Theoretical Study on the C-H Activation in Decarbonylation of Acetaldehyde by NiL_2(L=SO_3CH_3) Using Density Functional Theory

Density functional theory calculations were carried out to explore the potential energy surface（PES） associated with the gas-phase reaction of Ni L2（L=SO3CH3） with acetone. The geometries and energies of the reactants, intermediates, products and transition states of the triplet ground potential energy surfaces of [Ni, O, C2, H4] were obtained at the B3LYP/6-311＋＋G（d,p） levels in C,H,O atoms and B3LYP/ Lanl2 dz in Ni atom. It was found through our calculations that the decabonylation of acetaldehyde contains four steps including encounter complexation, C-C activation, aldehyde H-shift and nonreactive dissociation. The results revealed that C-C activation induced by Ni L2（L=SO3CH3） led to the decarbonylation of acetaldehyde.

Tunable Electronic and Magnetic Properties from Structure Phase Transition of Layered Vanadium Diselenide

The atomic geometry, structure stability, electronic and magnetic properties of VSe2 were systematically investigated based on the density functional theory（DFT）. Varying from 3D to 2D four VSe2 structures, bulk 2H-VSe2 and 1T-VSe2, monolayer H-VSe2 and T-VSe2 are all demonstrated as thermodynamically stable by lattice dynamic calculations. More interestingly, the phase transition temperature is dramatically different due to the lattice size. Finally, owing to different crystal structures, H-VSe2 is semimetallic whereas T-VSe2 is totally metallic and also they have different magnetic moments. Our main argument is that being exfoliated from bulk to monolayer, 2H-VSe2 transforms to T-VSe2, accompanied by both semimetallic-metallic transition and dramatic magnetic moment variation. Our calculations provide a novel structure phase transition and an efficient way to modulate the electronic structure and magnetic moment of layered VSe2, which suggests potential applications as high-performance functional nanomaterial.

Theoretical and Experimental Studies on the Reaction Mechanism of Cl_2 + I_2 = 2ICl

The gas phase reaction mechanism of Cl2 ＋ I2 = 2ICl has been theoretically investigated by DFF method at the B3LYP/3-21 G＊ level. Transition states of three reaction channels were consequently given. The results indicate that in the title reaction the least activation energy of bi-molecular reaction was smaller than the dissociation energies of I2 and Cl2, and thus the reaction mechanism was the course of molecule-molecule interaction at low reaction rate. If other factors such as illumination were taken into account, I2 could dissociate into I atoms and then react with Cl2, or Cl2 dissociates into CI atoms and reacts with I2. These were photochemical reactions with high reaction speed. The theoretical results were further validated with absorbance measurement at 516 nm.

Heat Kernel Estimates for Non-symmetric Finite Range Jump Processes

In this paper,we first establish the sharp two-sided heat kernel estimates and the gradient estimate for the truncated fractional Laplacian under gradient perturbation S^(b):=△^(α/2)+b·▽,where △^(α/2) is the truncated fractional Laplacian,α∈(1,2) and b ∈ K_(d)^(α-1).In the second part,for a more general finite range jump process,we present some sufficient conditions to allow that the two sided estimates of the heat kernel are comparable to the Poisson type function for large distance |x-y|in short time.

Estimation of 1-dimensional nonlinear stochastic differential equations based on higher-order partial differential equation numerical scheme and its application

A method based on higher-order partial differential equation （PDE） numerical scheme are proposed to obtain the transition cumulative distribution function （CDF） of the diffusion process （numerical differentiation of the transition CDF follows the transition probability density function （PDF））, where a transformation is applied to the Kolmogorov PDEs first, then a new type of PDEs with step function initial conditions and 0, 1 boundary conditions can be obtained. The new PDEs are solved by a fourth-order compact difference scheme and a compact difference scheme with extrapolation algorithm. After extrapolation, the compact difference scheme is extended to a scheme with sixth-order accuracy in space, where the convergence is proved. The results of the numericM tests show that the CDF approach based on the compact difference scheme to be more accurate than the other estimation methods considered; however, the CDF approach is not time-consuming. Moreover, the CDF approach is used to fit monthly data of the Federal funds rate between 1983 and 2000 by CKLS model.