1-丁基-3-甲基咪唑氯盐-水和2，6-二甲氧基苯酚混合物中分子相互作用的衰减全反射红外光谱研究

Molecular interactions of the ternary mixtures of 1-butyl-3-methylimidazolium chloride ([C₄C₁im]Cl)-water-2,6-dimethoxyphenol (2,6-DMP, a phenolic monomer lignin model compound) were investigated in comparison with the [C₄C₁im]Cl-water binary systems through attenuated total reflection infrared spectroscopy. Results indicated that the microstructures of water and [C₄C₁im]Cl changed with varying mole fraction of [C₄C₁im]Cl (^xIL) from 0.01 to 1.0. This change was mainly attributed to the interactions of [C₄C₁im]Cl-water and the self-aggregation of [C₄C₁im]Cl through hydrogen bonding. The band shifts of C-H on imidazolium ring and the functional groups in 2,6-DMP indicated that the occurrence of intermolecular interactions by different mechanisms (i.e., hydrogen bonding or π-π stacking) resulted in 2,6-DMP dissolution. In the case of ^xIL=0.12, the slightly hydrogen-bonded water was fully destroyed and [C₄C₁im]Cl existed in the form of hydrated ion pairs. Interestingly, the maximum 2,6-DMP solubility (238.5 g/100 g) was achieved in this case. The interactions and microstructures of [C₄C₁im]Cl-water mixtures influenced the dissolution behavior of 2,6-DMP.     

The effect of anti-hydrogen bond on Fermi resonance: A Raman spectroscopic study of the Fermi doublet ν1—ν12 of liquid pyridine

The effects of anti-hydrogen bond on the ν₁—ν₁₂ Fermi resonance (FR) of pyridine are experimentally investigated by using Raman scattering spectroscopy. Three systems, pyridine/water, pyridine/formamide, pyridine/carbon tetrachloride, provide varying degrees of strength for the diluent-pyridine anti-hydrogen bond complex. Water forms a stronger anti-hydrogen bond with pyridine than with formamide, and in the case of adding non-polar solvent carbon tetrachloride, which is neither a hydrogen bond donor nor an acceptor and incapable of forming hydrogen bond with pyridine, the intermolecular distance of pyridine will increase and the interaction of pyridine molecules will reduce. The dilution studies are performed on the three systems. Comparing with the values of Fermi coupling coefficient W of the ring breathing mode ν ₁ and triangle mode ν ₁₂ of pyridine at different volume concentrations, which are calculated according to the Bertran equations, in three systems, we find that the solution with the strongest anti-hydrogen bond, water, shows the fastest change in the ν₁—ν₁₂ Fermi coupling coefficient W with the volume concentration varying, followed by the formamide and carbon tetrachloride solutions. These results suggest that the stronger anti-hydrogen bond-forming effect will cause a greater reduction in the strength of the ν₁—ν₁₂ FR of pyridine. According to the mechanism of the formation of anti-hydrogen bond in the complexes and the FR theory, a qualitative explanation for the anti-hydrogen bond effect in reducing the strength of the ν₁—ν₁₂ FR of pyridine is given.     

Density functional study of uranyl （VI） amidoxime complexes

Uranyl (VI) amidoxime complexes are investigated using relativistic density functional theory. The equilibrium structures, bond orders, and Mulliken populations of the complexes have been systematically investigated under a generalized gradient approximation (GGA). Comparison of (acet) uranyl amidoxime complexes ([UO₂(AO)_n]^2-n, 1 ≤ n ≤ 4) with available experimental data shows an excellent agreement. In addition, the U-O(1), U-O(3), C(1)-N(2), and C(3)-N(4) bond lengths of [UO₂(CH₃AO)₄]^2- are longer than experimental data by about 0.088, 0.05, 0.1, and 0.056 Å. The angles of N(3)-O(3)-U, O(2)-N(1)-C(1), N(3)-C(3)-N(4), N(4)-C(3)-C(4), and C(4)-C(3)-N(3) are different from each other, which are due to existing interaction between oxygen in uranyl and hydrogen in amino group. This interaction is found to be intra-molecular hydrogen bond. Studies on the bond orders, Mulliken charges, and Mulliken populations demonstrate that uranyl oxo group functions as hydrogen-bond acceptors and H atoms in ligands act as hydrogen-bond donors forming hydrogen bands within the complex.     

