内嵌富勒烯[M@C_(70)](M=Li,Na,K,Be,Mg,Ca)与[Mg(H_2O)_6]~(2+)相互作用的密度泛函理论研究

使用密度泛函理论方法,对内嵌多种碱金属及碱土金属原子(M=Li,Na,K,Be,Mg,Ca)的富勒烯C70与水合Mg(II)离子之间的相互作用进行了理论研究.首先对各原子(M=Li,Na,K,Be,Mg,Ca)嵌入C70后的形成能进行了讨论,之后计算了[M@C70]各体系与[Mg(H_2O)6]2~+的相互作用能,并采用自然键轨道理论(NBO)研究了电荷转移的情况,最后进行了电子密度拓扑分析.结果表明,内嵌原子半径越大,[M@C70]各体系的热力学稳定性就越高,转移至[Mg(H_2O)6]2~+的电荷也随之增加,二者之间的相互作用属于闭壳层相互作用及共价作用.     

内嵌富勒烯[M@C70] (M=Li, Na, K, Be, Mg, Ca)与[Mg(H2O)6]2+相互作用的密度泛函理论研究

使用密度泛函理论方法, 对内嵌多种碱金属及碱土金属原子(M=Li, Na, K, Be, Mg, Ca)的富勒烯C70与水合Mg(II)离子之间的相互作用进行了理论研究. 首先对各原子(M=Li, Na, K, Be, Mg, Ca)嵌入C70后的形成能进行了讨论, 之后计算了[M@C70]各体系与[Mg(H2O)6]2+的相互作用能, 并采用自然键轨道理论(NBO)研究了电荷转移的情况, 最后进行了电子密度拓扑分析. 结果表明, 内嵌原子半径越大, [M@C70]各体系的热力学稳定性就越高, 转移至[Mg(H2O)6]2+的电荷也随之增加, 二者之间的相互作用属于闭壳层相互作用及共价作用.     

Galactic model of element formation

A cosmological model is presented that produces He, C, O, D, Li, Be, and B in their observed abundances without a Big Bang. The elements are produced during the 1.5-Gy formation period of a galaxy, with C, O, and other heavy elements produced by stars of M>12 M₃ , He by stars of 6 M_s<M<12 M_s, and D, Li, Be, and B by cosmic-ray reactions in a nearly pure H plasma halo. Thus, the model shows that the major elements used in astrophysical studies can be produced during galactic formation by exactly the same processes known to function today at much lower rates     

Elastic scattering of 9Be on light target nuclei

The elastic scattering of ⁹Be on the target nuclei ⁹Be, ¹²C, ¹³C and ¹⁶O was measured at projectile energies of 14, 20 and 26 MeV. All angular distributions show a diffraction-like structure. In addition, excitation curves were measured for the scattering of ⁹Be on ⁹Be at three different angles in the energy range of 9–22 MeV. An optical potential having parameters independent of mass number and energy and reproducing all the measured angular distributions in the forward angular region was found and compared with that for the scattering of ⁹Be on medium and heavy nuclei.     

Total reaction and transfer cross sections for 11B + 9Be and 13C + 9Be reactions at low energies

The total reaction cross sections for ¹¹B + ⁹Be and ¹³C + ⁹Be have been measured by the total γ-ray yield method over the energy intervals E_c.m. = 1.4–4.4 MeV and E_c.m. = 2.0–5.2 MeV, respectively. The cross sections for the neutron transfer reactions ¹¹B(⁹Be, ⁸Be)¹²B, leading to the ¹²B 0.953 and 1.674 MeV states, and ¹³C(⁹Be, ⁸Be)¹⁴C, leading to the ¹⁴C 6.094, 6.728 and 6.902 MeV states, have been obtained from the yields of the characteristic γ-rays. The α-transfer reaction ¹¹B(⁹Be, ⁵He)¹⁵N, leading to many unresolved ¹⁵N states, has been observed with large cross section. There is, however, no evidence for the ¹³C(⁹Be, ⁵He)¹⁷O transfer process in the ¹⁷O + nα channels. This different behaviour of the ¹¹B + ⁹Be and ¹³C + ⁹Be systems seems to indicate that the α-transfer reaction at sub-barrier energies is not a direct transfer process, and that it probably occurs via molecular state formation.     

