes L-Fe(CO)3

The HeI and NeI photoelectron spectra of irontricarboniyl complexes with cyclic diene ligands—αmethylstyrene, orthoquinodimethane, and cyclooctatetraene—were obtained. The results of quantum-chemical calculations of the molecules of these compounds in the approximation of the density functional theory (B3LYP/6-31G*) are presented. It is shown that this approximation describes well the excited ionic states of the π complexes under study. The relative ionization cross sections σ_π and σ_3d , which characterize the probability of removal of electrons from the molecular π-ligand and 3d-metal orbitals, are estimated. The mechanism of the selective coordination of the Fe(CO)₃ groups to corresponding organic ligands is discussed. The energies of the L-Fe(CO)₃ chemical bond are calculated.     

The electronic structure of dinuclear transition-metal complexes containing metal—metal interactions: II. He(I) and He(II) photoelectron spectra of hexacarbonyldi-irondisulfur and related complexes

The He(I) and He(II) photoelectron spectra of a series of Fe₂(CO)₆LL¹-type complexes (L = L¹ = S, (i-propyl)S; L,L¹ = t-but of an all-electron, ab initio SCF MO calculation on Fe₂(CO)₆S₂ and of extended CNDO calculations on related molecules. Assignments given ar He(I)/He(II) intensity differences, and on comparison with related molecules.The coordination of the bridging ligands to the metal centres and the nature of the metal—metal interactions are discussed.     

Study of cross sections for the loss of outer 1s, 2s, and 2p electrons by fast ions and atoms of light elements

In the case of light-element ions propagating with velocities V = 1.83 and 3.65 au in H₂, He, N₂, Ne, and Ar, the loss cross sections σ_{i, i+m} for m electrons (m = 1, 2, 3) are considered. The partial loss cross sections σ_i(nl) for one of the outer 1s, 2s, or 2p electrons are determined using the obtained data. It is shown that the experimental cross sections for the loss of the 1s and 2s electrons by positive ions qualitatively agree with the theoretical values calculated in the Born approximation. In the case of the ion velocity V = 1.83 au, the cross sections σ_i for 2p electrons are greater than the cross sections σ_i (1s) and σ_i (2s) by a factor of 1.2–3 for the same binding energies of electrons in the ion (I _nl > 20 eV). It is found experimentally that, at V = 1.83 au, the cross sections σ_i (2p) for I _nl ～ 10–20 eV are less than the cross sections σ_i (1s) by a factor of 2–3, which is probably caused by a decrease in the screening parameter (θ_2p < 1) of the outer shell of atoms.     

Analysis of the relationship between the electron-capture and electron-loss cross sections for carbon ions

The electron-loss cross sections σ _{i, i + 1} and the electron-capture cross sections σ _{i, i ? 1} for carbon ions with energies of 35–330 keV/nucleon in hydrogen and neon are determined from experimental data. It is demonstrated that, for particle energies which satisfy the condition σ _{i, i + 1} = σ _{i, i ? 1} or σ _{i, i ? 1} = σ _{i ? 1, i} , the average equilibrium ion charge can be evaluated without solving the system of differential equations for charge exchange. The dependence of the average equilibrium ion charge on the ion energy is investigated for carbon ions.     

Physical criteria for the reliability of data on the photodisintegration of the <Superscript>89</Superscript>Y nucleus

Experimental photonuclear reaction cross sections obtained in experiments using quasimonoenergetic annihilation, monoenergetic tagged photons, and bremsstrahlung γ-radiation are analyzed using physical criteria for the reliability of data on the ⁸⁹Y nucleus. It is found that the reliability of data on the cross sections of partial reactions (γ, 1n) and (γ, 2n), obtained by means of photoneutron multiplicity sorting, is highly doubtful. Reliable cross sections of reactions (γ, 1n) and (γ, 2n) are obtained using the experimental–theoretical method (ETM) for evaluating using both experimental cross sections of neutron yield reaction σ^exp(γ, xn) that are free of neutron multiplicity problems, and theoretically calculated F _i ^theor ratios of the cross sections of definite (i) partial reactions to cross section σ^theor(γ, xn). It is shown that the evaluated cross sections differ noticeably from the experimental data.     

Bestimmung des Wirkungsquerschnitts σ(Cs+→Cs) aus Sondenmessungen in einem thermischen Cs-Plasma

The ion currentI _i to a Langmuir probe was measured in a Cs-plasma which was produced by contact ionization and for which the neutral densityn _g is known and the plasma density is given by the Saha equation. Using the theory of Self and Shih the collision cross section σ(Cs⁺→Cs) was calculated from the measured ion currentI _i .     

