The electronic states of carbon monofluoride: Low-lying valence states

Multiconfiguration Hartree-Fock calculations are reported on the low-lying valence states, the X²Π, ⁴Σ^?, B²Δ, and ²Σ^± states, of carbon monofluoride. The wavefunctions describe dissociation of the molecule to the correct atomic limits and take account of the atomic 2s-2p near-degeneracy effect. For the ground state the calculations give (with experimental values in parentheses): a bond length of 1.286 Å (1.2667 Å), a fundamental frequency of 1292 cm^?1 (1308 cm¹), and a dissociation energy of 3.93 eV (5.5 ± 0.1 eV). A ⁴Σ^? state arising from the $\text{C}\text{(}{}^3\text{P) +}\text{F}\text{(}{}^2\text{P)}$ manifold is calculated to lie just 2.66 eV above the ground state. The B²Δ state, calculated adiabatic excitation energy 6.59 eV (6.12 eV), is found to dissociate to $\text{C}\text{(}{}^1\text{D) +}\text{F}\text{(}{}^2\text{P)}$ via a potential maximum. Calculations are also reported on a repulsive ²Δ state arising from ground state atoms.     

The electronic states of silicon monofluoride: Rydberg states

SCF-CI calculations are reported for the Rydberg states converging to the ground state of the SiF⁺ ion. The adjustment between the observed and calculated values for the energy of the first Rydberg B²Σ⁺ state has allowed the characterization of 15 observed ²Σ⁺ and ²Π Rydberg states. A value of 58960 cm^?1 has been obtained for the ionization potential of SiF. The A²Σ⁺ state appears to be a valence state with some Rydberg character.     

The electronic states of carbon monofluoride: Rydberg states

Hartree-Fock and multiconfiguration Hartree-Fock calculations are reported on some low-lying Rydberg states of CF and the ground state of CF⁺. For the CF⁺ ground state, ¹Σ⁺, the calculations give a bond length of 1.55 Å, a fundamental frequency of 1821 cm^?1, and a dissociation energy of 6.9 eV. Many interactions between the valence and Rydberg state manifolds are revealed. Also a strong mixing of the 3dσ and 4sσ components due to an accidental degeneracy is described.     

Low-lying electronic states of aluminum monoiodide

High-level ab initio calculations of aluminum monoiodide(AlI) molecule are performed by utilizing the multireference configuration interaction plus Davidson correction(MRCI+Q) method. The core-valence correlation(CV) and spin–orbit coupling(SOC) effect are considered. The adiabatic potential energy curves(PECs) of a total of 13 Λ–S states and 24 ? states are computed. The spectroscopic constants of bound states are determined, which are in accordance with the results of the available experimental and theoretical studies. The interactions between the Λ–S states are analyzed with the aid of the spin–orbit matrix elements. Finally, the transition properties including transition dipole moment(TDM),Frank–Condon factors(FCF) and radiative lifetime are obtained based on the computed PEC. Our study sheds light on the electronic structure and spectroscopy of low-lying electronic states of the AlI molecule.     

BO: Low-lying electronic states obtained by configuration-interaction studies

Configuration-interaction studies were performed on low-lying ²Σ⁺, ²Σ⁻, ²Π, ²Δ, ⁴Σ⁺, ⁴Σ⁻, ⁴Π, and ⁴Δ states of BO. Sixteen stable states have been found, among them four 3s_B Rydberg states. Spectroscopic constants are compared with those of the four observed states and with theoretical results obtained by others. Particular attention is given to the observed perturbations in the C²Π state, which can be explained by interaction with 1²Δ, 1²Σ⁻, 3²Σ⁺, and other states. Comparison with isoelectronic molecules CN and CO⁺ reveals many similarities.     

Spectroscopic constants of the known electronic states of lead monofluoride

Based on measurements made by mass-resolved 1 + 1′ + 1″ resonance-enhanced multiphoton ionization spectroscopy, we have determined new molecular constants describing the rotational and fine structure levels of the B, D, E, and F states of the most abundant isotopic variant ²⁰⁸Pb¹⁹F, and we summarize the spectroscopic constants for all the know electronic states of the radical. Many spectroscopic constants for the isotopologues ²⁰⁶Pb¹⁹F and ²⁰⁷Pb¹⁹F have also been determined. The symmetry of the D-state is found to be ²Π_1/2, and the F-state is found to be an Ω = 3/2 state.     

Low-lying valence and Rydberg states of NS, obtained by configuration-interaction studies

Using double-ζ plus polarization basis sets with diffuse s and p functions on N and S, configuration-interaction calculations were carried out for low-lying valence and Rydberg states of NS. In general, there is good agreement with experimentally obtained spectroscopic constants, and with theoretical results obtained by other groups. The avoided crossing of 2²Σ⁺(C) and 3²Σ⁺(I), and the reported predissociation from low vibrational levels of the C state received particular attention.     

