Multi-centre bonding in the carboranes: An ab initio and semi-empirical molecular orbital study

The electronic structures of the closo-carboranes 1,5-C₂B₃H₅, 1,2-C₂B₄H₆, 1,6-C₂B₄H₆ and 2,4-C₂B₅H₇ are discussed using the results of ab initio calculations in both minimal and extended bases of contracted gaussian type functions fitted to Slater type orbitals. A comparison is made with the results from semi-empirical INDO calculations, and the bonding in 1,7-C₂B₆H₈, 1,6-C₂B₇H₉, 5,9-C₂B₇H₁₃, 1,6-C₂B₈H₁₀ and the 1,2-, 1,7- and 1,12-isomers of C₂B₁₀H₁₂ studied using the latter method.

The delocalized molecular orbitals from both the ab initio and semi-empirical calculations are transformed to localized orbitals to provide an analysis of the multi-centre bonding in these electron-deficient molecules, which requires no prior assumptions about the nature of the bonding.     

Geometric and electronic structures of B12C6N6 fullerene

An electron deficient fullerene B₁₂C₆N₆ is studied by using ab initio calculations. The structure is generated by replacing N with C in the B₁₂N₁₂ cage to ensure only B–C and B–N bonds are formed. All the possible isomers are optimized and the low energy structures are determined. C and N atoms in the low energy isomers are inclined to segregate and form B₂C₂ and B₂N₂ squares. Natural bond analysis shows that the atomic orbitals of B, C and N in this cage hybrid approximately in sp^2.3 and then form B–C and B–N bonds. The 2p orbitals perpendicular to the cage surface are partially occupied and the molecular orbitals formed by these orbitals are highly delocalized. The natural charge on N is about −1.17 in both B₁₂N₁₂ and B₁₂C₆N₆, and the charge on C is −0.72 to −0.60. The molecular orbital compositions show that the B–N bonds are the same in B₁₂N₁₂ and B₁₂C₆N₆, and the B–C bonds possess stronger covalent character. The HOMO of B₁₂C₆N₆ is formed by 2p of B and C, and the LUMO is formed by 2p of C. The energy gap of C₂₄, B₁₂N₁₂ and B₁₂C₆N₆ is 2.52, 6.84 and 3.22 eV, respectively.     

Approximate SCF calculations on the [Mn(H2O)6]2+ complex with a minimal basis set

In the restricted Hartree-Fock scheme approximate SCF-LCAO calculations have been performed for the [Mn(H₂O)]₆ ²⁺ complex using a minimal basis set consisting of nine Slater-type orbitals of the manganese ion and four Slater-type orbitals of the water molecule. The 1s, 2s and 2p orbitals of the manganese ion and the 1s orbital of the oxygen atom are treated as frozen core orbitals. In evaluating the different parts of the Hartree-Fock operators we used a two-centre approximation for the multicentre integrals. A new aspect of the calculations is the use of the Hartree-Fock orbital energies of the free water molecule as a first approximation for the corresponding orbital energies of the complex. The calculations have been done for the ground states and six excited states of the complex with symmetry T _h and also for the ground states of two distorted complexes. From the resulting eigenvectors we calculated the hyperfine interaction of the valence electrons of the central ion with the protons of the water molecules for three different geometries. The excited states give two different ways of finding values of 10 Dq and the Racah parameters B and C. The results are encouraging.     

The electronic structure of 1,2-PCB10H11 molecular films: a precursor to a novel semiconductor

The band gaps and electronic structure of undoped films of molecular icosahedra of closo-1-phospha-2-carbadodecaborane (1,2-PCB₁₀H₁₁) are reported. 1,2-PCB₁₀H₁₁ adsorbs on Au and Ag substrates to generate molecular thin films with the Fermi level (chemical potential) placed closer to the lowest unoccupied molecular orbital than has been observed with closo-1,2-dicarbadodecaborane (1,2-C₂B₁₀H₁₂, orthocarborane) adsorbed on Co, Cu or Ag. Both 1,2-PCB₁₀H₁₁ and 1,2-C₂B₁₀H₁₂ molecular films exhibit an unoccupied molecular defect state above the Fermi level. The vibrational modes, observed in infra-red absorption, are close to the values expected for the isolated 1,2-PCB₁₀H₁₁ molecule. Consistent with the placement of the Fermi level in the molecular films, fabrication of heterojunction diodes from partially dehydrogenated 1,2-PCB₁₀H₁₁ indicates that the resultant PCB₁₀H_x semiconductor film is more n-type than the corresponding boron carbide semiconductor formed from 1,2-C₂B₁₀H₁₂, orthocarborane. PACS 68.43.-h; 73.20.Hb; 31.15.Ct; 79.60.-i     

Fourier analysis of spherically averaged momentum densities for some gaseous molecules