Charge exchange cross sections of carbon ions

Based on experimental data on the ion charge distributions, the cross sections of single electron loss σ _{i, i + 1} and single electron capture σ _{i, i ? 1} by carbon ions with velocities (2.7–8) × 10⁸ cm/s in different gaseous media (He, N₂, and Ar) have been obtained. Regularities of the cross section variation of the electron capture and loss by carbon ions as a function of the ion velocity, ion charge, and atomic number of the target have been for the first time studied in a wide range of the initial ion charge, from i = 0 to i = 6. A qualitative agreement of the obtained results with the published data has been established for a number of other ions. Theoretical calculations of the cross sections of single electron loss by carbon ions in helium have been carried out.     

Cross sections of the photoneutron reaction for <Superscript>141</Superscript>Pr and <Superscript>186</Superscript>W nuclei,estimated from physical criteria of data reliability

Using objective physical criteria for data reliability, cross sections of partial photoneutron reactions (γ, 1n), (γ, 2n) and (γ, 3n) that are free of the shortcomings of neutron multiplicity sorting methods used on beams of quasimonoenergetic annihilation photons are obtained for ¹⁴¹Pr and ¹⁸⁶W nuclei. Evaluation is performed using the experimental–theoretical method (ETM), based on the experimental cross section of neutron yield reaction σ^exp(γ, xn) = σ^exp(γ, 1n) + 2 σ^exp(γ, 2ⁿ) + 3 σexp(γ, 3n) + … and ratios F _i ^theor= σ^theor(γ, in)/σ^theor(γ, xn) calculated within the combined model (CM) of photonuclear reactions, which stipulates that σ^eval(γ, in) = F _i ^theor σ^exp(γ, xn). It is found that for ¹⁴¹Pr and ¹⁸⁶W, ratios F ^exp _i do not contradict the data reliability criteria only at energies up to ~21 and ~22 MeV, respectively. At the same time, there are notable discrepancies between F _i ^theor and F ^exp _i, and thus between the evaluated and experimental cross sections of reactions. It is shown that the discrepancies between the evaluated and experimental cross sections are due to the assumed unreliable experimental distribution of neutrons in the channels with multiplicities 1, 2, and 3.     

Spectroscopy and quantum-chemical calculations of nitro-bis-bipyridyl complexes of ruthenium(II) with 4-substituted pyridine ligands

The luminescence, absorption, and luminescence excitation spectra of complexes cis-[Ru(bpy)₂(L)(NO₂)]⁺ [bpy = 2,2′-bipyridyl, L = pyridine, 4-aminopyridine, 4-dimethylaminopyridine, 4-picoline, isonicotinamide, or 4,4′-bipyridyl] in alcoholic (4 : 1 EtOH–MeOH) solutions are studied at 77 K. A linear correlation is established between the energy of the lowest electronically excited metal-toligand charge transfer state d_π(Ru) → π*(bpy) of the complexes and the pK_a parameter of the free 4-substituted pyridines used as ligands L. The B3LYP/[6-31G(d)+LanL2DZ(Ru)] hybrid density functional method is used to optimize the geometry of complexes and calculate their electronic structure and the charge distribution on the atoms of the nearest environment of ruthenium(II) ions. It is shown that there exists a mutually unambiguous correspondence between the charge on the nitrogen atom of ligands L coordinated in the complex and the pK_a parameter of ligands. The calculated energies of the electronically excited metal-to-ligand charge transfer states of complexes linearly (correlation coefficient 0.99) depend on the charge on the nitrogen atom of ligands L, which completely agrees with the experimental data.     

Spectroscopic and quantum-chemical investigations of chloro-bis-bipyridyl complexes of ruthenium(II) with 4-substituted pyridine ligands

The luminescence spectra of cis-[Ru(bpy)₂(L)Cl]⁺ (bpy is 2,2′-bipyridyl; L is pyrazine, pyridine, 4-amino-pyridine, 4-picolin, isonicotinamide, 4-cyanopyridine, or 4,4′bipyridyl) complexes are studied in alcoholic (4: 1 EtOH-MeOH) solutions at 77 K. A linear correlation is found between the energy of the lowest electronically excited metal-to-ligand charge transfer (³MLCT) state d _π(Ru) → π* (bpy) and the parameter pK _a of the free 4-substituted pyridines and pyrazine used as ligands L. The [B3LYP/6-31G + LanL2DZ(Ru)] hybrid method of the density functional theory is used to optimize the geometry of complexes and calculate their electronic structure and the charge distribution on the atoms of the nearest environment of the ruthenium ion. It is shown that there exists a linear unambiguous correlation between the negative charge on the nitrogen atom (qN ^L) of ligands L coordinated in the complex and the parameters pK _a of free ligands. The calculated energies of ³MLCT excited states almost linearly (correlation coefficient 0.958) depend on the charge qN ^L, which completely agrees with experimental data.     

