III: PROPERTIES OF COMPLEX SYSTEMS

The molecular structures, vibrational frequencies, dissociation energies and electron affinities of the Br₂/Br^? ₂, Br₂O/Br₂O^?, Br₂O₂/Br₂O^? ₂, Br₂O₃/Br₂O^? ₃, and Br₂O₄/Br₂O^? ₄ systems have been investigated using density functional theory (DFT) and hybrid Hartree-Fock/density functional theory. The methods used have been carefully calibrated against a comprehensive tabulation of experimental electron affinities, (Rienstra-Kiracofe, J. C., Tschumper, G. S., Shaefer, H. F., Nandi, S. and Ellison, G. B., 2002, Chem. Rev., 102, 231). Four different types of neutral/anion energetic difference are reported in this work: the adiabatic electron affinity (EA_ad), the zero-point corrected EA_ad (EA_zero), the vertical electron affinity (EA_vert), and the vertical detachment energy (VDE). The basis set used in this work is of double-zeta plus polarization quality with additional s- and p-type diffuse functions, and is denoted as DZP⁺⁺. The BHLYP method does well in reproducing the very limited experimental energetics, while the B3LYP method does well for the few known vibrational frequencies. The final predicted electron affinities with the BHLYP method are 3.41 eV (Br, experiment 3.36 eV), 3.02 eV (Br₂, experiment 2.6 ± 0.2 eV), 3.27 eV (Br₂O), 2.93 eV (Br₂O₂), 3.07 eV (Br₂O₃), and 2.54 eV (Br₂O₄). The global minimum structures for several of the larger dibromine oxides and their anions are unusual. For neutral Br₂O₂ the peroxide structure (BrOOBr) lies lowest, but for the anion a loosely bound C_s symmetry BrO-BrO^? structure lies lowest for the hybrid functionals, while a C₂ symmetry peroxide BrOOBr^? structure lies lowest for the pure functionals. Furthermore, the C₂ structures are found to exhibit an inverse symmetry breaking problem, and should be interpreted with caution. For neutral Br₂O₃, a chain structure Br-O₃-Br lies lowest, while the complex Br···O₃···Br^? lies lowest for the negative ion. For neutral Br₂O₄, a chain structure Br-O₄-Br lies lowest, while the complex BrO^?···BrO₃ lies lowest for the negative ion.     

Photoelectron Spectroscopy of Nickel, Palladium, and Platinum Oxide Anions

The 364-nm negative ion photoelectron spectra of XO and OXO molecules (X=Ni, Pd, and Pt) are reported. The spectra yield the electron affinities (EAs): EA(NiO)=1.455±0.005 eV; EA(PdO)=1.672±0.005 eV; EA(PtO)=2.172±0.005 eV; EA(ONiO)=3.043±0.005 eV; EA(OPdO)=3.086±0.005 eV; EA(OPtO)=2.677±0.005 eV. In addition, for the diatomics, transitions from the anion X?²Π_3/2 and X?′²Π_1/2 states into neutral X?³Σ⁻, ³Π, and for NiO and PdO, ¹Π, are assigned. Several states have been reassigned from those in the existing literature. Anion ²Π_3/2-²Π_1/2 spin-orbit splittings are measured, as are neutral ³Π₂-³Π₁ spin-orbit splittings: the XO ³Π ₂-³Π₁ splittings increase from 405±30 cm⁻¹ (NiO) to 805±30 cm⁻¹ (PdO) to 3580±40 cm⁻¹ (PtO). A bond length shortening of 0.03±0.01 Å is measured upon electron detachment from NiO⁻, resulting in an anion bond length of 1.66±0.01 Å. The bond length does not change upon electron detachment from PdO⁻ using 3.4-eV photons. The Pt-O bond length decreases by 0.035±0.010 Å in the ³Π₁←²Π_3/2 transition. The spectrum of OPtO displays a significantly more extended vibrational progression than those of ONiO or OPdO, and the O-Pt bond length is found to decrease by 0.07±0.01 Å upon electron detachment. The spectra support the view that the Ni-O bond is largely ionic, the Pd-O bond is somewhat less so, and the Pt-O bond displays a substantial covalent character.     