Proton total cross sections on 1H, 2H, 4He, 9Be,C and O in the energy range 180 to 560 MeV

Proton total cross sections have been measured for the nuclei ¹H, ²H, ⁴He, ⁹Be, C and O from 180 to 560 MeV (610 to 1170 MeV/c). The standard transmission technique was used with a resulting total error of 1 % to 2 %. Statistical errors were small (< 1 %) and the major contribution to the final error comes from uncertainties in applying the correction for Coulomb-nuclear interference in elastic scattering at small angles. For ⁴He, ⁹Be, ¹²C. and ¹⁶O this experiment also gives new information on the real part of the spin-independent forward scattering amplitude for proton-nucleus elastic scattering. Total cross sections have been calculated using a Glauber model approach and poor agreement with the data is obtained, even for deuterium.     

Reactions of 14N and 16O ions with light nuclei at Elab = 16–58 MeV

Yield curves for formation of ⁷Be and other radio-nuclides from bombardment of C, Al and Si targets with 16–58 MeV ¹⁴N and ¹⁶O ions were measured. The ⁷Be yields disagree by several orders of magnitude with Hauser-Feshbach and transition-state predictions. The other yields are in order-of-magnitude agreement with nucleon and/or α-particle evapolation calculations.     

Complexes between H2 and neutral oxyacid beryllium derivatives. The role of angular strain

ABSTRACT

The complexes between 14 different Be-salts of oxyacids from groups 13 to 16 with one and two molecules of H₂ have been investigated by means of the MP2/aug-cc-pVTZ ab initio molecular orbital theory method, which was found to be reliable for the treatment of these weakly bound species. The main conclusion is that these Be-salts yield rather stable complexes with dihydrogen, with binding energies one order of magnitude larger than other typical H₂ complexes reported in the literature. This strong binding is shown to be due to an enhancement of the electron-deficient nature of Be when attached to an oxyacid moiety, which depends more on the type of coordination of the central atom of the oxyacid moiety. The formation of these complexes is followed by a significant lengthening of the H₂ internuclear distance and a concomitant red-shift of the H–H stretching frequency, which becomes a good indicator of the strength of the interaction. The charge shifting from the bonding region of the H₂ molecule to the interboundary Be···H₂ region is the physical phenomenon behind the stability of these complexes. Accordingly, the most important contributor to this stability is the inductive term, followed by the electrostatic interactions. The ability of Be to bind H₂ is enhanced by the angular arrangement of the O–Be–O electron-acceptor group.     

A computational study of model hydrogen-, halogen-, beryllium- and magnesium-bonded complexes of aziridine derivatives

ABSTRACT

A computational study of the complexes F^?/H₂O…Z-aziridine, Z-aziridine…BeH₂/MgH₂ and F^?/H₂O…Z-aziridine…BeH₂ /MgH₂ (Z = Cl, H, Li) was undertaken in order to investigate the non-covalent interactions operative in the dimers and to assess their interplay in the trimer complexes. The halogen- and hydrogen-bonds between the O and Z atoms in F^?/H₂O…Z-aziridine are enhanced in the trimers by the Be(Mg) bond and vice versa, but the lithium bond is hardly affected. In the trimers containing F^?, the H bond is more dominant than the Be(Mg) bond, whereas the Be(Mg) bond is more dominant in the halogen- and lithium-bonded analogues. On the other hand, the Be(Mg) bond makes the major contribution to the energetic stability of all of the trimers containing H₂O.     