Reliability of the data on the cross sections of the partial photoneutron reaction for <Superscript>63,65</Superscript>Cu and <Superscript>80</Superscript>Se nuclei

The cross sections of partial photoneutron reactions are evaluated for the ^63,65Cu and ⁸⁰Se isotopes. The cross sections are free of systematic uncertainties from shortcomings of the experimental methods for neutron multiplicity sorting based on measurements of neutron energy used in experiments with quasimonoenergetic annihilation photon beams. An experimental-theoretical method is used to evaluate cross sections σ^eval(γ, in)= F_i^theor σ^exp(γ, xn), where ratios F_i^theor = σ^theor(γ, in)/σ^theor(γ, xn) = σ^theor(γ, in)/σ^theor[(γ, 1n) + 2(γ, 2n) + …] are calculated using a combined model of photonuclear reactions, and σ^exp(γ, xn) is the experimental cross section of the neutron yield reaction free from neutron multiplicity sorting problems. The cross sections are evaluated for reactions (γ, 1n) and (γ, 2n) for the ^63,65Cu and ⁸⁰Se isotopes, and for the total photoneutron reaction σ(γ, Sn) = σ[(γ, 1n) + (γ, 2n) + …]. It is shown that noticeable deviations of the experimental cross sections from the evaluated values result from the unreliable sorting of neutrons between the channels with multiplicities 1 and 2.     

Ab initio calculation of the dipole moment of cyanamide

The He(I) photoelectron spectra of the isoelectronic series Fe(CO)₂(NO)₂, Co(CO)₃NO and Ni(CO)₄ are reported and interpreted by means of ab initio SCF-MO calculations. For the nitrosyl complexes it is found that ionization potentials calculated assuming Koopmans' theorem are seriously in error due to the considerably greater orbital relaxation accompanying ionization from metal than from NO valence orbitals. When such allowance is made for orbital relaxation by performing restricted Hartree-Fock (RHF) calculations on the ionic states, the experimental spectra are accurately reproduced and the observed similarity of the spectra of all three molecules is explained.     

磁瓶式光电子能谱和速度成像光电子能谱对APS-(A=C14H10,蒽)的研究:电子结构,APS·的自旋轨道耦合和APS-的自旋偶极态

Gaseous dibenzo-7-phosphanorbornadiene P-sulfide anions APS^-(A=C₁₄H₁₀ or anthracene) were generated via electrospray ionization, and characterized by magnetic-bottle photoelectron spectroscopy, velocity-map imaging (VMI) photoelectron spectroscopy, and quantum chemical calculations. The electron affinity (EA) and spin-orbit (SO) splitting of the APS^· radical are determined from the photoelectron spectra and Franck-Condon factor simulations to be EA=(2.62±0.05) eV and SO splitting=(43±7) meV. VMI photoelectron images show strong and sharp peaks near the detachment threshold with an identical electron kinetic energy (eKE) of 17.9 meV at three different detachment wavelengths, which are therefore assigned to autodetachment from dipole-bound anion states. The B3LYP/6-31++G(d,p) calculations indicate APS^· has a dipole moment of 3.31 Debye, large enough to support a dipole-bound electron.     

Electron spectroscopy using excited atoms and photons: II. Penning ionization of diatomic molecules

A high resolution electrostatic electron analyser has been used to study Penning ionization electron spectra of H₂, HD, D₂, N₂, CO, NO and O₂ using helium metastable atoms (2¹S, 2³S). Results for H₂, N₂ and CO are in good agreement with other work. New data are presented for HD, D₂, NO and O₂. The Penning electron spectra are also compared to the 584 Å photoelectron spectra obtained in the same apparatus. The relative vibrational intensifies for the given electronic bands indicate that in most cases Franck—Condon factors for Penning ionization and photoionization are very similar. However for the O₂⁺(X²Π_g) band, the (2³S) Penning electron and photoelectron spectra show significant differences in the Franck—Condon envelopes This perturbation of the envelope for the Penning ionization may be explained by a competing autoionization process. The relative electronic transition probabilities are in many cases found to be different for Penning ionization and photoionization.     