The spherically averaged autocorrelation function,B(r), of the position-space wavefunction, ψ($\text{r}$), is calculated by numerical Fourier transformation from spherically averaged momentum densities, ?(p), obtained from either theoretical wavefunctions or (e,2e) electron-impact ionization experiments. Inspection of B(r) for the π molecular orbitals of C₄ H₆ establishes that autocorrelation function differences, ΔB(r), can be qualitatively related to bond lengths and numbers of bonding interactions. Differences between B(r) functions obtained from different approximate wavefunctions for a given orbital can be qualitatively understood in terms of wavefunction difference,Δψ($\text{r}$), maps for these orbitals. Comparison of the B(r) function for the 1a_u orbital of C₄H₆ obtained from (e,2e) momentum densities with that obtained from an ab initio SCF MO wavefunction shows differences consistent with expected correlation effects. Thus, B(r) appears to be a useful quantity for relating spherically averaged momentum distributions to position-space wavefunction differences.     

First-principles study on the structural and electronic properties of LiB and its hydrides (Li2BnHn, n=5, 8, 12, LiBH4)

Structural, electronic and vibrating properties of LiB and its hydrides (Li₂B_nH_n, n=5, 8, 12, LiBH₄) were calculated by the first-principles using density functional theory in its generalized gradient approximation. The calculated results are in good agreement with experimental studies. The deviation between theory and experimental results are also discussed. With the increasing of H atoms in range of 5-12, the band gap energy increases and the width of the conduction band decreases. Comparing with LiB, the band gap of LiBH₄ is broadened, which indicates the enhancement of Li-B and Li-H bond strength. Valence electrons mainly transfer from Li atoms to B and H atoms. As a result, Li atoms are thought to be partially ionized as Li⁺ cations. There is little contribution of Li orbital to the occupied states, resulting in Li-H and Li-B bond exhibiting an ionic nature, and B-H bond showing a covalent nature.     

The UV spectra of tetraborane(10) and pentaborane(9) in the gas phase

The UV spectra of gaseous B₄H₁₀ and B₅H₉ are measured down to about 187 nm and are compared to the already known spectrum of B₂H₆. All the spectra are completely continuous, which suggests repulsive excited states. With respect to B₂H₆ absorption, that of B₄H₁₀ appears shifted to the blue, while that of B₅H₉ appears shifted to the red.     

Spectral properties of chlorines and electron transfer with their participation in the photosynthetic reaction center of photosystem II

Structural factors that provide localization of excited states and determine the properties of primary donor and acceptor of electron in the reaction center of photosystem II (PSII RC) are studied. The results of calculations using stationary and time-dependent density functional theory indicate an important role of protein environments of chlorophylls P_A, P_B, B_A, and B_B and pheophytins H_A and H_B in the area with a radius of no greater than ≤10 Å in the formation of excitonic states of PSII RC. When the neighboring elements are taken into account, the wavelength of long-wavelength Q _y transition of chlorophyll molecules is varied by about 10 nm. The effect is less developed for pheophytin molecules (Δλ ? 2 nm). The following elements strongly affect energy of the transition: His^A198 and His^D197 amino-acid residues that serve as ligands of magnesium atoms affect P_A and P_B, respectively; Met^A183 affects P_A; Met^A172 and Met^D198 affect B_A; water molecules that are located above the planes of the B_A and B_B macrocycles form H bonds with carbonyl groups; and phytol chains of P_A and P_B affect B_A, B_B, H_A, and H_B. The analysis of excitonic states, mutual positions of molecular orbitals of electron donors and acceptors, and matrix elements of electron transfer reaction shows that (i) charge separation between B_A and H_A and P_B and B_A is possible in the active A branch of cofactors of PSII RC and (ii) electron transfer is blocked at the B_B - H_B fragment in inactive B branch of PSII RC.     

Direct minimization of the energy functional in the LCAO-MO density matrix formalism

The previously proposed method of direct energy minimization by a gradient approach is here applied to the separated electronic pair functions (strongly orthogonal geminals). The minimization of the energy is achieved by an alternate iterative procedure in which the geminal occupation coefficients are optimized making each geminal self-consistent in the field of the others and the orbital forms are directly optimized using a sequence of orthogonal transformations of an arbitrary orthonormal basis set. The method is tested on H₂, He₂, LiH, NH₃ and H₂O molecules.

Possible generalizations of the formalism to other geminal models are briefly presented.     