Primordial beryllium as a big bang calorimeter

Many models of new physics including variants of supersymmetry predict metastable long-lived particles that can decay during or after primordial nucleosynthesis, releasing significant amounts of nonthermal energy. The hadronic energy injection in these decays leads to the formation of ?Be via the chain of nonequilibrium transformations: Energy(h)→T, 3He→?He, ?Li→?Be. We calculate the efficiency of this transformation and show that if the injection happens at cosmic times of a few hours the release of O(10 MeV) per baryon can be sufficient for obtaining a sizable ?Be abundance. The absence of a plateau structure in the ?Be/H abundance down to a O(10?1?) level allows one to use beryllium as a robust constraint on new physics models with decaying or annihilating particles.     

Molecular dynamics simulation studies of cryoprotective agent solutions: the relation between melting temperature and the ratio of hydrogen bonding acceptor to donor number

Molecular dynamics simulations have been carried out for glycerol–water–sodium chloride ternary solution due to its important role in cryopreservation engineering. The radial distribution functions for atom pairs potentially related to C–H ··· O and O–H ··· O hydrogen bonds were calculated. The radial distribution functions for the H (connected to C)–O atom pair do not exhibit peaks between 2 and 3 Å, whereas the radial distribution functions for the C–O atom pair exhibit distinct peaks between 3 and 4 Å. The reason for this is because most C–H ··· O geometries are bent and deviate from linearity. The ratios of acceptor to donor numbers for water and glycerol molecules decrease as the solute concentration increases. A characteristic concentration has been found that divides solutions with different mechanisms. Below the characteristic concentration, the melting temperature is linearly related to the ratio of acceptor to donor number for water molecules, whereas above the characteristic concentration, the melting temperature is linearly related to the ratio of acceptor to donor number for glycerol molecules. Further studies indicate that the relations are independent of hydrogen bonding criteria and temperature.     

水热法祖母绿激光晶体的光谱性质研究

报道了温差水热法生长的祖母绿激光晶体(Cr3+:Be3Al2Si6O18)的光学参量特点.通过对祖母绿晶体的吸收光谱和荧光光谱的测量,计算了晶体场强度Dq、Racah参量B和C, Dq/B≈2.3,说明了祖母绿晶体中的Cr3+离子处于中等晶场.室温下的荧光光谱特点显示4T2→4A2的跃迁为700～840nm的宽带辐射跃迁.此外该晶体的有效声子能量h－ω=409.6cm－1,Huang-Rhys因子S=3.5较小,说明祖母绿的电-声子耦合作用较弱.     

The breakup of24Mg into16O and8Be

The breakup of²⁴Mg into¹⁶O and⁸Be fragments has been studied using the reactions¹²C(²⁴Mg,¹⁶O⁸Be)¹²C and¹²C(²⁰Ne,¹⁶O⁸Be)⁸Be. In the latter case, discrete states are observed near 24–28 MeV of excitation in²⁴Mg and the yield from this reaction is an order of magnitude greater than that of the former. This implies the excited configuration populated in²⁴Mg is favoured by the transfer of an alpha-particle and would therefore suggest an association with a 4-particle 4-hole configuration. This suggests a link with the octupole stabilised deformed minimum which appears in Nilsson-Strutinsky calculations of the potential energy surface in²⁴Mg, and also with theα —¹⁶O —α structure predicted in cranked cluster model calculations. In the excitation spectrum no states appear above 31 MeV indicating a possible band termination in disagreement with recent results using the¹⁶O+¹²C reaction. These results are discussed in terms of the Harvey model.     

Interaction of water molecules with bare and deuterated polycrystalline diamond surface studied by high resolution electron energy loss and X-ray photoelectron spectroscopies