Low-lying electronic states of CuN calculated by MRCI method

The high accuracy ab initio calculation method of multi-reference configuration interaction(MRCI) is used to compute the low-lying eight electronic states of CuN.The potential energy curves(PECs) of the X~3∑~-,1~3Π,2~3∑~-,1~3△,1~1△,1~1∑~-,1~1Π,and ~5∑~- in a range of R=0.1 nm-0.5 nm are obtained and they are goodly asymptotes to the Cu(~2S_g) + N(~4S_u) and Cu(~2S_g)+N(~2D_u) dissociation limits.All the possible vibrational levels,rotational constants,and spectral constants for the six bound states of X~3∑~-,1~3Π,2~3∑~-,1~1△,1~1∑~-,and 1~1 Π are obtained by solving the radial Schrdinger equation of nuclear motion with the Le Roy provided Level 8.0 program.Also the transition dipole moments from the ground state X~3∑~- to the excited states 1~3Π and 2~3∑~- are calculated and the result indicates that the 2~3∑-X~3∑ transition has a much higher transition dipole moment than the 1~3Π-X~3∑~- transition even though the l~3Π state is much lower in energy than the 2~3∑~- state.     

Low-lying electronic states of LiF molecule with inner electrons correlation

The potential energy curves and dipole moments of the low-lying electronic states of LiF molecule are performed by using highly accurate multi-reference configuration interaction with Awcv5z basis sets. 1s, the inner shell of Li is considered as the closed orbit, which is used to characterise the spectroscopic properties of a manifold of singlet and triplet states. 16 electronic states correlate with two lowest dissociation channels Li(²S)+F(²P) and Li(²P)+F(²P) are investigated. Spectroscopic parameters of the ground state X¹Σ⁺ have been evaluated and critically compared with the available experimental values and the other theoretical data. However, spectroscopic parameters of 1³Π, 1¹Δ, 1¹Σ^?, 1¹Π, 1³Σ⁺, 2³Σ⁺, 1³Δ, 1³Σ^?, 2³Π, 2¹Π, 3³Π, 3¹Π and 3³Σ⁺ states are studied for the first time. These 13 excited states have shallow potential wells, and the dispersion coefficients of these excited states are predicted. In additional, oscillator strengths of excited states at equilibrium distances are also predicted.     

Low-dimensional electronic states at silicon surfaces

Self-assembled atomic chains can be triggered at stepped Si(111) surfaces by adding sub-monolayer amounts of metals, such as gold, silver, platinum, alkali metals, alkaline earths, and rare earths. A common feature of all these structures is the honeycomb chain, a graphitic strip of Si atoms at the step edge that is lattice matched in the direction parallel to the edge but completely mismatched perpendicular to it. This honeycomb chain drives one-dimensional surface reconstructions even on the flat Si(111) surface, breaking its three-fold symmetry. Particularly interesting are metallic chain structures, such as those induced by gold. The Au atoms are locked rigidly to the Si substrate but the electrons near the Fermi level completely decouple from the substrate because they lie in the band gap of silicon. The electronic structure of one-dimensional electrons is predicted to be qualitatively different from that of higher dimensions, since electrons cannot avoid each other when moving along the same line. The single-electron picture has to be abandoned, making way for collective excitations, such as spinons and holons, where the spins and charges of electrons become separated. Although such excitations have yet to be confirmed definitively, the band structure seen in angle-resoled photoemission exhibits a variety of unusual features, such as a fractional electron count and a doublet of nearly half-filled bands. Chains of tunable spins can be created with rare earths. The dimensionality can be controlled by adjusting the step spacing with intra- and inter-chain coupling ratios from 10:1 to >70:1. Thus, metal-induced chain structures on stepped silicon provide a versatile class of low-dimensional materials for approaching the one-dimensional limit and exploring the exotic electronic states predicted for one dimension. PACS 73.20.At; 71.10.Pm; 79.60.Jv; 81.07.Vb; 73.21.Hb     

Low-lying electronic states of BeH+ with the effect of inner electrons

The potential energy curves of the low-lying electronic states of BeH⁺ molecular ion are performed by using highly accurate multi-reference configuration interaction with AV5Z basis sets for H atom and ACV5Z basis set for Be atom, 1s inner shell of Be is considered as the core orbit and the active orbit, respectively, which are used to characterise the spectroscopic properties of a manifold of singlet and triplet states. Fourteen electronic states correlated with eight dissociation channels are investigated, we have found that the a³Σ⁺ and c³Σ⁺ both are bound states, the 3³Σ⁺ possesses double wells, and the C¹Σ⁺, 3³Σ⁺, 2³Π, 2¹Π, 1¹Δ, 1³Δ, 2³Δ and 2¹Δ states are studied for the first time. Transition dipole moment, Franck–Condon factors q_υ′υ^″ and Einstein coefficients A_υ′υ^″ for A¹Σ⁺–X¹Σ⁺, 2¹Π–B¹Π, c³Σ⁺–a³Σ⁺ and b³Π–a³Σ⁺ systems have been calculated. Radiative lifetime of A¹Σ⁺–X¹Σ⁺ band system has also been determined.     