Characterizations of B and N heteroatoms as substitutional doping on structure,stability, and aromaticity of novel heterofullerenes evolved from the smallest fullerene cage C20: a density functional theory perspective

The structural stabilities and electronic properties of C₂₀ fullerene and some its incorporated boron and nitrogen derivatives are probed at B3LYP/AUG‐cc‐pVTZ level of theory. According to density functional theory results, the topology of inserted B or N heteroatoms in [20]‐fullerene perturbs strongly the stability, energy, geometry, charge, polarity, nucleus‐independent chemical shifts, aromaticity, and highest‐occupied molecular orbital and lowest‐unoccupied molecular orbital (HOMO–LUMO) gap of the resulting heterofullerenes. Vibrational frequency (υ_min) calculations show that except N₁₀C₁₀, all other B_bN_nC_{20‐(b + n)} heterofullerenes with b, and n = 0, 4, 5, 8, and 10 are true minima. The calculated band gaps (?E_HOMO–LUMO) of B₈C₁₂, and N₈C₁₂ (2.86 eV), show them the most stable heterofullerenes against electronic excitations. While 10 B substituting in equatorial position increase the conductivity of B₁₀C₁₀ through decreasing its band gaps, 10 N doping in equatorial position enhance stability of N₁₀C₁₀ against electronic excitations via increasing its band gaps. High natural bond orbital and Mulliken charge transfer on the surfaces of B atoms, especially B₅N₅C₁₀with five B–N bonds in the equatorial position, provokes further investigation on its possible application for hydrogen storage. Nucleus‐independent chemical shift values show that B₅N₅C₁₀ is the most aromatic species. The calculated heat of atomization per carbon (ΔH_at/C) of B₈C₁₂ shows it the most thermodynamic stable heterofullerenes of each. Copyright © 2016 John Wiley & Sons, Ltd.     

Photoelectron spectroscopy of some thiocyanates,isocyanates and isothiocyanates

Photoelectron spectra of some thiocyanates (RSCN, R = CH₃, C₂H₅, n-C₄H₉), isocyanates (RNCO, R = C₂H₅, n-C₄H₉) and isothiocyanates (RNCS, R = C₂H₅, n-C₄H₉) have been measured, to study interactions between nonbonding and π orbitals, mainly localized on the SCN, NCO or NCS fragments. The spectral interpretation of CH₃SCN is based on semiempirical CNDO/S calculations, sum-rule considerations, and intensity differences between He(I) and HE(II) spectra. For the larger molecules, comparison of the spectra is used as an aid in the interpretation. In a number of aromatic isocyanates (o?, m?, p-tolylisocyanate and m?, p-chlorophenylisocyanate), interactions between the isocyanate group and the highest occupied π and σ orbitals of the phenyl ring are studied. Spectra are assigned on the basis of semiempirical INDO/S calculations.     

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.     

High pressure phases of different tetraboranes

High pressure phases of boron hydrides B₄H₁₀, B₄H₈ and B₄H₆ and their stability against dissociation into H and smaller B–H units are reported. Structure predictions based on particle swarm optimization reveal that all the boron hydrides studied show a tendency to separate into smaller structural units at low pressure. Under high pressure, the three-dimensional network in all the stoichiometries selected seems to be the most favourable arrangement. A study of the dissociation of B₄H₁₀ reflects an affinity to dissociate into B₄H₈ and H₂ in all the studied pressure range. Nevertheless, B₄H₈ does not seem to segregate in the studied pressure range and B₄H₆ may dissociate at 150 GPa.     

Photoelectron spectra and electronic structure of boron acetylacetonates with organic substituents

Based on experimental data and theoretical results obtained by photoelectron spectroscopy and density functional theory, the electronic structure of the valence levels of boron diethyl acetylacetonate (C₂H₅)₂BAA, boron diphenyl acetylacetonate (C₆H₅)₂BAA, and 1,2-phenylene dioxyboron acetylacetonate C₆H₄O₂BAA is examined. For the compounds studied, in contrast to F₂BAA, a significant mixing of the π₃ MO of the chelate ring with the orbitals localized on the boron atom, as well as on the (C₂H₅)₂, and (C₆H₅)₂ fragments, is revealed. The C₆H₄O₂BAA complex is demonstrated to have MOs mainly localized on the oxygen atoms of the C₆H₄O₂ fragment. It is shown that the calculated results closely reproduce the experimental sequences of energy levels and the energy intervals between the ionized states of the complex.     

Photoelectron spectroscopic assignment of symmetry to the ground state and first excited state of the 1,4-cyclohexadiene radical cation

The empirical correlation of the photoelectron spectra of 1,4-cyclohexadiene (molecule 4), 1, 4, 5, 8-tetrahydronaphthalene (molecule 5), 1, 4, 5, 6, 9, 1 0-hexahydroanthracene (molecule 6), and 1, 4, 5, 6, 7, 10, 11, 12-octahydronaphthacene (molecules 6) proves that the electronic ground state of these molecules is ²B_1u, assuming that they have D_2h symmetry. In particular this confirms previous predictions for 1,4-cyclohexadiene (molecule 4), for which the “inverted” orbital sequence 2b_1u(π) above lb_3g(π) had been proposed under the assumption that hyperconjugative “through-bond” interaction dominates the “through-space” interaction of the two semi-localized π-orbitals.     

