Biomedical subjects

Heming Xiao

Publications and source records attributed to Heming Xiao.

5 recordsLinked to original sources

PubMed2006

Ab initio study of energetic solids: cupric azide, mercuric azide, and lead azide.

We presented a detailed study on the electronic structure and optical properties of cupric azide (Cu(N(3))(2)), mercuric azide (alpha-Hg(N(3))(2)), and lead azide (alpha-Pb(N(3))(2)) by using density functional theory within the generalized gradient approximation. Relaxed crystal structures compare well with experimental data. An analysis of electronic structure, charge transfer, and bond order shows that Cu(N(3))(2) and alpha-Hg(N(3))(2) are covalent-type solids, whereas alpha-Pb(N(3))(2) is an ionic-type solid but has weak covalent character. The valence bands of Cu(N(3))(2) and alpha-Hg(N(3))(2) arise from the contributions of the metal-d and N-p states, whereas that of alpha-Pb(N(3))(2) are strongly dominated by N-p states and not from Pb-d states. The general shapes of the real and imaginary parts of the dielectric function, adsorption coefficient, and photoconductivity spectra for the three azides are similar. Our calculated optical properties are found to be in agreement with available experimental data. The absorption spectra show a number of absorption peaks in the fundamental absorption region. All the photoconductivity spectra display a broad photocurrent response in the fundamental absorption region. The density of states of the three azides reveal the effects of the metal states on the valence electron of the azide group and so are correlated with their impact sensitivity.

Journal Article↗

PubMed2006

Crystal density predictions for nitramines based on quantum chemistry.

An efficient and convenient method for predicting the crystalline densities of energetic materials was established based on the quantum chemical computations. Density functional theory (DFT) with four different basis sets (6-31G(**), 6-311G(**), 6-31+G(**), and 6-311++G(**)) and various semiempirical molecular orbital (MO) methods have been employed to predict the molecular volumes and densities of a series of energetic nitramines including acyclic, monocyclic, and polycyclic/cage molecules. The relationships between the calculated values and experimental data were discussed in detail, and linear correlations were suggested and compared at different levels. The calculation shows that if the selected basis set is larger, it will expend more CPU (central processing unit) time, larger molecular volume and smaller density will be obtained. And the densities predicted by the semiempirical MO methods are all systematically larger than the experimental data. In comparison with other methods, B3LYP/6-31G(**) is most accurate and economical to predict the solid-state densities of energetic nitramines. This may be instructive to the molecular designing and screening novel HEDMs.

Aniline Compounds↗

PubMed2006

Comparative first-principles study of structural and optical properties of alkali metal azides.

A comparative first-principles study of the structural and optical properties of the alkali metal azides has been performed with density functional theory within the generalized gradient approximation. The crystal structures of the alkali azides compare well with experimental data. Their ionic character is manifested by the closeness of their internitrogen distances to the calculated N-N bond length for the free azide ion. An analysis of electronic structure, charge transfer, and bond order shows that the alkali azides are all wide-gap insulators and ionic compounds. The energy band and density of states for lithium azide and alpha-sodium azide are very similar, while these for potassium azide, alpha-rubidium azide, and alpha-cesium azide are alike, but some modifications are observed with the increment of alkali metals' electropositivity. These changes are closely related to the differences of the crystal structures. The general shapes of the real and imaginary parts of the dielectric function, adsorption coefficient, and electron energy-loss spectra are quite similar. The peaks originate from the electron transitions from the alkali metal s and p states to the conduction band. Our calculated optical properties for the alkali azides are found to be in good agreement with available experimental data. The absorption spectra of the alkali azides show a number of absorption peaks, which are believed to be associated with different exciton states, in the fundamental absorption region. In general, the electron energy-loss spectra have two plasma frequencies.

Journal Article↗

PubMed2006

Theoretical studies on the structures, thermodynamic properties, detonation properties, and pyrolysis mechanisms of spiro nitramines.

Density function theory (DFT) has been employed to study the geometric and electronic structures of a series of spiro nitramines at the B3LYP/6-31G level. The calculated results agree reasonably with available experimental data. Thermodynamic properties derived from the infrared spectra on the basis of statistical thermodynamic principles are linearly correlated with the number of nitramine groups as well as the temperature. Detonation performances were evaluated by the Kamlet-Jacobs equations based on the calculated densities and heats of formation. It is found that some compounds with the predicted densities of ca. 1.9 g/cm3, detonation velocities over 9 km/s, and detonation pressures of about 39 GPa (some even over 40 GPa) may be novel potential candidates of high energy density materials (HEDMs). Thermal stability and the pyrolysis mechanism of the title compounds were investigated by calculating the bond dissociation energies (BDE) at the B3LYP/6-31G level and the activation energies (E(a)) with the selected PM3 semiempirical molecular orbital (MO) based on the unrestricted Hartree-Fock model. The relationships between BDE, E(a), and the electronic structures of the spiro nitramines were discussed in detail. Thermal stabilities and decomposition mechanisms of the title compounds derived from the B3LYP/6-31G BDE and the UHF-PM3 E(a) are basically consistent. Considering the thermal stability, TNSHe (tetranitrotetraazaspirohexane), TNSH (tetranitrotetraazaspiroheptane), and TNSO (tetranitrotetraazaspirooctane) are recommended as the preferred candidates of HEDMs. These results may provide basic information for the molecular design of HEDMs.

Journal Article↗

PubMed2005

Non-isothermal kinetics of the dehydration reaction of 3-nitro-1,2,4-triazol-5-one rubidium and cesium complexes.

3-Nitro-1,2,4-triazol-5-one (NTO) rubidium and cesium complexes were synthesized by mixing the aqueous solution of NTO and their respective metal carbonates. Their thermal decomposition and the non-isothermal kinetics of the dehydration reaction were studied under the non-isothermal condition by DSC and TG-DTG methods. The kinetic parameters were obtained from analysis of the DSC and TG-DTG curves by Kissinger method, Ozawa method, the differential method and the integral method. The most probable mechanism functions for the dehydration reaction of the title complexes were suggested by comparing the kinetic parameters. The dehydration decomposition reaction of RbNTO.H2O and CsNTO.H2O appears to be the same as Avrami-Erofeev equation: f(alpha) = (5/2)(1-alpha)[-ln(1-alpha)](3/5), G(alpha)=[-ln(1-alpha)](2/5), n = 2/5. The critical temperature of thermal explosion is 240.88 degrees C for RbNTO.H2O and 246.27 degrees C for CsNTO.H2O.

Cesium↗