Penetration of electronic states from silicon substrate into silicon oxide

The depth profiling of O 1s energy loss in silicon oxide near the SiO₂/Si interface was performed using extremely small probing depth. As a result, the energy loss of O 1s photoelectrons with threshold energy of 3.5 eV was found. This value of 3.5 eV is much smaller than the SiO₂ bandgap of 9.0 eV, but quite close to direct interband transition at Γ point in energy band structure of silicon. This can be explained by considering the penetration of electronic states from silicon substrate into silicon oxide up to 0.6 nm from the interface. In addition, the penetrating depth is larger than the thickness of the compositional transition layer.     

The electronic structures of the core and valence ion states of metal oxides

SCF-Xα SW MO calculations on metal core ion hole states and X-ray emission (XES) and X-ray photoelectron (XPS) transition states of the non- transition metal oxidic clusters MgO₆^10?, AlO₄^5? and SiO₄^4? show relative valence orbital energies to be virtually unaffected by the creation of valence orbital or metal core orbital holes. Accordingly, valence orbital energies derived from XPS and XES are directly comparable and may be correlated to generate empirical MO diagrams. In addition, charge relaxation about the metal core hole is small and valence orbital compositions are little changed in the core hole state. On the other hand, for the transition metal oxidic clusters FeO₆^10?, CrO₆^9? and TiO₆^8? relative valence orbital energies are sharply changed by a metal core orbital or crystal field orbital hole, the energy lowering of an orbital increasing with its degree of metal character. Consequently O 2p nonbonding → M 3d-O 2p antibonding (crystal field) energies are reduced, while M 3d bonding → O 2p nonbonding and M 3d-O 2p antibonding → M 4s,p-O 2p antibonding (conduction band) energies increase. Charge relaxation about the core hole is virtually complete in the transition metal oxides and substantial changes are observed in the composition of those valence orbitals with appreciable M 3d character. This change in composition is greater for e _g than for t_2g orbitals and increases as the separation of the e_g crystal field (CF) orbitals and the O 2p nonbonding orbital set decreases. Based on the hole state MO diagrams the higher energy XPS satellite in TiO₂ (at about 13 eV) is assigned to a valence → conduction band transition. The UV PES satellites at 8.2 eV in Cr₂O₃ and 9.3 eV in FeO are tentatively assigned to similar transitions to conduction band orbitals, although the closeness in energy of the crystal field and O 2p nonbonding orbitals in the valence orbital hole state prevents a definite assignment on energy criteria alone. However the calculations do clearly show that charge transfer transitions of the e_g bonding → e_g crystal field orbital type would generally occur at lower energy than is consistent with observed satellite structure.A core electron hole has little effect upon relative orbital energies and is only slightly neutralized by valence electron redistribution for MgO and SiO₂. For the transition metal oxides a core hole lowers the relative energies of M3d containing orbitals by large amounts, reducing O → M charge transfer and increasing M 3d crystal field → conduction band energies. Large and sometimes overcomplete neutralization of the core hole is observed, increasing from CrO₆^9? to FeO₆^10? to TiO₆^8?. as the O → M charge transfer energy declines.High energy XPS satellites in TiO₂ may be assigned to O 2p nonbonding → conduction band transitions while lower energy UV PES satellites in FeO and Cr₂O₃ arise from crystal field or O 2p nonbonding → conduction band excitations. Our “shake-up” assignment for FeO₆^10?, CrO₆^9? and TiO₆^8? are less than definitive because no procedure has yet been developed to calculate “shake-up” intensities resulting from transitions of the type described. However the results do allow a critical evaluation of earlier qualitative predictions of core and valence hole effects. First, we find that the comparison of hole or valence state ionic systems with equilibrium distance systems of higher nuclear and/or cation charge (e.g. the comparison of the FeO₆^10? Fe 2p core hole state to Co₃O₄) is dangerous. For example, larger MO distances in the ion states substantially reduce crystal field splittings. Second, core and CF orbital holes sharply reduce O → M charge transfer energies, giving 2e_g → 3e_g energy separations which are generally too small to match observed satellite energies. Third, highest occupied CF-conduction band energies are only about 4–5 eV in the ground states, but increase to about 7–11 eV in the core and valence hole states of the transition metal oxides studied. The energetic arguments presented thus support the idea of CF and/or O 2p nonbonding → conduction band excitations as assignments for “shake-up” satellites, at least in oxides of metals near the beginning of the transition series.     