In this work we study the interaction of water molecules with deuterated and bare polycrystalline diamond surfaces upon exposure to water vapor by X-ray photoelectron spectroscopy (XPS) and high resolution electron energy loss spectroscopy (HR-EELS). To distinguish the molecular origin of hydrogen bonds (i.e. C–H, O–H, C–O–H, etc.) formed on the diamond surface upon interaction with the water molecules, deuterated and hydrogenated gases were used in our experiments. Diamond films were deposited from a deuterated gas mixture to induce C(di)-D surface terminations. Water adsorption on bare diamond surface gives rise to the appearance of well defined and pronounced C–H and C–OH vibrational HR-EELS peaks and an intense O (1s) XPS peak. These chemically adsorbed water fragments survive 300 °C anneal temperature under ultra-high vacuum conditions. Annealing at 600 °C of the water exposed bare diamond surface results in disappearance of the C–OH vibrational modes alongside with a pronounced reduction of the C–H vibrational modes, whilst only upon annealing to ~ 800 °C the O (1s) XPS peak decreased substantially in intensity. We associate these effects with dissociative adsorption of the water molecules on the bare diamond surfaces.Water exposure onto a deuterated surface, on the other hand, does not result in the appearance of the C–OH vibrational peaks but only to an increase of the C–H vibrational HR-EELS mode along side with the appearance of a weaker XPS O (1) peak, as compared to the same experiment, performed on the bare surface. 300 °C anneal significantly diminishes surface oxygen concentration, as monitored by XPS. We associate these results with H₂O decomposition reactions and also with molecular adsorption on deuterated diamond surfaces. Annealing of the water exposed deuterated diamond surface, results in a pronounced decrease and disappearance of the O (1s) XPS peak at a temperature of ~ 800 °C.     

Computational study on structures,thermochemical properties,and bond energies of disulfide oxygen (S–S–O)‐bridged CH3SSOH and CH3SS(=O)H and radicals

Cleavage of disulfide bonds is a common method used in linking peptides to proteins in biochemical reactions. The structures, internal rotor potentials, bond energies, and thermochemical properties (Δ_fH°, S°, and Cp(T)) of the S–S bridge molecules CH₃SSOH and CH₃SS(=O)H and the radicals CH₃SS?=O and C?H₂SSOH that correspond to H‐atom loss are determined by computational chemistry. Structure and thermochemical parameters (S° and Cp(T)) are determined using density functional Becke, three‐parameter, Lee–Yang–Parr (B3LYP)/6‐31++G (d, p), B3LYP/6‐311++G (3df, 2p). The enthalpies of formation for stable species are calculated using the total energies at B3LYP/6‐31++G (d, p), B3LYP/6‐311++G (3df, 2p), and the higher level composite CBS–QB3 levels with work reactions that are close to isodesmic in most cases. The enthalpies of formation for CH₃SSOH, CH₃SS(=O)H are ?38.3 and ?16.6 kcal mol^?1, respectively, where the difference is in enthalpy RSO–H versus RS(=O)–H bonding. The C–H bond energy of CH₃SSOH is 99.2 kcal mol^?1, and the O–H bond energy is weaker at 76.9 kcal mol^?1. Cleavage of the weak O–H bond in CH₃SSOH results in an electron rearrangement upon loss of the CH₃SSO–H hydrogen atom; the radical rearranges to form the more stable CH₃SS· = O radical structure. Cleavage of the C–H bond in CH₃SS(=O)H results in an unstable [CH₂SS(=O)H]* intermediate, which decomposes exothermically to lower energy CH₂ = S + HSO. The CH₃SS(=O)–H bond energy is quite weak at 54.8 kcal mol^?1 with the H–C bond estimated at between 91 and 98 kcal mol^?1. Disulfide bond energies for CH₃S–SOH and CH3S–S(=O)H are low: 67.1 and 39.2 kcal mol^?1. Copyright © 2011 John Wiley & Sons, Ltd.     

First-principles study on the electronic and magnetic properties of InN nanosheets doped with 2p elements

The electronic structure of InN nanosheets doped by light elements (Be, B, C, and O) is studied based on spin-polarized density functional theory within the generalized gradient approximation. The results show that the Be and C dopants in InN nanosheets induce spin polarized states in the band gap, or near the valence band, which generates local magnetic moments of 1.0 µ_B with one dopant atom. Due to the exchange spin-splitting, the three 2p electrons of Be atom are all in p_x and p_y orbitals (↑↑↓). So Be will coordinate with host atoms by σ coordination bond. The long-range ferromagnetic order above room temperature is attributed to p–p coupling. For C atom, the configuration of the five 2p electrons is (↑↑↑↓↓), and the unpaired electron is in p_z(↑) orbital. So the π bond will be formed between C atom and other atoms. Due the weak π bond cannot support long-range coupling, no stable magnetism is sustained if two C dopants are separated by longer than 3.58 Å.     

