Electronic structure and stability of BP clusters: theoretical calculations for (BP)n (n = 2–4)

The geometry, electronic configurations, harmonic vibrational frequencies, and stability of the structural isomers of boron phosphide clusters have been investigated using density functional theory (DFT). CCSD(T) calculations show that the lowest‐energy structures are cyclic (IIt, IVs) with D_nh symmetry for dimers and trimers. The caged structure for B₄P₄ lie higher in energy than the monocyclic structure with D_2d symmetry (VIs). The B–P bond dominates the structures for many isomers, so that one preferred dissociation channel is loss of the BP monomer. The hybridization and chemical bonding in the different structures are also discussed. Comparisons with boron nitride clusters, the ground state structures of B_nP_n (n = 2, 3) clusters are analogous to those of their corresponding B_nN_n (n = 2, 3) counterparts. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2006     

Ethanol production from cellulose by coupled saccharification/fermentation usingSaccharomyces cerevisiae and cellulase complex fromSclerotiun rolfsii UV-8 mutant

Using cellulase/hemicellulase complex of Sclerotium rolfsii UV-8 mutant and Saccharomyces cerevisiae for fermentation, the coupled saccharification/fermentation (CSF) of 15% AT-rice straw was carried out at 40 degrees C, pH 4.5 for the first 24 h and further incubation was performed at 30 degrees C for 72 h. Increasing the amount of cellulase activity from 3-12 IU FPA/g of substrate resulted in increased yields of ethanol from 1.5-3.6% in 96 h. It has been observed that the coupled system was advantageous over the two stage (separate hydrolysis/fermentation) system as it produced higher amounts of ethanol from cellulose (3.6% as compared to 2.3% ethanol from rice straw).     

Hylleraas method for many‐electron atoms. I. The Hamiltonian

A general expression for the nonrelativistic Hamiltonian for n‐electron atoms with the fixed nucleus approximation is derived in a straightforward manner using the chain rule. The kinetic energy part is transformed into the mutually independent distance coordinates r_i, r_ij, and the polar angles θ_i, and φ_i. This form of the Hamiltonian is very appropriate for calculating integrals using Slater orbitals, not only of states of S symmetry, but also of states with higher angular momentum, as P states. As a first step in a study of the Hylleraas method for five‐electron systems, variational calculations on the ²P ground state of boron atom are performed without any interelectronic distance. The orbital exponents are optimized. The single‐term reference wave function leads to an energy of ?24.498369 atomic units (a.u.) with a virial factor of η = 2.0000000009, which coincides with the Hartree–Fock energy ?24.498369 a.u. A 150‐term wave function expansion leads to an energy of ?24.541246 a.u., with a factor of η = 1.9999999912, which represents 28% of the correlation energy. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Symmetry breaking and finite-size effects in quantum many-body systems

We consider a quantum many-body system on a lattice which exhibits a spontaneous symmetry breaking in its infinite-volume ground states, but in which the corresponding order operator does not commute with the Hamiltonian. Typical examples are the Heisenberg antiferromagnet with a Néel order and the Hubbard model with a (superconducting) off-diagonal long-range order. In the corresponding finite system, the symmetry breaking is usually obscured by quantum fluctuation and one gets a symmetric ground state with a long-range order. In such a situation, Horsch and von der Linden proved that the finite system has a low-lying eigenstate whose excitation energy is not more than of orderN ^–1, whereN denotes the number of sites in the lattice. Here we study the situation where the broken symmetry is a continuous one. For a particular set of states (which are orthogonal to the ground state and with each other), we prove bounds for their energy expectation values. The bounds establish that there exist ever-increasing numbers of low-lying eigenstates whose excitation energies are bounded by a constant timesN ^–1. A crucial feature of the particular low-lying states we consider is that they can be regarded as finite-volume counterparts of the infinite-volume ground states. By forming linear combinations of these low-lying states and the (finite-volume) ground state and by taking infinite-volume limits, we construct infinite-volume ground states with explicit symmetry breaking. We conjecture that these infinite-volume ground states are ergodic, i.e., physically natural. Our general theorems not only shed light on the nature of symmetry breaking in quantum many-body systems, but also provide indispensable information for numerical approaches to these systems. We also discuss applications of our general results to a variety of interesting examples. The present paper is intended to be accessible to readers without background in mathematical approaches to quantum many-body systems.     

Sampling of benzene in tar matrices from biomass gasification using two different solid-phase sorbents

Biomass tar mainly consists of stable aromatic compounds such as benzene and polyaromatic hydrocarbons, benzene being the biggest tar component in real biomass gasification gas. For the analysis of individual tar compounds, the solid-phase adsorption method was chosen. According to this method, tar samples are collected on a column with an amino-phase sorbent. With a high benzene concentration in biomass tar, some of the benzene will not be collected on the amino-phase sorbent. To get over this situation, we have installed another column with activated charcoal which is intended for collection of volatile organic compounds, including benzene, after the column with the amino-phase sorbent. The study of maximal adsorption amounts of various compounds on both adsorbents while testing different sampling volumes led to the conclusion that benzene is a limiting compound. The research proved that the use of two sorbents (500 mg + 100 mg) connected in series allows for assessment of tar in synthesis gas with a tar concentration up to 30-40 g m(-3), which corresponds to the requirements of most gasifiers.     