The photoelectron spectra of some iron tricarbonyl complexes of 4π-electron donor ligands

The photoelectron spectra of eighteen compounds which are dienes or diene—iron tricarbonyl complexes have been investigated. A comparison of the photoelectron spectra of the dienes and corresponding iron carbonyl complexes has yielded the values of the perturbation energies for the two π orbitals of the diene moiety caused by interaction with Fe(CO)₃. These perturbation energies are relatively constant (Δπ₁ = 0.89 ± 0.07 eV, Δπ₂ = 0.22 ± 0.06 eV) throughout the series. They have been employed to estimate the π ionization energies of the organic transient species cyclobutadiene (8.29 and 11.95 eV) and trimethylenemethane (8.36 and 11.79 eV), two novel molecules which have not been studied successfully by photoelectron spectroscopy to date.     

Reliable cross sections of partial photoneutron reactions on 188,189Os isotopes free of neutron multiplicity sorting problems

Experimental data on the cross sections of partial photoneutron reactions, obtained for ^188,189Os isotopes using quasimonoenergetic annihilation photon beams and neutron multiplicity sorting method, are analyzed. Using special criteria (transition multiplicity functions F _i = σ(γ, in)/σ(γ, xn), the ratios of the cross section of the corresponding partial reaction to the total neutron yield reaction’s cross section σ(γ, xn) = σ(γ, 1n)+ 2σ(γ, 2n) + 3σ(γ, 3n) free of the problems associated with experimental neutron multiplicity sorting), it is demonstrated that the data contain significant systematic errors. New data are evaluated for cross sections of partial photoneutron reactions (γ, 1n), (γ, 2n), (γ, 3n) and total photoneutron reaction (γ, sn) for ^188,189Os isotopes within an experimental-theoretical approach proposed earlier. It is shown that the significant systematic errors in the experimental cross sections of partial reactions can be attributed to the ambiguity of the relation between the photoneutrons’ multiplicity and their kinetic energy.     

About the effect of a bound state on ionization cross sections in ion-atom collisions

The cross sections σ_nl for ionization of hydrogen-like ions by heavy particles from the nl = 3s, 3p, 3d, 4s and 4p states have been calculated in the Born approximation. A structure in the energy dependence of the cross sections σ_nl and the ratios of the cross sections σ_nl/σ_1s due to the radial wave function of a bound state is discussed.     

Rb(62D)原子与基态Rb原子,H2分子碰撞转移截面

本文用荧光法测量Rb(6²D)原子与基态Rb原子,H₂分子碰撞转移截面。结果表明:Rb(6²D)-Rb(5²s)转移截面为σ_fs=67×10^-14cm²,σ_tr=4.3×10^-14cm²,Rb(6²D)—H₂转移截面为σ_fs 关键词：     

Calculation of the cross sections for the photoionization of H2 and D2 into different vibrational states of the ion

The dependence of the electronic transition moment on the internuclear distance is explicitly taken into account in the calculation of the photoionization cross section. Thus, the partial ionization cross sections for producing different vibrational states of the residual ion are obtained without invoking the Franck-Condon factor approximation. The exact electrostatic potential of H₂⁺, as well as the two-center Coulomb field, is used in the evaluation of the continuum wave function. The result can explain fairly well the ratios of the partial cross sections measured at 584 Å. The effect of the polarization of H₂⁺ due to the departing photoelectron is also studied and found to be small as far as the relative cross section is concerned. The total photoionization cross sections of H₂ and D₂ are compared with previous results obtained by other authors.     

Odd autoionizing 2p<Subscript>1/2</Subscript><Superscript>5</Superscript>n(s<Superscript>′</Superscript>/d<Superscript>′</Superscript>) resonances of Ne excited from the 2p<Superscript>5</Superscript>3p[K]<Subscript>J</Subscript> states

Absolute photoionization cross sections for Ne atoms in the excited levels (Paschen notation ) were calculated at near threshold energies within the configuration interaction Pauli-Fock approach including core polarization. The computed spectra and the lineshape parameters of the odd parity 2p_1/2 ⁵ns^′/d^′ autoionizing resonances are found to be in good agreement with high resolution laser spectroscopic results. Guided by the theoretical results, improved analyses of the measured spectra by superimposed Fano-type profiles were achieved. Theoretical predictions are presented for resonances which have not yet been studied experimentally. In addition, we report the absolute partial photoionization cross sections for the ²P_3/2 and ²P_1/2 channel at photoelectron energies up to 7 eV. Except for the highest lying 2p₁(¹S₀) level, these cross sections monotonically decrease with energy (as reported earlier in single-electron calculations for the Ne(2p⁵3p) configuration) with branching ratios which essentially reflect the core composition of the 2p_x levels. For the 2p₁ level the resonance structure and the partial cross sections are strongly influenced by a Cooper-Seaton minimum in the d_3/2 ^′ channel,located just above the ²P_1/2 ionization limit.