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利用分子动力学方法研究了H原子与C/Be样品的相互作用过程,当H原子轰击C/Be样品时,发现有一些H原子渗入样品中并且滞留在样品中,H原子的滞留率随H原子的初始入射能量的升高呈线性增长,有些沉积在样品中H原子与C原子相互作用形成H-C键。溅射产物以H原子和H2分子为主。H和H2的产额率随初始入射能量的变化趋势相反,分析了不同机制下产物H和H2的产额率随初始入射能量的关系,且通过分析H原子的入射能量和样品的原子密度的关系来研究轰击后的样品,发现样品中原子分布变化很小,同时分析了化合物中的化学键分布变化较小,只是其化学键的分布峰向样品表面移动。     

Hydrogen-bonding studies of amino acid side-chains with DNA base pairs

The interactions of the amino acid side-chains arginine (ARG), aspartic acid (ASP), asparagine (ASN), lysine (LYS) and serine (SER) with nucleic acid base pairs have been investigated using theoretical methods. The interaction energy of the short intermolecular N–H?···?N, N–H?···?O, O–H?···?O, O–H?···?N, C–H?···?O and C–H?···?N hydrogen bonds present in both isolated base pairs and complexes and its role in providing stability to the complexes have been explored. The homonuclear interactions are found to be stronger than the heteronuclear interactions. An improper hydrogen bond has been observed for some of the N–H?···?O and N–H?···?N hydrogen-bond interactions with the contraction of the N–H bond varying from 0.001 to 0.0260?Å and the corresponding blue shift of the stretching frequency by 4–291?cm^?1. Localized molecular orbital energy decomposition analysis (LMOEDA) reveals that the major contributions to the energetics are from the long-range polarization (PL) interaction, and the short-range attractive (ES, EX) and repulsive (REP) interactions. The Bader's atoms in molecules (AIM) theory shows good correlation for the electron density and its Laplacian at the bond critical points (BCP) with the N–H?···?N and N–H?···?O hydrogen-bond lengths in the complexes, and gives a proper explanation for the stability of the structure. The charge-transfer from the proton acceptor to the antibonding orbital of the X–H bond in the complexes was studied using natural bond orbital (NBO) analysis.     

Effect of proton donors on the intramolecular coordination C=O→Si–F in (acyloxymethyl)trifluorosilanes. Ab initio,DFT and FTIR study,QTAIM analysis

The intramolecular С=O→Si coordination in H‐complexes of (acetoxymethyl)trifluorosilane and (benzoyloxymethyl)trifluorosilane with proton donors HCl, PhOH, MeOH, and CHCl₃ was investigated by density functional theory and second‐order Møller‐Plesset perturbation theory (MP2) methods. Interrelation and mutual influence of the intramolecular coordination bond С=O→Si and intermolecular hydrogen bonds C=O···H and Si–F···H in H‐complexes was established using the AIM and NBO analyses. The С=O→Si coordination is weakened by the C=O···H hydrogen bonding but enhanced by the Si–F_ax···H hydrogen bonding. The structure of H‐complexes of (acetoxymethyl)trifluorosilane with proton donors in solution was determined by comparing the ν(C=O) and ν(Si–F) frequencies calculated using the conductor‐like polarizable continuum model and their experimental Fourier transform infrared values. Copyright © 2014 John Wiley & Sons, Ltd.     

Shell-model studies of the N=14 and 16 shell closures in neutron-rich nuclei

Shell-model studies on the N=14 and 16 shell closures in neutron-rich Be, C, O and Ne isotopes are presented. We calculate, with the WBT interaction, the excited states in these nuclei. The calculations agree with recent experiment data. Excited energies and B(E2) values are displayed to discuss the shell closures. Our results support the N=16 shell closure in these isotopes, while indicating a disappearance of N=14 shell closure in Be and C isotopes.