Vibrational Spectroscopic Characterization of the Sulphate-Carbonate Mineral Burkeite: Implications for Evaporites

Burkeite formation is important in saline evaporites and in pipe scales. Burkeite is an anhydrous sulphate-carbonate with an apparent variable anion ratio. Such a formula with two oxyanions lends itself to vibrational spectroscopy. Two symmetric sulphate stretching modes are observed, indicating at least at the molecular level the nonequivalence of the sulphate ions in the burkeite structure. The strong Raman band at 1065 cm^?1 is assigned to the carbonate symmetric stretching vibration. The series of Raman bands at 622, 635, 645, and 704 cm^?1 are assigned to the ν₄ sulphate bending modes. The observation of multiple bands supports the concept of a reduction in symmetry of the sulphate anion from T _d to C _3v or even C _2v.     

SiX2(X=H，F)分子的结构与势能函数

应用QCISD/6-311++G(3df,3pd)和B3P86/6-311++G(3d2f)对SiH₂,SiF₂的结构进行了优化,优化出SiH₂分子的稳定构型为C_2v,电子态为¹A₁,其平衡核间距R_e=0.15149nm、键角∠HSiH=92.5025°、离解能为3.7098eV. SiF _{关键词： 2}')" href="#">SiH₂ 2')" href="#">SiF₂ 多体项展式理论 势能函数     

Optische Messung der Elektronenstoß-Anregung von Xenon und molekularem Stickstoff im Schwellenbereich mit hoher Energieauflösung

Relative optical excitation functions of Xe and N₂ have been measured in the threshold region. The inciting electron beam had a FWHM of 50 meV. The threshold behaviour of the excitation functions ofp-levels of Xenon is strongly influenced by resonances. The onset is step-like, in some cases resonance structure is to be seen just above threshold. In some excitation functions resonance structure is found immediatly above the ionization limit. This is believed to be caused by two compound states the parent states of which could be the 6d′ and the 8s′ autoionizing state of Xenon. In nitrogen, the excitation functions of two bands of the second positive group have been measured (3371 and 3755 Å), the upper levels of which are thev=0 and thev=1 levels of theC ³Π _u state. The excitation raises linear from threshold. In the 3371 Å excitation function a resonance maximum at 11.50 eV is observed, where the cross section is increased due to resonance population by about 100%, as measured with a FWHM of 50meV of the electron beam. The broad absolute maximums of the excitation functions are found to lie at 14.0±0.1 eV in the case of the 3371 Å- and at 14.3±0.1 eV in the 3755 Å-band.     

Ferromagnetic and antiferromagnetic ordering in the wurtzite-type diluted magnetic semiconductors

We determined the magnetic symmetry groups (Shubnikov groups) of the wurtzite-type crystals doped with magnetic atoms periodically distributed at cation sites. The magnetic groups of doped crystals with ferro- or antiferromagnetic properties arise from the P6₃ mc (C _6v ⁴), P3m1 (C _3v ¹), C _s ³ (Cm) or C ₁¹ (P1) ordinary space groups. Those arising from the P6₃ mc or P3m1 group can present macroscopic ferromagnetic polarization only along the wurtzite symmetry axis whereas those arising from the C _s ³ (Cm) group can present ferromagnetic polarization only in the symmetry plane and those arising from the C ₁¹ (P1) group can present polarization along any direction. Actual structures do not keep in general long-range order for magnetic atom distribution but the samples with macroscopic polarization should present local symmetries close to those listed above. Therefore, orientation of easy magnetization can provide information about the most frequent local symmetry.     

