Probing the structural and electronic properties of aluminum-sulfur Al n S m (2 ≤ n + m ≤ 6) clusters and their oxides

Using the first-principle density functional calculations, the equilibrium geometries and electronic properties of anionic and neutral aluminum-sulfur Al _n S _m (2?≤?n?+?m?≤?6) clusters have been systematically investigated at B3PW91 level. The optimized results indicate that the lowest-energy structures of the anionic and neutral Al _n S _m clusters prefer the low spin multiplicities (singlet or doublet) except the Al₂￣, Al₂, S₂, Al₄ and Al₂S₄ clusters. A significant odd-even oscillation of the highest occupied-lowest unoccupied molecular orbital (HOMO-LUMO) energy gaps for the Al _n S _m ￣ clusters is observed. Electron detachment energies (both vertical and adiabatic) are discussed and compared with the photoelectron spectra observations. Furthermore, a good agreement between experimental and theoretical results gives confidence in the most stable clusters considered in the present study and validates the chosen computational method. In addition, the variation trend of chemical hardness is in keeping with that of HOMO-LUMO energy gaps for the Al _n S _m clusters. Upon the interaction of oxygen with the stable AlS _m ￣ clusters, the dissociative chemisorptions are favorable in energy. The binding energy and Gibbs free energy change show completely opposite oscillating behaviors as the cluster size increases.     

Theoretical study on aluminum carbide endohedral fullerene-Al4C@C80

The possibility of a new endohedral fullerene with a trapped aluminum carbide cluster, Al₄C @C₈₀-I _h , was theoretical investigated. The geometries and electronic properties of it were investigated using density functional theory methods. The Al₄C unit formally transfers six electrons to the C₈₀ cage which induces stabilization of Al₄C@C₈₀. A favorable binding energy, relatively large HOMO-LUMO gap, electron affinities and ionization potentials suggested the Al₄C@C₈₀ is rather stable. The analysis of vertical ionization potential and vertical electron affinity indicate Al₄C@C₈₀ is a good electron acceptor.

Stability and electronic properties of praseodymium-doped silicon clusters PrSin (<Emphasis Type="Italic">n</Emphasis> = 12–21)

The neutral PrSi _n (n = 12–21) species considering various spin configurations were systematically studied using PBE0 and B3LYP schemes in combination with relativistic small-core potentials (ECP28MWB) for Pr atoms and cc-pVTZ basis set for Si atoms. The total energy, growth-pattern, equilibrium geometry, relative stability, hardness, charge transfer, and magnetic moments are calculated and discussed. The results reveal that when n < 20, the ground-state structure of PrSi _n evaluated to be prolate clusters. Starting from n = 20, the ground-state structures of PrSi _n are evaluated to be endohedral cagelike clusters. Although the relative stabilities based on various binding energies and different functional is different from each other, the consensus is that the PrSi₁₃, PrSi₁₆, PrSi₁₈, and PrSi₂₀ are more stable than the others, especially the PrSi₂₀. Analyses of hardness show that introducing Pr into Si _n (n = 12–21) elevates the photochemical sensitivity, especially for PrSi₂₀. Calculated result of magnetic moment and charge transfer shows that the 4f electrons of Pr in the clusters are changed, especially in endohedral structures such as PrSi₂₀, in which one electron transfers from 4f to 5d orbital. That is, the 4f electron of Pr in the clusters participates in bonding. The way to participate in bonding is that a 4f electron transfers to 5d orbital. Although the 4f electron of Pr atom participates in bonding, the total magnetic moment of PrSi _n is equal to that of isolated Pr atom. The charge always transfers from Pr atom to Si _n cluster for the ground state structures of PrSi_n (n = 12–19), but charge transfer is reverse for n ≥ 20. The largest charge transfer for endohedral structure reveals that the bonding between Pr and Si _n is ionic in nature and very strong. The fullerenelike structure of PrSi₂₀ is the most stable among all of these clusters and can act as the building blocks for novel functional nanotubes.     