Noncanonical localized orbitals and chemisorption

A localization scheme is applied to the Hückel N-atom linear chain in the limit that the chain becomes semi-infinite. It is shown that eigenvalues which arise from the localization procedure serve to separate a set of orbitals localized near the surface from a set of bulk orbitals. The effect of localization on the binding energy of an adatom is also reported where the adatom is assumed to be identical to the bulk atoms. Approximate binding energies are computed by taking combinations of the adatom orbital plus localized orbitals. Agreement to within 10% with the exact energy is found for the case of localization to two end atoms.     

Isotope effect and cluster size dependence for water and hydrated hydrogen halide clusters: multi-component molecular orbital approach

In order to explore the proton/deuteron (H/D) isotope effect on the structures, wavefunctions, and size dependence of water clusters, both electronic and nuclear wavefunctions are determined simultaneously. The optimized centres and the exponents for the nuclear orbitals indicate the Ubbelohde effect, i.e. the deuteron has weaker hydrogen bonding than the proton. Calculations are made also of hydrogen halide water clusters, Such as HF(H₂O)_n, HB_r(H₂O)_n, (n = 0–4), and their deuterated species. Only the hydrogen transferred ring structure is optimized for the protonic HBr (H₂O)₃ cluster, while both the hydrogen transferred and the non-transferred structures are obtained for the deuterated DBr (H₂O)₃ cluster under the one-particle multi-component treatment. The proton in the HF molecule is localized more than those in the HCl and HBr molecules, and no hydrogen transferred structures are obtained for HF water clusters.     

Classical trajectory calculations for state-resolved Penning ionisation reactions of polycyclic aromatic hydrocarbon C10H8 in collision with He*(23S)

ABSTRACT

The reaction dynamics of Penning ionisation of a polycyclic aromatic hydrocarbon (PAH), naphthalene C₁₀H₈, in collision with the metastable He*(2³S) atom is studied by classical trajectory calculations using an approximate interaction potential energy surface between He* and the molecule, which is constructed based on ab initio calculations for the isovalent Li?+?C₁₀H₈ system. The ionisation width (rate) around the molecular surface are obtained from overlap integrals of the He 1s orbital and the molecular orbital. The calculated collision energy dependences of partial Penning ionisation cross sections (CEDPICS) in the range 50–500?meV at 300?K have reproduced the experimental results semi-quantitatively. The opacity functions, which represent the reaction probability with respect to the impact parameter b, are discussed in connection with collision energy, interaction with He* and the exterior electron density of molecular orbitals. They indicate that the collisional ionisations of C₁₀H₈ can be classified into three types: π electron ionisations with negative collision energy dependences which are predominantly determined by attractive interaction with He*; σ orbitals ionisations of the hardcore type; σ orbital ionisations which reflect interaction potentials around CH bonds. The critical impact parameters b_c become larger with increasing collision energy due to the centrifugal barrier.     

Molecular-orbital models for the catalytic activity and selectivity of coordinatively unsaturated platinum surfaces and complexes

Electronic structures have been calculated for 5-, 6-, and 10-atom Pt clusters, as well as for a Pt(PH₃)₄ coordination complex, using the self-consistent-field X-alpha scattered-wave (SCF-Xα-SW) molecular-orbital technique. The 10-atom cluster models the local geometry of a flat, unreconstructed Pt(100) surface, while the 5- and 6-atom clusters show features of a stepped Pt surface. Pt(PH₃)₄ resembles the chemically similar homogeneous catalyst Pt(PPh₃)₄. Common to all these coordinatively unsaturated complexes are orbitals lying near or coinciding with the highest occupied molecular orbital (“Fermi level”) which show pronounced d lobes pointing directly into the vacuum. Under the hypothesis that these molecular orbitals are mainly responsible for the chemical activities of the above species, one can account for the relative similarities and differences in catalytic activity and selectivity displayed by unreconstructed Pt(100) surfaces, stepped Pt surfaces or particles, and isolated Pt(PPh₃)₄ coordination complexes. The relevance of these findings to catalyst-support interactions is also discussed. Finally, relativistic corrections to the electronic structures are calculated and their implications on catalytic properties discussed.     

清洁Si(111)表面电子结构的理论研究

本文报道在原子集团模型下用CNDO-SCF方法对清洁Si(111)表面电子结构的系统研究结果:(1)计算了表面上的净电荷分布、电荷转移以及局域在各原子轨道上的电荷;发现T₃⁰,T₃⁺和T₃^-式的表面悬挂键结构较难存在;表面原子趋于形成带有分数电荷的悬挂键,而实际上这些悬挂键彼此结合成弯键;表面原子及其悬挂键上有净电荷积累,且有很强的定域性和取向性。(2)计算了原子集团模型的静 关键词：