Microwave spectrum,structure, and dipole moment of 7-oxabicyclo[2.2.1]heptane

The microwave spectrum of 7-oxabicyclo[2.2.1]heptane has been assigned in the ground and two excited vibrational states. Relative intensity measurements indicate that these two vibrations have wavenumbers of 120(30) and 330(30) cm^?1. The dipole moment obtained from Stark effect measurements is 1.621(10) D. The molecule is shown to have C_2v symmetry and the assignment of the two singly substituted ¹³C species gives the following skeletal structure: C₁-C₂ = 1.537(5) Å; C₂-C₃ = 1.551(5) Å; C₁-O = 1.452(10) Å; ?C₁OCC₄ = 95.3(10)° φ = 113.1(5)°.     

Electron paramagnetic resonance of deep boron acceptors in 4H-SiC and 3C-SiC crystals

EPR spectra of deep boron in 4H-SiC and 3C-SiC crystals have been observed and studied. Two sites in 4H-SiC produced deep-boron EPR signals, quasi-cubic k and hexagonal h. In both cases the deep-boron center symmetry is close to axial along the c crystal axis, and the g factor anisotropy is about an order of magnitude larger than that for shallow boron centers. In the 3C-SiC crystal, the deep-boron symmetry is also close to axial along one of the four 〈111〉 directions. The model proposed for the deep boron center with acceptor properties is B_Si-v _C, where B_Si is the boron substituting for silicon, and v _C is the carbon vacancy, with the B_Si-v _C direction coinciding in 4HSiC with the hexagonal axis of the crystal for both k and h positions. In the cubic 3C-SiC crystal, there are four equivalent deep boron centers, which represent B_Si-v _C pairs with the bond directed along one of the four 〈111〉 crystal directions. Fiz. Tverd. Tela (St. Petersburg) 40, 36–40 (January 1998)     

Infrared absorption investigation of the role of octahedral groups upon the phase transition in the Rb2KMoO3F3 crystal

The infrared absorption spectra of the oxyfluoride Rb₂KMoO₃F₃ have been measured in the frequency range corresponding to stretching vibrations of the Mo-O anion octahedron with the purpose of clarifying their role in the phase transition. A semi-empirical calculation of two possible configurations of quasioctahedral MoO₃F₃ groups has been performed. The results of the investigations have demonstrated that some octahedra in the crystal structure change the local symmetry from C _3v to C _2v due to the phase transition (T = 197 K).     

Effect of CO and H adsorption on the compositional structure of binary nanoalloys via DFT modeling

Theoretical methods (DFT/B3LYP and MP2) have been used to optimize the geometries of the Al _x Sb _y (x + y = 3, 5) clusters and their anions. Single point energy computations at CCSD(T) level have also been performed using the optimized B3LYP and MP2 structures. The basis sets used for Al and Sb atoms are 6-311+G(2d) and LANL2DZdp ECP, respectively. Harmonic vibrational frequency computations were carried out to confirm the nature of the stationary points. We report the structural and spectroscopic parameters of the named clusters. We also report the relative energy of the clusters, the vertical electron detachment energy, the adiabatic electron detachment energy and the adiabatic electron affinity. The most stable structures at the CCSD(T)//MP2 level are, the D _∞h linear structure (AlSb₂) and the C _2v V-bent structure (AlSb ₂ ^? ), the C _2v V-bent structure (Al₂Sb and its anion), the C _2v edge-capped tetrahedron (Al₂Sb₃ and its anion), the C _2v trigonal bipyramidal structure (Al₃Sb₂ and its anion), the C _4v square pyramidal (AlSb₄) and a C _2v ground structure for its anion, the C _2v planar trapezoidal structure (Al₄Sb) and the C _2v edge-capped tetrahedron (Al₄Sb^?). The adiabatic electron affinities calculated at the CCSD(T)//MP2 level are 2.17 eV (AlSb₂), 2.17 eV (Al₂Sb), 2.38 eV (Al₂Sb₃), 2.76 eV (Al₃Sb₂), 2.21 eV (AlSb₄) and 2.03 eV (Al₄Sb). The findings of this research are analysed, discussed and compared with the analogous picnogenides clusters.     