The structures and stabilities of small diarsenic-doped silicon clusters

The structures and stabilities of As₂-doped Si_n (n = 1-7) clusters have been investigated at the B3LYP level of theory, incorporating the 6-311+G^∗ basis set. An isosceles triangle is predicted to be the lowest-energy structure of the As₂Si cluster, whereas the global minimum of As₂Si₂ possesses an As-As-butterfly structure. The ground state structures for As₂Si₃, As₂Si₄ and As₂Si₅ are all bipyramids: trigonal, tetragonal and pentagonal, respectively, which could have important applications as building blocks to synthesize silicon nanowires. The most stable isomer of As₂Si₆ possesses a tricapped trigonal bipyramid structure. The lowest energy structure of As₂Si₇ can be viewed as a substitutional structure of the tricapped trigonal prism Si₉ isomer. In the majority of the lowest energy isomers, the two As atoms tend to be separated from each other, in order to maximize the number of Si-As bonds, and therefore locate at the axial vertex or face-capping atomic positions, especially for As₂Si₄-As₂Si₇. According to results of the incremental binding energies, the HOMO-LUMO gaps and the vertical ionization potentials, the As₂Si₃ and As₂Si₆ clusters are relatively stable compared to their neighbors. Natural bond orbital analyses suggest that delocalized electrons and multi-centered bonds play an important role in stabilizing the low-energy As₂Si_n structures.     

Reexamination of structures,stabilities, and electronic properties of holmium-doped silicon clusters HoSi<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript> (<Emphasis Type="Italic">n</Emphasis> = 12–20)

The total energies, growth patterns, equilibrium geometries, relative stabilities, hardnesses, intramolecular charge transfer, and magnetic moments of HoSi _n (n?=?12–20) clusters have been reexamined theoretically using two different density functional schemes in combination with relativistic small-core Stuttgart effective core potentials (ECP28MWB) for the Ho atoms. The results show that when n?=?12–15, the most stable structures are predicted to be exohedral frameworks with a quartet ground state, but when n?=?16–20, they are predicted to be endohedral frameworks with a sextuplet ground state. These trend in stability across the clusters (gauged from their dissociation energies) was found to be approximately the same regardless of the DFT scheme used in the calculations, with HoSi₁₃, HoSi₁₆, HoSi₁₈, and HoSi₂₀ calculated to be more stable than the other clusters. The results obtained for cluster hardness indicated that doping the Ho atom into Si₁₃ and Si₁₆ leads to the most stable HoSi _n clusters, while doping Ho into the other Si _n clusters increases the photochemical sensitivity of the cluster. Analyses of intracluster charge transfer and magnetic moments revealed that charge always shifts from the Ho atom to the Si _n cluster during the creation of exohedral HoSi _n (n?=?12–15) structures. However, the direction of charge transfer is reversed during the creation of endohedral HoSi _n (n?=?16–20) structures, which implies that Ho acts as an electron acceptor when it is encapsulated in the Si _n cage. Furthermore, when the most stable exohedral HoSi _n (n?=?12–15) structures are generated, the 4f electrons of Ho are virtually unchanged and barely participate in intracluster bonding. However, in the most stable endohedral HoSi _n (n?=?16–20) frameworks, a 4f electron does participate in bonding. It does this by transferring to the 5d orbital, which hybridizes with the 6s and 6p orbitals and then interacts with Si valence sp orbitals. Meanwhile, the total magnetic moments of the HoSi _n (n?=?16–20) clusters are considerably higher than those of HoSi _n (n?=?12–15). Interestingly, the endohedral HoSi₁₆ and HoSi₂₀ clusters can be viewed as the most suitable building blocks for novel high-density magnetic storage nanomaterials and for novel optical and optoelectronic photosensitive nanomaterials, respectively.     

Studies on structures and electron affinities of the simplest alkyl dithio radicals and their anions with gaussian-3 theory and density functional theory

The equilibrium geometries and electron affinities of the R-SS/R-SS^-(R=CH₃, C₂H₅, n-C₃H₇, i-C₃H₇, n-C₄H₉, t-C₄H₉, n-C₅H₁₁) species have been studied using the higher level of the Gaussian-3(G3) theory and 21 carefully calibrated pure and hybrid density functionals (five generalized gradient approximation (GGA) methods, seven hybrid GGAs, three meta GGA methods, and six hybrid meta GGAs) in conjunction with diffuse function augmented double-ζ plus polarization (DZP++) basis sets. The geometries are fully optimized with each method and discussed. The reliable adiabatic electron affinity has been presented by means of the high level of G3 technique. With the DZP++ DFT method, three measures of neutral/anion energy differences reported in this work are the adiabatic electron affinity, the vertical electron affinity, and the vertical detachment energy. The adiabatic electron affinities, obtained at the BP86, M05-2X, B3LYP, M06, B98, M06-2X, mPW1PW91, HCTH, B97-1, M05, PBE1PBE, and VSXC methods, are in agreement with the G3 results. These methods perform better for EA prediction and are considered to be reliable.     