二甲基亚砜溶剂中All-trans-astaxanthin的拉曼和红外光谱

The Raman and infrared spectra of all-trans-astaxanthin (AXT) in dimethyl sulfoxide (DMSO) solvent were investigated experimentally and theoretically. Density functional cal-culations of the Raman spectra predict the splitting of the υ₁ band into υ_1-1 and υ_1-2 compo-nents. The absence of splitting in Raman experimental spectra is ascribed to the competition between the two symmetric C=C stretching vibrations of the backbone chain. The υ₁ band is very sensitive to the excitation wavelength: resonance excitation stimulates the higher-frequency υ_1-2 mode, and off-resonance excitation corresponds to the lower-frequency υ_1-1 mode. Analyses of the intramolecular hydrogen bonding between C=O and O-H in the AXT/DMSO system reveal that the C4=O1...H1-O3 and C4''=O2...H2-O4 bonds are strengthened and weakened, respectively, in the electronically excited state compared with those in the ground state. This result reveals significant variations of the AXT molecular structure in different electronic states.     

First-principles calculation of the lattice compressibility, elastic anisotropy and thermodynamic stability of V2GeC

We investigate the elastic and the thermodynamic properties of nanolaminate V₂GeC by using the ab initio pseudopotential total energy method. The axial compressibility shows that the c axis is always stiffer than the a axis. The elastic constant calculations demonstrate that the structural stability is within 0-800 GPa. The calculations of Young's and shear moduli reveal the softening behaviour at about 300 GPa. The Possion ratio makes a higher ionic or a weaker covalent contribution to intra-atomic bonding and the degree of ionicity increases with pressure. The relationship between brittleness and ductility shows that V₂GeC is brittle in ambient conditions and the brittleness decreases and ductility increases with pressure. Moveover, we find that V₂GeC is largely isotropic in compression and in shear, and the degree of isotropy decreases with pressure. The Gr黱eisen parameter, the Debye temperature and the thermal expansion coefficient are also successfully obtained for the first time.     

Water adsorption on the Be(0001) surface: from monomer to trimer adsorption

In this paper, the density functional theory has been used to perform a comparative theoretical study of water monomer, dimer, trimer, and bilayer adsorptions on the Be(0001) surface. In our calculations, the adsorbed water molecules are energetically favoured adsorbed on the atop sites, and the dimer adsorption is found to be the most stable with a peak adsorption energy of ～437 meV. Further analyses have revealed that the essential bonding interaction between the water monomer and the metal substrate is the hybridization of the water 3a₁-like molecular orbital with the (s, p_z) orbitals of the surface beryllium atoms. While in the case of the water dimer adsorption, the 1b₁-like orbital of the H₂O molecule plays a dominant role.     

Local structure distortion and spin Hamiltonian parameters for Cr3＋-Vzn tetragonal defect centre in Cr3＋ doped KZnF3 crystal

The quantitative relationship between the spin Hamiltonian parameters (D, g_‖, Δg) and the crystal structure parameters for the Cr³⁺—V_Zn tetragonal defect centre in a Cr³⁺:KZnF₃ crystal is established by using the superposition model. On the above basis, the local structure distortion and the spin Hamiltonian parameter for the Cr³⁺—V_Zn tetragonal defect centre in the KZnF_3 crystal are systematically investigated using the complete diagonalization method. It is found that the V_Zn vacancy and the differences in mass, radius and charge between the Cr³⁺ and the Zn²⁺ ions induce the local lattice distortion of the Cr³⁺ centre ions in the KZnF₃ crystal. The local lattice distortion is shown to give rise to the tetragonal crystal field, which in turn results in the tetragonal zero-field splitting parameter D and the anisotropic g factor Δg. We find that the ligand F^- ion along [001] and the other five F^- ions move towards the central Cr³⁺ by distances of Δ₁ = 0.0121 nm and Δ₂ = 0.0026 nm, respectively. Our approach takes into account the spin—orbit interaction as well as the spin—spin, spin—other-orbit, and orbit—orbit interactions omitted in the previous studies. It is found that for the Cr³⁺ ions in the Cr³⁺:KZnF₃ crystal, although the spin—orbit mechanism is the most important one, the contribution to the spin Hamiltonian parameters from the other three mechanisms, including spin—spin, spin—other-orbit, and orbit—orbit magnetic interactions, is appreciable and should not be omitted, especially for the zero-field splitting (ZFS) parameter D.     

