Computational study on the addition of HCN to methanimine catalyzed by formamidine and formamide

In this paper, we have carried out a theoretical study on the addition of HCN to methanimine with formamidine or formamide using second-order Moller-Plesset perturbation (MP2) method with 6-31 + G(d,p) basis sets. At MP2 level. a high-energy, intermediate has been located for each pathway. The addition of HCN to methanimine with formamidine has the lowest free energy barrier according to the calculations at MP2 level. (C) 2004 Elsevier B.V. All rights reserved.

A DFT study on isomorphously substituted MCM-22 zeolite

The density functional theory has been used to study the isomorphously substituted MCM-22 zeolite for the first time. The effect of the basis sets on the calculation results is discussed in details. Data of several index properties for characterizing the relative acidity of T-MCM-22 (T = B, Al, Ga, and Fe), including proton affinity, bond length and bond angle, OH stretching frequency, and charge on the acidic proton, show that the acidity of T-MCM-22 increases in the sequence of B-MCM-22 < Fe-MCM-22 < Ga-MCM-22 < Al-MCM-22. After making a correction, the calculated OH stretching frequencies for Al-MCM-22 and Fe-MCM-22 show a reasonable agreement with the experimental data. On the basis of an equilibrium structure of the B-MCM-22 zeolite, the effect of the B element in the synthesis of the Ti-MCM-22 is also discussed. The adding of the B element during the synthesis of the Ti-MCM-22 can decrease greatly the Ti substitution energy because of the forming of a structure quite similar to the terminal silanol group. The results can provide some constructively information for zeolite synthesis.

Analytical potential energy function and spectroscopic parameters for the ground and excited states of NaH

set of energies at different internuclear distances for the ground electronic state and two excited electronic states of NaH molecule have been calculated using valence internally contracted multireference configuration interaction(MRCI) including Davidson correction and three basis sets. Then, a potential energy curve (PEC) for each state was determined by extrapolating MRCI energies to the complete basis sets limit. Based on the PECs, accurate vibrational energy levels and rotational constants were determined. The computational PECs are were fitted to analytical potential energy functions using the Murrell-Sorbie potential function. Then, accurate spectroscopic parameters were calculated. Compared with experimental results, values obtained with the basis set extrapolation yield a potential energy curve that gives accurate vibrational energy levels, rotational constants and spectroscopic parameters for the NaH molecule. (C) 2004 Elsevier B.V. All rights reserved.

Theoretical study on analytical potential function and spectroscopic parameters for CaF molecule

The equilibrium properties and potential energy curves of the ground electronic state of CaF have been calculated using the Brueckner Doubles calculation with a triples contribution added [BD(T)] and the gradient-corrected density functional theory with three-parameter exact exchange mixing (B3LY-P) method, with 6-311 + G*,6-311 + G(2df,2pd) and 6-311 + G(3df,3pd) basis sets. All the computational PECs are fitted to analytical potential energy functions using Murrell-Sorbie, Huxley and Tang-Toennies potentials. Based on this, the spectroscopic parameters are calculated, and then compared with some other theoretical and experimental data. (C) 2004 Elsevier B.V. All rights reserved.

Density functional studies of diatomic LaO to LuO

Bond distances, vibrational frequencies, electron affinities, ionization potentials, dissociation energies and dipole moments of the title molecules in neutral, positively and negatively charged ions were studied by use of density functional method. Ground electronic state was assigned for each molecule. The bonding patterns were analyzed and compared with both the available data and across the series. It was found that besides ionic component, covalent bonds are formed between the metal s, d and f orbitals and oxygen p orbitals. Contrary to the well known lanthanide contraction, the bond distance is not regular from LaO to LuO for both neutral and charged molecules. An obvious population at 5d orbital was observed through the lanthanide series. 4f electrons also participate the chemical bonding for CeO to NdO and TbO to TmO. For EuO, GdO, YbO and LuO, 4f electrons tend to be localized. The spin multiplicity is regular for neutral and charged molecules. The spin multiplicity of the charged molecules can be obtained by -1 (or +1 for TbO+, DyO+, YbO- and YbO+) compared with the corresponding neutral molecules.