Photoelectron spectrum of a polycyclic aromatic nitrogen heterocyclic anion: quinoline−

We report a joint photoelectron spectroscopic and theoretical study on the molecular anion, quinoline^?. Analysis of the vibrationally resolved photoelectron spectrum found the adiabatic electron affinity, EA_a(C₉H₇N), to be 0.16 ± 0.05 eV. These findings were supported by density functional theory calculations. Our experimental and computational results demonstrate the unusual electrophilicity for a polycyclic aromatic heterocycle.     

New Bands in the Shock Excited NbO Blue/Visible and Near Infrared Systems

Abstract

Band systems of the astrophysically important molecule Niobium Oxide (NbO) have been excited in helium-driven shock waves through argon containing powdered Nb₂O₅. Of the 25 bands of the Δv = +3, +2, +1,0, -1, -2 and -3 sequences of the C ⁴Σ^? – X ⁴Σ^? blue/visible system which were excited between 4220Å and 5608Å, 16 are newly reported here. The Δv = +3 and -3 sequences are completely new. 12 new bands were also excited in the near infrared region 7952Å - 8450Å.     

Coupled cluster calculations for the interstellar molecule HC3NH+

An accurate equilibrium structure has been established for the linear interstellar molecular cation HC₃NH⁺: r _1e(CH) = 1.0703Å, R _1e(C₍₁₎C₍₂₎) = 1.2097 Å, R _2e(C₍₂₎C₍₃₎) = 1.3509Å, R _3e(C₍₃₎N) = 1.1448 Å and r _2e(NH) = 1.0079Å. Ground-state rotational constants for less abundant isotopomers are predicted with an uncertainty of about 0.02 MHz. The equilibrium dipole moment of HC₃NH⁺ is calculated to be 1.61 D.     

Electron affinities of cyano-substituted ethylenes

Electron affinities of ethylene and six cyano-substituted ethylenes (cyanoethylene, 1, 1-dicyanoethylene, cis-1, 2-dicyanoethylene, trans-1, 2-dicyanothylene, tricyanoethylene, and tetracyanoethylene) were determined using six different density functional or hybrid Hartree-Fock/density functional methods. Equilibrium geometries and harmonic vibrational frequencies for each species were determined with each density functional method. Experimental electron affinities exist for three of the six systems studied (cyanoethylene, trans-1, 2-dicyanoethylene, and tetracyanoethylene); for the three systems, the absolute average EA errors for the different methods are 0.10eV (BLYP), 0.19ev (BHLYP), 0.22eV (B3LYP), 0.20eV (BP86), 0.78eV (B3P86), and 0.81eV (LSDA). The electron affinities of gem-dicyanoethylene, cis-discyanoethylene, and tricyanoethylene are not known from experiment but are predicted here to be 1.23eV (gem-dicyanoethylene), 1.32eV (cis-dicyanoethylene), and 2.41eV (tricyanoethylene). Contrary to earlier suggestions, tetracyanoethylene is predicted to be planar, rather than twisted. Density functional theory predicts that the ²B_1u state of the ethylene anion lies lower than the ²B_2g state, which is reported by experimentalists as the (transient) ground state, and lower than the ²A_g state. Coupled-cluster results indicate that the ²A_g state is lower than either the ²B_2g or ²B_1u states. The energetic stabilization of cyano substitution on ethylene results from the π and π? conjugation of multiple cyano groups. The HOMO-LUMO gap in ethylene decreases with increasing cyano substitution, from 7.2eV in C₂H₄ to 3.8eV in C₂(CN)₄, explaining the extreme difference between the electron affinities of ethylene (negative) and tetracyanoethylene (～T3.0eV).     

Luminescence centers in thin films of yttrium oxide and yttrium-aluminum garnet activated with bismuth