Density functional studies of the stepwise substitution of pyrrole, furan, and thiophene with BCO

The structures, stabilities, and aromaticities of a series of (BCO) _n (CH)_4–n NH (n?=?0–4), (BCO) _n (CH)_4–n O (n?=?0–4), and (BCO) _n (CH)_4–n S (n?=?0–4) clusters were investigated at the B3LYP density functional level of theory. The most stable positional isomers of the individual clusters were obtained. All of the calculated CO binding energies were exothermic, suggesting that these BCO-substituted species are stable. Calculated differences in strain energy between the BCO-substituted structures and their corresponding hydrocarbon clusters were all exothermic, indicating that the BCO-substituted structures are less strained. The negative nucleus-independent chemical shift (NICS) values obtained show that these BCO-substituted clusters are aromatic compounds, in good agreement with the aromaticities of the corresponding hydrocarbon species. To aid further experimental investigations, CO-stretching frequencies were also computed.     

Asymmetric binuclear titanocenes linked by alkyl benzyl ethers: Synthesis, characterization and use as catalysts for ethylene polymerization

A series of novel asymmetric binuclear titanocenes linked with alkyl benzyl ethers p-[(C₅H₅TiCl₂)C₅H₄CH₂]C₆H₄O(CH₂)_n[C₅H₄(TiCl₂C₅H₅)] (n = 2-5) (13-16) have been synthesized by treating p-(LiC₅H₄CH₂)C₆H₄O(CH₂)_n(C₅H₄Li) (n = 2-5) (9-12) with C₅H₅TiCl₃. The new complexes have been characterized by elemental analysis and NMR spectra. Their catalytic activity for ethylene polymerization was investigated in the presence of aluminoxane (MAO). The results show that 13-16 are efficient catalysts for producing polyethylene (PE) with a broad molecular weight distribution (MWD). Their catalytic activity is highly dependent on the length of the alkyl chain and the polymerization conditions. A longer alkyl chain increases the catalytic activity, whereas the molecular weight of the produced polyethylene decreases.     

Ab initio calculation of the geometries, stabilities, and electronic properties for the bimetallic Be2Au(n) (n = 1-9) clusters: comparison with pure gold clusters

Ab initio methods based on density functional theory at BP86 level were applied to the study of the geometrical structures, relative stabilities, and electronic properties of small bimetallic Be₂Au _n (n = 1–9) clusters. The optimized geometries reveal that the most stable isomers have 3D structures at n = 3, 5, 7, 8, and 9. Here, the relative stabilities were investigated in terms of the averaged atomic binding energies, fragmentation energies and second-order difference of energies. The results show that the planar Be₂Au₄ structure is the most stable structure for Be₂Au _n clusters. The HOMO−LUMO gap, vertical ionization potential, vertical electron affinity and chemical hardness exhibit a pronounced even–odd alternating phenomenon. In addition, charge transfer and natural electron configuration were analyzed and compared.     

Structural transitions in mixed ternary noble gas clusters

The properties of noble gas systems can be greatly extended by heterogeneous mixtures of elements. The geometrical structures and energies of mixed Ar–Kr–Xe clusters were investigated using ternary Lennard-Jones (TLJ) potential. For the Ar₁₉Kr _n Xe₁₉, Ar₁₉Kr₁₉Xe _n , and Ar _n Kr₁₉Xe₁₉ (n?=?0–17) clusters investigated, the results show that only two minimum energy configurations exist, i.e., polytetrahedron and six-fold pancake. The inner core of all these clusters is composed mainly of Ar atoms, and Kr and Xe atoms are distributed on the surface with well mixed pattern for polytetrahedral and segregate pattern for six-fold pancake configurations. The relative stability property of Ar–Kr–Xe clusters with a certain composition is discussed. Moreover, the role of heterogeneity on the strain was investigated, and reduced strain energies in Ar–Kr–Xe clusters were studied to find possible ways of reducing strain. The results showed that the strain energies were affected mainly by Ar–Ar, Ar–Kr, and Xe–Xe bonds.

Cyclic and high molecular weight chiral binaphthoxy-phosphazene polymers carrying Br or trimethylsilyl-acetylene groups

The new chiral and functionalized cyclic binaphthoxyphosphazenes R,R,R-[N₃P₃(O₂C₂₀H₁₀Br₂)₃] (R-1), R,R,R-[N₃P₃(O₂C₂₀H₁₀(CCSiMe₃)₂)₃] (R-2), and the high molecular weight linear polymers R/S-[NP(O₂C₂₀H₁₀Br₂)]_n (R/S-3), R-[NP(O₂C₂₀H₁₀Br₂)]_n (R-3), and R-{NP[O₂C₂₀H₁₀(CCSiMe₃)₂]}_n, (R-4), with M_w on the order of 10⁶ and very high T_g, have been synthesized and characterized by IR and NMR spectroscopy. The optically active polymer (R-3) was configurationally stable below 300 °C, but at higher temperatures an atropisomerization process took place that became faster near the glass transition temperature (ca. 350 °C).     