Structural stability and electronic state of transition metal trimers

Ground state geometries were searched for transition metal trimers Sc-3, Y-3, La-3, Lu-3, Ti-3, Zr-3, and Hf-3 by density functional methods. For all the studied trimers, our calculation indicates that the ground state geometries are either equilateral triangle (Zr-3 and Hf-3) or near equilateral triangle (Ti-3, Sc-3, Y-3, La-3, and Lu-3). For rare earth trimers Sc-3, Y-3, La-3, and Lu-3, isosceles triangle (near equilateral triangle) at quartet state is the ground state. Isosceles triangle at doublet state is the competitive candidate for the ground state. For Zr-3 and Hf-3, equilateral triangle at singlet state is the most stable. For Ti-3, isosceles triangle (near equilateral triangle) at quintet state gives the ground state. For Sc-3, Zr-3, and Hf-3, where experimental results are available, the predicted geometries are in agreement with experiment in which the ground state is equilateral triangle (Zr-3) or fluxional (Sc-3 and Hf-3). For Y-3, the calculated geometry is in agreement with experimental observation and previous theoretical study that Y-3 is a bent molecule for the ground state.

Ground state of lutetium dimer by density functional methods

Bond distances, vibrational frequencies and dissociation energies for the ground state of Lu-2 were studied by density functional methods B3LYP, B3PW91, BLYP, BHLYP, BP86, B3P86, MPW1PW91, PBE1PBE and SVWN with CEP-121G and SDD basis sets. Singlet state is predicted to be the most stable. CEP-121G has a better overall performance than SDD. At CEP-121G basis set, all density functional methods used in this study perform well in reproducing the spectroscopic constants.

Electron affinities and ionization potentials of 4d and 5d transition metal atoms by CCSD(T), MP2 and density functional theory

The electron affinities and ionization potentials of 4d and 5d transition metal atoms were studied by CCSD(T), MP2 and density functional methods. The calculated results indicate that density functional method B3LYP has the best overall performance in predicting both electron affinity and ionization potential. SVWN gives largest IP and EA for 4d and 5d atoms. For the two basis sets used in this study, LANL2DZ and SDD, the performance of B3LYP/SDD combination is better than B3LYP/LANL2DZ, in particular for electron affinity calculation.

FUZZY SOLID SETS FOR MATHEMATICAL MORPHOLOGY AND OPTICAL IMPLEMENTATION

Fuzzy sets in the subject space are transformed to fuzzy solid sets in an increased object space on the basis of the development of the local umbra concept. Further, a counting transform is defined for reconstructing the fuzzy sets from the fuzzy solid sets, and the dilation and erosion operators in mathematical morphology are redefined in the fuzzy solid-set space. The algebraic structures of fuzzy solid sets can lead not only to fuzzy logic but also to arithmetic operations. Thus a fuzzy solid-set image algebra of two image transforms and five set operators is defined that can formulate binary and gray-scale morphological image-processing functions consisting of dilation, erosion, intersection, union, complement, addition, subtraction, and reflection in a unified form. A cellular set-logic array architecture is suggested for executing this image algebra. The optical implementation of the architecture, based on area coding of gray-scale values, is demonstrated. (C) 1995 Optical Society of America

Practical Criterion for Universal Laws and Practical Methods for Construction of Co-variance Sets

给出相对论力学中普遍定律的实用判别法和协变集的实用构造法,还给出实现非普遍定律的“可导出性”的一种实用方法．

Phase-step calibration technique based on a two-run-times-two-frame phase-shift method

A novel phase-step calibration technique is presented on the basis of a two-run-times-two-frame phase-shift method. First the symmetry factor M is defined to describe the distribution property of the distorted phase due to phase-shifter miscalibration; then the phase-step calibration technique, in which two sets of two interferograms with a straight fringe pattern are recorded and the phase step is obtained by calculating M of the wrapped phase map, is developed. With this technique, a good mirror is required, but no uniform illumination is needed and no complex mathematical operation is involved. This technique can be carried out in situ and is applicable to any phase shifter, whether linear or nonlinear. (c) 2006 Optical Society of America.