Bulk chemical properties of new elements from one-atom-at-a-time data

For the volatile (oxo)halides of known elements the energies of desorption from the surface of fused silica measured in radiochemical gas-solid chromatographic experiments proved close to the sublimation energies. This could hardly be expected for interaction of isolated molecules with bare surface of ionic SiO₂. Because such regularity shows great promise for evaluation of bulk properties of transactinoid compounds we need to understand the origin of apparent inconsistency. The clue seems to be the real structure of the surface. It is initially rough (from μm down to nm scale), inherently heterogeneous at the molecular level, and contains atoms and groups with excessive energy. Exposing to ambient air produces numerous surface ≡SiOH groups. The halogenating agents employed in transactinoid studies chemically modify such surface: it gets tightly covered by halogen atoms and fragments of the agent molecule attached to the Si and O atoms. Now the molecules of new compounds cannot touch SiO₂ lattice; moreover, in some initially geometric wells (due to roughness), they get surrounded by halogen atoms bonded to the surface — the situation resembling that in their own bulk condensed phase. Hence, there must be sites with desorption energies up to the sublimation energy.     

Investigations of spectroscopic parameters and molecular constants for X1Σg+, w3Δu, and W1Δu electronic states of P2 molecule

The potential energy curves (PECs) of three low-lying electronic states (X¹Σ_g⁺, w³Δ_u, and W¹Δ_u)of P₂ molecule are investigated using the full valence complete active space self-consistent field (CASSCF) method followed by the highly accurate valence internally contracted multireference configuration interaction (MRCI) approach in conjunction with the correlation-consistent basis set in the valence range. The PECs of the electronic states involved are modified by the Davidson correction and extrapolated to the complete basis set (CBS) limit. With these PECs, the spectroscopic parameters of the three electronic states are determined and compared in detail with the experimental data. The comparison shows that excellent agreement exists between the present results and the available experimental data. The complete vibrational states are computed for the w³Δ_u, and W¹Δ_u electronic states when the rotational quantum number J equals zero and the vibrational level G(v), the inertial rotation constant B_v, and the centrifugal distortion constant D_v of the first 30 vibrational states are reported, which accord well with the experimental data. The present results show that the two-point extrapolation scheme can obviously improve the quality of spectroscopic parameters and molecular constants.     

丙烷与O(3P)反应机理和动力学的理论研究

The reaction of C₃H₈+O(³P)→C₃H₇+OH is investigated using ab initio calculation and dynamical methods. Electronic structure calculations for all stationary points are obtained using a dual-level strategy. The geometry optimization is performed using the unrestricted second-order Møller-Plesset perturbation method and the single-point energy is computed using the coupled-cluster singles and doubles augmented by a perturbative treatment of triple excitations method. Results indicate that the main reaction channel is C₃H₈+O(³P)→i-C₃H₇+OH. Based upon the ab initio data, thermal rate constants are calculated using the variational transition state theory method with the temperature ranging from 298 K to 1000 K. These calculated rate constants are in better agreement with experiments than those reported in previous theoretical studies, and the branching ratios of the reaction are also calculated in the present work. Furthermore, the isotope effects of the title reaction are calculated and discussed. The present work reveals the reaction mechanism of hydrogen-abstraction from propane involving reaction channel competitions is helpful for the under-standing of propane combustion.     

双金属纳米团簇Au2@Cu6电子结构的稳定性：闭壳层作用和多中心键

采用密度泛函理论方法，研究了近年来实验报道的双金属纳米团簇Au₂@Cu₆的电子结构和成键特征. 一般认为，纳米团簇Au₂@Cu₆中(CuSH)₆环和(Au₂PH₃)₂两部分之间的相互作用可以看作是d¹⁰-σ闭壳相互作用. 然而，化学成键分析表明，两个部分之间存在一个十中心两电子(10c-2e)的多中心键. 将该结构与其他双金属纳米团簇M₂@Cu₆(M=Ag、Cu、Zn、Cd、Hg)做对比分析，结果表明除了d¹⁰-σ闭壳层相互作用外，多中心键也是配合物的电子结构稳定性的原因. 这一结果将为理解闭壳层相互作用提供有利的帮助.     