Hydrocarbons,phenols and sterols of the testa and pigment strand in the grain of Hordeum distichon

Material from the testa of decorticated barley grains contained hydrocarbons, esters, triglycerides, free sterols, 5-n-alkylresorcinols, and traces of free alcohols, carbonyl compounds, and various polar, acidic materials. The hydrocarbon fraction was mainly a series of n-alkanes, extending at least from C₁₁ to C₃₆, in which the C₂₉ and C₃₁ components were prominent. Two minor series of alkanes were also present. Sometimes a trace of an unsaturated hydrocarbon was detected. The ester fraction contained sterols and alkanols esterified by fatty acids, which differed in relative amounts from the fatty acids found in the triglycerides. The triglycerides were thought to have leached from within the grain. At least five free sterols were present, including sitosterol and campesterol. The 5-n-alkylresorcinols were at least twelve members of a homologous series, of which four, C₂₅, C₂₇, C₂₉, and C₃₁, made 98% of the total. Members of the series with even numbers of carbon atoms were also present. It is suggested that they are partly responsible for excluding microorganisms from the interior of the grain. The testa membrane, with the associated pigment strand, contained an estolide of fatty acids and various hydroxyacids, a polysaccharide component, and uncharacterized material.     

Structures and stabilities of ScBn (n = 1–12) clusters: an ab initio investigation

The geometries, stabilities, and electronic properties of ScB_n (n?=?1–12) clusters have been systematically investigated by using density functional theory B3LYP method and coupled–cluster theory CCSD(T) method. It is found that the ground state isomers of ScB_n have planar or quasi–planar structure when n?≤?6, which can be viewed as a B atom of the corresponding B_n+1 cluster is substituted by a Sc atom. From n?≥?7, the ground state isomers favor nest–like structure, in which the Sc atom sits on a nest–like B_n cluster. The calculated second–order differences of energies manifest that the magic numbers of stability are n?=?3, 7, 8, 9 and 11 for the ScB _n clusters. Further analysis indicates that the ScB₇ cluster with C _6v symmetry represents the outstanding stable ScB_n cluster, as confirmed by its electronic structure and molecular orbitals.     

2D Holodirected lead(II) bromide coordination polymers constructed of rigid and flexible ligands

Three new 2D Pb^II coordination polymers containing 4,4′-bipyridine (4,4′-bipy), 1,2-bis(4-pyridyl)ethane (bpa) and 1,2-bis(4-pyridyl)ethene (bpe) with bromide anions, [Pb(μ-4,4′-bipy)(μ-Br)₂]_n (1), [Pb(μ-bpa)(μ-Br)₂]_n (2) and [Pb(μ-bpe)(μ-Br)₂]_n (3) have been synthesized and characterized by elemental analysis, IR spectroscopy and their structures studied by X-ray crystallography. The thermal stability of compounds 1-3 was studied by thermal gravimetric (TG) and differential thermal analyses (DTA). The single-crystal X-ray data shows that the Pb²⁺-ions have coordination numbers of six and contain the rarely holodirected geometries.     

C14-Oxylipin glucosides isolated from Lemna paucicostata

Oxylipin glucosides (2-4) were isolated from Lemna paucicostata with their structures and absolute configurations elucidated by spectroscopic and chemical methods. Compounds 2-4 were glucosides of C₁₄ oxylipin which were synthesized from α-linolenic acid via the 9-lipoxygenase pathway.     

Structures of some botryococcenes: branched hydrocarbons from the b-race of the green alga Botryococcus braunii

Nine branched hydrocarbons of the botryococcene type (C_nH_2n-10 30 ? n ? 37) have been isolated from the green alga Botryococcus braunii. Hydrocarbon mixtures were recovered from wild algae collected in fresh water lakes or from the same strains growing in laboratory; they were further separated by reversed-phase, and in some cases by normal phase, HPLC. From chemical investigations, GC/MS analyses, ¹H and ¹³C NMR spectroscopy, the structures of four new botryococcenes (one C₃₃H₅₆, two C₃₄H₅₈ and one C₃₇H₆₄) were elucidated.     