Luminescence spectra and photoluminescence excitation spectra of Y₂O₃:Bi and Y₃Al₅O₁₂:Bi thin films were investigated. Luminescence was stimulated by the emission from two types of centers that were associated with the substitution of Bi³⁺ for Y³⁺ in sites of the crystal lattice of Y₂O₃ (Y₃Al₅O₁₂) with point symmetries C₂ and C_3i (D₂ and C_3i). The emission of Bi³⁺ in the site with point symmetry C_3i causes blue luminescence in both Y₂O₃:Bi and Y₃Al₅O₁₂:Bi films with maxima at 3.03 eV and 3.15 eV, respectively, that is related to the ³P₁-¹S₀ transition. The emission of Bi³⁺ in the site with point symmetry C₂ gives green luminescence in Y₂O₃:Bi with the maximum at 2.40 eV that is also related to the ³P₁-¹S₀ transition. The emission of Bi³⁺ in the site with point symmetry D₂ leads to ultraviolet luminescence in Y₃Al₅O₁₂:Bi with the maximum at 3.75 eV that corresponds to the ³P₁-¹S₀ transition. The red luminescence band with the maximum at 1.85 eV in Y₂O₃:Bi is due to the presence of structural defects. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 2, pp. 202–207, March–April, 2008.     

The aluminum arsenides Al<Subscript>m</Subscript>As<Subscript>n</Subscript> (m + n = 2–5) and their anions: Structures,electron affinities and vibrational frequencies

Geometries, electronic states and electron affinities of Al_mAs_n and Al_mAs _n (m+n=2–5) clusters have been examined using four hybrid and pure density functional theory (DFT) methods. Structural optimization and frequency analyses are performed using a 6-311+G(2df) one-particle basis set. The geometries are fully optimized with each DFT method independently. The three types of energy separations reported in this work are the adiabatic electron affinity (EA_ad), the vertical electron affinity (EA_vert), and the vertical detachment energy (VDE). The calculation results show that the singlet structures have higher symmetry than that of doublet structures. The best functional for predicting molecular structures was found to be BLYP, while other functionals generally underestimated bond lengths. The largest adiabatic electron affinity, vertical electron affinity and vertical detachment energy, obtained at the 6-311+G(2df)/BP86 level of theory, are 2.20, 2.04 and 2.27 eV (AlAs), 2.13, 1.94 and 2.38 eV (AlAs₂), 2.44, 2.39 and 2.47 eV (Al₂As), 2.09, 1.80 and 2.53 eV (Al₂As₂), 2.01, 1.57 and 2.36 eV (AlAs₃), 2.32, 2.11 and 2.55 eV (Al₂As₃), 2.40, 1.45 and 3.26 eV (AlAs₄), 1.94, 1.90 and 2.07 eV (Al₄As), respectively. However, the BHLYP method gives the largest values for EA_ad and EA_vert of Al₃As and EA_ad of Al₃As₂, respectively. For the vibrational frequencies of the Al_nAs_m series, the B3LYP method produces good predictions with the average error only about 10 cm^-1 from available experimental and theoretical values. The other three functionals overestimate or underestimate the vibrational frequencies, with the worst predictions given by the BHLYP method.     

Structures,thermochemistry, and electron affinities of the disilicon fluorides,Si2F n /Si2F− n (n = 1–6)

A systematic investigation of Si₂F_n/Si₂F^? _n systems is carried out with five density functional (DFT) methods in conjunction with DZP++ basis sets. For each system, various structures, including minima, transition states, and energetically low lying saddle points, are optimized. The geometries and the relative energies are discussed and compared. Three kinds of electron affinity and dissociation energy pertaining to the global minimum for each compound are reported. The theoretical predictions are in good agreement with the limited experimental results. The zero-point vibrational energy (ZPVE) corrected adiabatic electron affinities (EA_ad) are predicted as 1.97 (Si₂F), 1.92 (Si₂F₂), 2.39 (Si₂F₃), 2.02 (Si₂F₄), 2.68 (Si₂F₅), and 0.73 (Si₂F₆)eV by the BHLYP method, which is considered to be the most reliable method in the present study for predicting the EAs. These theoretical predictions are quite different from those for the analogous silicon hydrides and fluorocarbons. For example, both Si₂F₂ and its anions have vinylidene-like (Si-SiF₂) global minima. The anion SiSi bond distance is about 0.1 Å shorter than that for the Si—SiF₂ neutral. Both Si₂F₃ and its anion have carbyne-like (Si-SiF₃) global minima, with the anion SiSi distance about 0.05 Å shorter. Both Si₂F₄ and its anion have carbene-like (FSi-SiF₃) global minima, again with the negative ion SiSi distance ～0.05 Å shorter. Surprisingly, doubly bridged structures of Si₂F₄ are energetically competitive. For the ethyl-radical-like Si₂F₅, the expected longer SiSi distance (by 0.13 Å) for the anion is predicted. Whereas Si₂H₄, C₂F₄, Si₂H₆, and C₂F₆ do not have significant electron affinities, Si₂F₄ and Si₂F₆ do bind an electron. However, the unexpected Si₂F^? ₆ species has a significantly longer SiSi distance (by 0.15 Å) than that of neutral Si₂F₆.     