Ab initio study of synergetic effects of two strong interactions of cation–π interaction and lithium bond in M+ ··· phenyl lithium ··· N (M = Li,Na, K; N = H2O and NH3) complex

Quantum chemical calculations have been performed to investigate the interplay between the cation–π interaction and lithium bonding in the M⁺?···?phenyl lithium?···?OH₂ and M⁺?···?phenyl lithium?···?NH₃ (M?=?Li, Na, K) complexes. The cation–π interaction and lithium bonding in the trimers become stronger relative to the dimers. The interaction energy of cation–π interaction is increased by about 4.4–6.3%, while that of lithium bonding is increased by about 5.2–15.9%. The cooperative energy becomes larger for the stronger cation–π interaction and lithium bond. The F atom and methyl group in the phenyl ring impose a reverse effect on the cation–π interaction and lithium bond. The interaction mechanism in the complexes has been understood with the many-body interaction analysis, electrostatic potentials, and energy decomposition.     

Bonding nature of the actinide tetrafluorides AnF4 (An = Th−Cm)

The knowledge of chemical bonding for actinide fluoride compounds is essential to understand and predict the physical and chemical behaviour of actinide elements in fluoride molten salt. In this work, the bonding nature of actinide tetrafluorides AnF₄ (An = Th?Cm) is investigated by using scalar relativistic density functional theory. Bond order analyses show relatively stronger An–F bonds for An = U?Np and weaker ones for An = Th, Am, and Cm. Despite the dominant ionic character of An–F bonds, a considerable covalent interaction is indicated by the overlap integral value of F 2p and actinide 5f, 6d orbitals. Both natural population analyses and electron density analyses show that An–F covalency rises initially before reducing in the latter systems with the maximum at Np and Pu and the obviously strong ionic bonding character in An = Th, Am, and Cm. Compared to AnCp₄ (Cp = η⁵–C₅H₅) reported in the literature, our study on AnF₄ suggests a much more prominent actinide–ligand covalent interaction. And the roles of orbital overlap and near-degeneracy in driving covalency are discussed.     

Mechanisms responsible for chemical shifts of core-level binding energies and their relationship to chemical bonding

A comprehensive review of different mechanisms which contribute to the chemical shifts of core-level binding energies, BEs, is made. A principle focus is on showing how the mechanisms can be used to relate the BE shifts to features of the chemical bonding and chemical interactions in the studied system. Several initial state mechanisms are identified; while some are well known, the importance of others has been only recognized fairly recently. A theoretical framework is presented which places the analysis and interpretation of these BE shifts on a firm foundation. A rigorous definition and distinction of initial and final state effects is presented. This definition is applied to show that initial state effects are often the dominant factors for the chemical BE shifts. It is also shown that, in many cases, theoretical approaches involving the use of constrained variations can permit a clear and definitive separation of the contributions of the different mechanisms. Several representative applications to the analysis and interpretation of core-level BE shifts are described which show how the theoretical methods of analysis can be used to identify the mechanisms important for the BE shifts. Often more than one mechanism makes an important contribution to the shifts and it is common that the contributions will be canceling. When all of the relevant mechanisms are taken into account in the analysis of the BE shifts, these shifts do provide valuable information about the chemical bonding and electronic structure of the materials being studied. The mechanisms presented and the theoretical frameworks described provide a unified view of BE chemical shifts.     

氢键对2-(N-甲基)氨基-5-硝基吡啶分子非线性光学性质的影响

本文在杂化密度泛函理论水平上研究了溶剂对2-(N-甲基)氨基-5-硝基吡啶分子非线性光学性质的影响.在溶剂中,构造了包括氢键作用的超分子体系,在优化结构的基础上分别研究了由极化连续模型模拟的溶剂与该分子的长程相互作用、溶剂与该分子的氢键相互作用以及溶剂与包括氢键作用的超分子体系整体的相互作用对分子的几何结构、非线性光学性质、紫外吸收光谱和电荷分布等特性的影响.结果表明,溶剂中分子电偶极矩、线性极化率和第一超极化率都增大,而溶剂与溶质分子通过氢键形成的超分子结构与单体有着明显区别.因此,氢键对分子结构和性质的影响较大,从而将明显的影响该类分子的非线性光学性质.     

Cooperative and diminutive interplay between the sodium bonding with hydrogen and dihydrogen bondings in ternary complexes of NaC3N with HMgH and HCN (HNC)

Ternary complexes of NaC₃N with HMgH and HCN (HNC) are connected by sodium, hydrogen and dihydrogen bonds. Molecular geometries and interaction energies of dyads and triads are investigated at the MøllerPlesset perturbation theory of the second order/aug-cc-pVDZ computational level. Particular attention is paid to parameters, such as cooperative energies and many-body interaction energies. Triads with the HMgH molecule located at the end of the chain show an energetic cooperativity ranging between ?2.13 and ?10.53 kJ mol^?1. When the HMgH molecule is located in the middle, the obtained cluster is diminutive with an energetic effect with values 4.39 and 6.77 kJ mol^?1. The electronic properties of the complexes are analysed using parameters derived from the atoms in molecules methodology. Based on the energy decomposition analysis, it can be seen that the stabilities of the complexes are predicted to be attributable mainly to electrostatic effects.     