一氟化碳电子态的光谱性质和预解离机理的理论研究

采用考虑Davidson修正的内收缩多参考组态相互作用(icMRCI+Q)方法结合相关一致基组aug-cc-pV5Z和aug-cc-pV6Z首次计算了一氟化碳(CF)11个Λ-S 态(X²Π , a⁴Σ^-, A²Σ⁺, B²Δ, 1⁴Π, 1²Σ^-, 2⁴Π, 1^{4}Δ , 1⁴Σ⁺, 2²Σ^-和2⁴Σ^-) 所产生的25个Ω 态的势能曲线. 计算中考虑了旋轨耦合效应、核价相关和标量相对论修正以及将参考能和相关能分别外推至完全基组极限. 基于得到的势能曲线, 获得了束缚和准束缚的Λ-S态和Ω 态的光谱常数, 与已有的实验结果非常符合. 分析了束缚和准束缚的Λ-S态在各自平衡核间距R_e处的主要电子组态. 由于1⁴Π 和2⁴Π态的避免交叉, 发现准束缚态2⁴Π. 由Λ-S态势能曲线的交叉现象, 借助于计算的旋轨耦合矩阵元, 分析了a⁴Σ^-和B²Δ 态的预解离机理. 计算了25个Ω 态的离解关系, 给出了它们的离解极限. 最后研究了A²Σ⁺-X²Π 跃迁特性, 本文计算得到的A²Σ⁺-X²Π跃迁的Frank-Condon 因子和辐射寿命与已有实验值也符合得非常好.     

Low-lying states of F2 +

Calculated potential energy curves for the 13 lowest electronic states of F₂ ⁺ are presented. Nine of the potential curves are found to possess substantial binding energies, while two others also display shallow, stable minima. The ordering, binding energies, relative equilibrium separations and vibrational frequencies of these curves should be of utility in helping to assign the large number of observed vibration-rotation lines in the electronic emission spectrum of F₂ ⁺. The calculated curves are in reasonable agreement with the available data on the two experimentally observed states.     

Adsorption and valence electronic states of nitric oxide on metal surfaces

Among fundamental diatomic molecules, the adsorption of carbon monoxide (CO) and nitric oxide (NO) on metal surfaces has been a subject of intensive research in the surface science community, partly owing to its relevance to heterogeneous catalysis used for environmental control. Compared to the rather well-defined adsorption mechanism of CO, that of NO is less understood because the adsorption results in much more complex reactions. The complexity is ascribed to the open-shell structure of valence electrons, making the molecule readily interact with the metal surface itself as well as with co-adsorbed molecules. Furthermore, the interaction crucially depends on the local structure of the surface. Therefore, to elucidate the interaction at the molecular scale, it is essential to study the valence state as well as the bonding geometry for individual NO molecules placed in a well-defined environment on the surface. Scanning tunneling microscopy (STM) is suitable for this purpose. In this review, we summarize the knowledge about the interaction of NO with metal surfaces, mainly focused on the valence electronic states, followed by recent studies using STM and atomic force microscopy (AFM) at the level of individual molecules.     

Low-lying states in112In

Low-lying states below 500 keV excitation in¹¹²In have been investigated via the¹¹²Cd(p, nγ) reaction. New levels have been established atE ^x=206.5keV and 456.1 keV from the measuredγ-ray excitation functions,γ?γ coincidences and the precision measurements of the (p, n) threshold energy of the ground state and of the 206.5 keV state of¹¹²In. Spins and parities of the 206.5 keV state (2⁺) and the 456.1 keV state (3⁺) and multipolarities and mixing ratios of the deexcitationγ-rays have been determined from the angular distributions and linear polarizations of the deexcitation γ-rays as well as the excitation functions of the residual levels. Possible configurations of the newly-found levels are discussed. Half-lives of two states have been remeasured:T _1/2=15.2±0.1 min for the ground state andT _1/2=20.9±0.1 min for the 156.4 keV (4⁺) state. The ground stateQ-value for the¹¹²Cd(p, n)¹¹² In reaction has been measured to be ?3.376±0.006 MeV.     

Low-lying vibrational states of145,147,149Nd

The fragmented neutron states in^145,147,149Nd detected through¹⁴⁴Nd(d, p) and^148,150Nd(d, t) reactions can be accounted for in terms of quasiparticles coupled with anharmonic vibrator model. The wave functions, obtained from diagonalisation of the Hamiltonian matrices are utilised to calculate B(E2), B(M1) and branching ratios in^145,147Nd. The calculated results are discussed in the light of the recent experimental findings.