The 5v 3 bands of 18O enriched ozone: line positions of 16O16O18O, 16O18O16O, 16O18O18O and 18O16O18O

The four 5v ₃ bands of ¹⁸O enriched ozone have been observed and analysed for the first time. Two species (¹⁶O¹⁸O¹⁶O and ¹⁸O¹⁶O¹⁸O) belong to the C_2v symmetry group and two other (¹⁸O¹⁸O¹⁶O and ¹⁶O¹⁶O¹⁸O) to the C_s symmetry group. They have been recorded at a resolution of 0.008 cm^?1 with a pathlength of 32.16 m. Despite the very weak absorptions observed, almost 250 energy levels have been derived for each of the 4 species, with J ? 35 and K _a ? 13, and suitable sets of Hamiltonian parameters have been determined. For 3 species it has been necessary to account for the resonance between the (005) and (311) states to correctly reproduce the spectra observed. These resonances, anharmonic for C_2v, and hybrid (both anhar-monic and Coriolis) for C_s symmetry confirm the accidentally extremely strong coupling between the (005) and (311) states for ¹⁶O₃, due in that case to the very close distance between unperturbed energy levels. This work also confirms the excellent prediction of band centres of these four species derived from the recently determined isotopically invariant molecular potential function.     

Electronic structures of trithiapentalene analogues

The electronic structures of trithiapentalene analogues are studied by ab initio molecular orbital methods and density functional theory. Calculation of the normal vibration frequencies for substituted trithiapentalenes with C_2v symmetry indicates that σ-substituted trithiapentalene structures with C_2v symmetry are more destabilized than by substitution with the π-type group. CiLC-IRC analysis of the electronic structures for trithiapentalene analogues is performed for the pathway between the C_2v and C_s structures for 1,6,6aλ⁴-trithiapentalene and 1,6-dithia-6aλ⁴-oxapentalene, and it is found that the diradical states in both compounds are a critical factor in determining the stability of the structures with C_2v symmetry. Furthermore, the electronic state of 1,6,6aλ⁴-trithiapentalene with C_2v symmetry has less diradical character than that of 1,6-dithia-6a-oxapentalene.     

Electron capture by HCl trimers: an ab initio study

The structures and energies of three neutrals and four different anions formed by HCl trimers have been examined by theoretical calculations at MP2 and CCSD(T) levels with large basis sets. In order of increasing binding energy for three HCl molecules, the neutrals are: the Y-shaped species, an open chain Z-shaped form and the cyclic C_3h form. Dipole bound anion states are possible for both the Z and Y neutrals, but the DBS of the latter is likely to be short lived. The threshold energies for dissociative attachment (DA) of an electron in the reaction: e^- + (HCl)₃↦ H^• + Cl(HCl)₂^- at the CCSD(T) level are 0.0 and 0.06 eV, respectively for the Y and Z forms. The cyclic species has no dipole moment and does not attach thermal electrons. The structure of the D_3h solvated electron (SE) type trimer anion, was also investigated. Although the structure provides for a high electron affinity (0.33 eV relative to the cyclic trimer) it was unstable and rearranged into a ClH.ClH^•HCl^- (SE(2+1)) species. The latter has an EA of 0.59 eV. Vertical detachment energies were also found for these structures. The EAs and vertical detachment energies of the four HCl anion species are discussed and compared to the corresponding species of HF.