钴超分子络合物中的氢键相互作用—59Co核磁共振研究及分子模拟

钴超分子络合物[12]aneN₄[Co(CN)₆], [18]aneN₆[Co(CN)_6^], [24] aneN₈[Co(CN)₆], [16] aneN₄[Co(CN)₆], [24] aneN₆[Co(CN)₆]以及[32] aneN₈[Co(CN)₆]中, 氢键相互作用的程度与它们在水溶液中的构象密切相关, 从而引起⁵⁹Co的化学位移向高场移动, 并且其四极矩耦合作用也随构象发生了变化. 实验证明, 络合物中的氢键越强, 化学位移越向高场移动, 四极矩耦合作用也越大. 另一方面, 尺寸大的超分子具有较长的分子转动相关时间,也导致⁵⁹Co具有较短的纵向弛豫时间. 简而言之,⁵⁹Co核磁共振不仅在小分子甚至在超分子络合物中都可以用作理想的探针研究分子的次层或弱相互作用.     

固体酪氨酸^13C化学位移屏蔽张量研究中的氢键作用

应用规范不变原子轨道方法，考虑分子间的氢键作用，对固体酪氨酸＾１３Ｃ化学位移屏蔽张量进行了理论模拟，并对本文结果和以前的计算结果与实验值进行了比较。结果表明：对羧基碳，其理论值和实验值的方均根偏差（不考虑氢键作用）为３３．４ｐｐｍ；而考虑氢键作用，其相应的方均根偏差为２３ｐｐｍ，这表明在氨基酸羧基碳的化学屏蔽研究中考虑分子间的氢键作用是很重要的，特别是δ２２分量，对氢键作用非常敏感，这和ＭｃＤｅｒ     

Theoretical analysis of trends in hydrogen bonding involving halogen acceptors (F−At) covalently bonded to a group 14 atom (C−Pb)

In this work, extensive quantum-chemical calculations have been carried out to identify and elucidate trends in the hydrogen-bonding (HB) interaction involving halogen acceptors covalently bonded to a group 14 atom. A series of 25 heterodimers composed of MH₃X (where M = C?Pb and X = F?At) and HNC molecules have been selected as model complexes stabilised by the HB interaction occurring between the X atom of MH₃X and the H atom of HNC. The interaction energy (E_int) between MH₃X and HNC in the MH₃X···HNC complexes falls in the range from ?2.7 to ?10.8 kcal/mol, indicating weak or medium strength of HB in these complexes. The strength of HB in the complexes remains consistent with the well-known HB weakening as X gets heavier. Regarding the effect of M on E_int, the gradual strengthening of HB is observed while descending group 14, but only from M = Si to M = Pb. The trends in E_int are compared with various HB-related parameters obtained from vibrational analysis, the natural bond orbital (NBO) method, the symmetry-adapted perturbation theory (SAPT) and the quantum theory of atoms in molecules (QTAIM). The parameters that present clear (possibly linear) relationships with E_int have been selected to characterise the effect of M and X on the HB interaction.     

Reorientation dynamics in liquid alcohols from Raman spectroscopy

Polarized Raman spectroscopy has been employed to study the reorientational, or more specifically the translational relaxation dynamics, of alcohol molecules in pure liquids and aqueous solutions. It is found from the spectral width measurements that alcohol molecules in pure liquids have typically translational relaxation times on the order of picoseconds, following the order methanol < ethanol < i‐propanol < n‐propanol. Temperature‐dependent measurements show that hydrogen‐bonding (HB) and hydrophobic interactions control the translational motion. The hydrophobic interaction reduces the relaxation time more apparently in view of the  CH₃ group than the skeleton motion. For alcohol–water mixtures, the increase of water concentration generally slows down the relaxation process in a non‐monotonic behavior. However, the trend stops at a certain point and the motion of alcohol molecules becomes faster when the alcohol concentration further drops. Different mechanisms have been proposed to interpret these observations, which might be helpful to gain deeper insight into the HB networks of alcohols with water. Our study strongly illustrates that Raman spectroscopy can be applied to the study of fast translational motion of molecules in HB systems. Copyright © 2011 John Wiley & Sons, Ltd.