B30H8, B39H9 2−, B42H10, B48H10, and B72H12: polycyclic aromatic snub hydroboron clusters analogous to polycyclic aromatic hydrocarbons

Calculations performed at the ab initio level using the recently reported planar concentric π-aromatic B₁₈H₆ ²⁺(1) [Chen Q et al. (2011) Phys Chem Chem Phys 13:20620] as a building block suggest the possible existence of a new class of B_3n H _m polycyclic aromatic hydroboron (PAHB) clusters—B₃₀H₈(2), B₃₉H₉ ^2?(3), B₄₂H₁₀(4/5), B₄₈H₁₀(6), and B₇₂H₁₂(7)—which appear to be the inorganic analogs of the corresponding C _n H _m polycyclic aromatic hydrocarbon (PAHC) molecules naphthalene C₁₀H₈, phenalenyl anion C₁₃H₉ ^?, phenanthrene/anthracene C₁₄H₁₀, pyrene C₁₆H₁₀, and coronene C₂₄H₁₂, respectively, in a universal atomic ratio of B:C?=?3:1. Detailed canonical molecular orbital (CMO), adaptive natural density partitioning (AdNDP), and electron localization function (ELF) analyses indicate that, as they are hydrogenated fragments of a boron snub sheet [Zope RR, Baruah T (2010) Chem Phys Lett 501:193], these PAHB clusters are aromatic in nature, and exhibit the formation of islands of both σ- and π-aromaticity. The predicted ionization potentials of PAHB neutrals and electron detachment energies of small PAHB monoanions should permit them to be characterized experimentally in the future. The results obtained in this work expand the domain of planar boron-based clusters to a region well beyond B₂₀, and experimental syntheses of these snub B_3n H _m clusters through partial hydrogenation of the corresponding bare B_3n may open up a new area of boron chemistry parallel to that of PAHCs in carbon chemistry.

Resonance Raman spectroscopy of chemically modified retinals: Assigning the carbon-methyl vibrations in the resonance Raman spectrum of rhodopsin

To assign the observed vibrationsl modes in the resonance Raman spectrum of the retinylidene chromophore of rhodopsin, we have studied chemically modified retinals. The series of analogs investigated are the n-butyl retinals substituted at C₉ and C₁₃. The results obtained for the 11-cis isomer have clearly assigned the CCH₃ vibrational frequencies observed in the spectrum of the retinylidene chromophore. The data show that the C₍₉₎CH₃ stretching vibration can be assigned to the vibrational mode observed in the 1017 cm^?1 region, and the vibration detected at 997 cm^?1 can be assigned to the C₍₁₃CH₃ vibration. The C₍₅₎CH₃ stretching mode does not contribute to the vibrations observed in this region. The splitting in the C_(n)CH₃ (n = 9, 13) vibration is characteristic of the 11-cis conformation. The results on the modified retinals do not support the hypothesis that the splitting arises from equilibrium mixtures of 11-cis, 12-s-cis and 11-cis, 12-s-trans in solution. Thus, this splitting cannot be used to determine whether the chromophore in rhodopsin is in a 12-s-cis or 12-s-trans conformation. However, our results demonstrate that there are other vibrational modes in the spectra which are sensitive to this conformational equilibrium and we use the presence of a strong ~ 1271 cm^?1 mode in bovine and squid rhodopsin spectra as an indication that the chromophore in these pigments is 11-cis, 12-s-trans.     

An insight into the structures,stabilities, and bond character of BnPt (n=1∼6) clusters

We perform a systematical investigation on the geometry, thermodynamic/kinetic stability, and bonding nature of low-lying isomers of B_nPt (n=1-6) at the CCSD(T)/[6-311+G(d)/LanL2DZ]//B3LYP/[6-311+G(d)/LanL2DZ] level. The most stable isomers of B_nPt (n=1-6) adopt planar or quasi-planar structure. B_nPt (n=2-5) clusters can be generated by capping a Pt atom on the B-B edge of pure boron clusters. However, For B₆Pt with non-planar structure, a single doped Pt atom significantly affects the shape of the host boron cluster. The dopant of the Pt atom can improve the stability of pure boron clusters. The valence molecular orbital (VMO), electron localization function (ELF), and Mayer bond order (MBO) are applied to gain insight into the bonding nature of B_nPt (n=2-6) isomers. The aromaticity for some isomers of B_nPt (n=2-6) is analyzed and discussed in terms of VMO, ELF, adaptive natural density partitioning (AdNDP), and nucleus-independent chemical shift (NICS) analyses. Results obtained from the energy and cluster decomposition analyses demonstrate that B₂Pt and B₄Pt exhibits as highly stable. Importantly, some isomers of B_nPt (n=2-5) are stable both thermodynamically and kinetically, which are observable in future experiment.