On the asymptotics of solutions of the Lane-Emden problem for the p-Laplacian

In this paper we consider the Lane–Emden problem adapted for the p-Laplacian

Synergistic UV protection effects of the lignin nanodiamond complex

There are various concerns with current sunscreen actives in the sun care industry which pushes for a natural-based active that is sustainable as well as effective. Lignin is a natural polymer, capable of ultraviolet (UV) filtration and maintaining photostability. In this study, a variety of tuneable lignin-poly(ethylene glycol) (LP) nanodiamond (LP–ND) complexes were developed with varying ratios of LP to NDs. There are two fractions of LP–NDs, which use detonation NDs (LP–rNDs) and furnace NDs (LP–mNDs). Both complexes demonstrated favorable UV filtration, enhanced photostability, and uniform dispersion in water and cream. The LP–mND had maintained its particle size at <200 nm with an increasing LP ratio from 0.5 to 20 times as opposed to the increased particle size of the LP–rND. The LP–mND complex excelled in its photostability during solar radiation from 1 h to 6 h, demonstrating its effectiveness in absorbing 70% in the UV B region. Results had indicated enhanced synergistic effect of LP–rNDs and LP–mNDs with commercial sunscreen. The LP–rND complex had enhanced the sunscreen from 29 to 62, whereas the LP–mND had further boosted the sun protection factor to 89. In a nutshell, the lignin nanodiamond complexes offer a sustainable alternative to current actives in the industry.     

Structure and dynamics of cationic van-der-Waals clusters

Ar_nHCl⁺ van-der-Waals clusters for n = 1–13 are investigated with the “minimal diatomics-in-molecules (DIM) model” using ab-initio input data obtained from multi-reference configuration-interaction calculations plus subsequent projection onto valence-bond wavefunctions. The results for the complexes with n = 1–3 are checked against ab-initio calculations at the coupled-cluster (CCSD) level with the same one-electron atomic basis set as for the input data generation (aug-cc-pVTZ from Dunning). In addition to the electronic ground state, the first excited state for the triatomic complex (n = 1) is also studied. The results from the DIM model are shown to be in fair agreement with those from advanced conventional ab-initio calculations, although there are differences in detail. The comparison justifies the extension of the DIM approach to n > 3. Systematic analysis of the local minima of the multi-dimensional potential-energy surfaces (PESs), carried out with the combined method described in part I (Monte-Carlo sampling plus subsequent steepest-descent optimization), reveals simple building-up regularities for the most stable structures (i.e. those corresponding to the global PES minimum) at each n: apart from always having a nearly linear (Ar–H–Cl)⁺ fragment as core, the aggregates show little or no symmetry. Secondary local minima are also determined and their structures interpreted. The PESs for the low-lying excited states reveal a much more complicated topography compared to the Ar_nH⁺ clusters allowing a variety of photo-processes. The energy level sequence of the first five excited electronic states and the stability of the clusters in these states is studied as a function of the cluster size n.     

A quantum chemical approach towards the electronically excited states of helium clusters

We have investigated the electronic energies of the ground and excited states of an octahedral helium cluster by quantum chemical ab initio calculations. The excited levels were calculated for the central atom for a set of different inter atomic separations. Our approach yields potential energy curves which are suited to describe a density dependence of the spectral features as previously observed in photo excitation experiments. The potential energy curves of the 2s and 2p states show a hump at ? caused by the strong perturbation of neighbouring atoms. The existence of this hump explains the experimentally observed blue shift and its dependence on the cluster size or density, respectively. The potential curves of the higher levels show almost constant energies. Perturbations of these levels are small, because the overlap between the Rydberg orbital and the orbitals of the surrounding atoms is small. This is the case for both small R values where the Rydberg orbital is well outside the cluster as well as for large R where the density drastically decreases. These findings coincide with the un-shifted features of small clusters observed in experiments.     

Ni-Fe-Al-O双金属催化剂在生物质基2-羟基四氢吡喃还原胺化合成5-氨基-1-戊醇中的性能研究北大核心CSCD

采用共沉淀法制备了不同Fe/Ni摩尔比(0、0.125、0.25、0.5和0.75)的Al_(2)O_(3)负载型NiFe单、双金属催化剂,并考察了它们在生物糠醛衍生2-羟基四氢吡喃(2-HTHP)还原胺化合成高附加值5-氨基戊醇反应中的催化性能.研究发现当Fe/Ni摩尔比为0.25时表现出最高的5-氨基戊醇收率(在80℃和2 MPa优化条件下达90%).利用N_(2)吸脱附、X射线衍射(XRD)、氢气程序升温还原(H_(2)-TPR)、透射电镜(TEM)等技术对催化剂进行了表征,结果表明适量Fe的掺入可以提高催化剂的分散性和还原性,同时在还原活化催化剂中形成Ni-Fe合金相,继而使相应催化剂表现出更优异的催化活性.通过固定床对比考察了催化剂的稳定性,NiFe(0.25)-Al-O双金属催化剂表现出明显优于NiFe(0)-Al-O单金属催化剂的稳定性,运行120 h前者只有微弱失活而后者显著失活.对比反应后催化剂表征发现,金属Fe的修饰可以有效抑制金属活性颗粒的烧结和流失,从而显著提高其反应稳定性.