Nitrogen molecules Nx have been the subject of much recent research because of their potential as high-energy materials. Many nitrogen molecules dissociate with very low barriers, including molecules such as acyclic N...Nitrogen molecules Nx have been the subject of much recent research because of their potential as high-energy materials. Many nitrogen molecules dissociate with very low barriers, including molecules such as acyclic N4 that are essentially unbound. A number of studies have reported the ability of heteroatoms to stabilize complex nitrogen molecules. In the present study, the energetic and electronic properties of scandium（Ⅰ） and titanium（Ⅱ） complexes with N2 and N4 are calculated and discussed. Dissociation energies and singlet-triplet energies are determined by theoretical calculations using second-order perturbation theory （MP2） in conjunction with the Dunning basis sets.展开更多
The ultrafast dynamics and dissociative ionization of CS2 were studied using the pump-probe method with time-of-flight mass spectroscopy. The transient behavior of both parent ion (CS2+) and fragment ions (S+ and CS+)...The ultrafast dynamics and dissociative ionization of CS2 were studied using the pump-probe method with time-of-flight mass spectroscopy. The transient behavior of both parent ion (CS2+) and fragment ions (S+ and CS+) was observed. It was found that all the ionic signals decay exponentially with lifetimes that were different for delay times, t>0 and t<0, which can be attributed to the evolution of different Rydberg states pumped by 267-nm and 400-nm laser pulses. The lifetimes of two Rydberg states were obtained simultaneously from one fitting of the transients. The fragment ions were produced by the dissociation of CS2+, and it is suggested that the final ionic state is the C2Σg+ state of CS2+ based on the measured S+/CS+ branching ratio. The S+/CS+ ratio is dependent on the delay time of the two lasers, indicating that the dissociation process of CS2+ is related to the evolution of the intermediate Rydberg state.展开更多
The properties of dissolution in different solvents,the specific heat capacity and thermal decomposition process under the non-isothermal conditions for energetic triazole ionic salts 1,2,4-triazolium nitrate(1a),1,2,...The properties of dissolution in different solvents,the specific heat capacity and thermal decomposition process under the non-isothermal conditions for energetic triazole ionic salts 1,2,4-triazolium nitrate(1a),1,2,3-triazolium nitrate(1b),3,4,5triamino-1,2,4-triazolium nitrate(2a),3,4,5-triamino-1,2,4-triazolium dinitramide(2b)were precisely measured using a Calvet Microcalorimeter.The thermochemical equation,differential enthalpies of dissolution(△difH m ),standard molar enthalpies of dissolution(△difH m ),apparent activation energy(E),pre-exponential constant(A),kinetic equation,linear relationship of specific heat capacity with temperature over the temperature range from 283 to 353 K,standard molar heat capacity(C p,m)and enthalpy,entropy and Gibbs free energy at 283–353 K,taking 298.15 K as the benchmark for 1a,1b,2a and 2b were obtained with treating experimental data and theoretical calculation method.The kinetic and thermodynamic parameters of thermal decomposition reaction,critical temperature of thermal explosion(Tb),self-accelerating decomposition temperature(TSADT)and adiabatic time-to-explosion(t)of 1a,1b,2a and 2b were calculated.Their heat-resistance abilities were evaluated.Information was obtained on the relation between molecular structures and properties of 1a,1b,2a and 2b.展开更多
基金The Alabama Supercomputer Authority is gratefully acknowledged for a grant of computer time on the SGI Altix in Huntsville, AL. This work was supported by the National Science Foundation （NSF/HBCU-UP grant 0505872）. SJ is supported by NSF/HBCU-UP as an undergraduate scholar. This work was also supported by the National Institutes of Health （NIHINCMHD 1P20MD000547-01） and the Petroleum Research Fund, administered by the American Chemical Society （PRF 43798-B6）. AH is supported by the NIH as an undergraduate scholar in the Minority Access to Research Careers program （NIH/NIGMS 2T34GM008167-22A 1）. The taxpayers of the state of Alabama in particular and the United States in general are gratefully acknowledged.
文摘Nitrogen molecules Nx have been the subject of much recent research because of their potential as high-energy materials. Many nitrogen molecules dissociate with very low barriers, including molecules such as acyclic N4 that are essentially unbound. A number of studies have reported the ability of heteroatoms to stabilize complex nitrogen molecules. In the present study, the energetic and electronic properties of scandium（Ⅰ） and titanium（Ⅱ） complexes with N2 and N4 are calculated and discussed. Dissociation energies and singlet-triplet energies are determined by theoretical calculations using second-order perturbation theory （MP2） in conjunction with the Dunning basis sets.
基金supported by the National Natural Science Foundation of China (10874056 and 10534010)
文摘The ultrafast dynamics and dissociative ionization of CS2 were studied using the pump-probe method with time-of-flight mass spectroscopy. The transient behavior of both parent ion (CS2+) and fragment ions (S+ and CS+) was observed. It was found that all the ionic signals decay exponentially with lifetimes that were different for delay times, t>0 and t<0, which can be attributed to the evolution of different Rydberg states pumped by 267-nm and 400-nm laser pulses. The lifetimes of two Rydberg states were obtained simultaneously from one fitting of the transients. The fragment ions were produced by the dissociation of CS2+, and it is suggested that the final ionic state is the C2Σg+ state of CS2+ based on the measured S+/CS+ branching ratio. The S+/CS+ ratio is dependent on the delay time of the two lasers, indicating that the dissociation process of CS2+ is related to the evolution of the intermediate Rydberg state.
基金supported by the National Natural Science Foundation of China (20573098)the Science and Technology Foundation of National Key Lab of Science and Technology on Combustion and Explosion in China (9140C3503030805)
文摘The properties of dissolution in different solvents,the specific heat capacity and thermal decomposition process under the non-isothermal conditions for energetic triazole ionic salts 1,2,4-triazolium nitrate(1a),1,2,3-triazolium nitrate(1b),3,4,5triamino-1,2,4-triazolium nitrate(2a),3,4,5-triamino-1,2,4-triazolium dinitramide(2b)were precisely measured using a Calvet Microcalorimeter.The thermochemical equation,differential enthalpies of dissolution(△difH m ),standard molar enthalpies of dissolution(△difH m ),apparent activation energy(E),pre-exponential constant(A),kinetic equation,linear relationship of specific heat capacity with temperature over the temperature range from 283 to 353 K,standard molar heat capacity(C p,m)and enthalpy,entropy and Gibbs free energy at 283–353 K,taking 298.15 K as the benchmark for 1a,1b,2a and 2b were obtained with treating experimental data and theoretical calculation method.The kinetic and thermodynamic parameters of thermal decomposition reaction,critical temperature of thermal explosion(Tb),self-accelerating decomposition temperature(TSADT)and adiabatic time-to-explosion(t)of 1a,1b,2a and 2b were calculated.Their heat-resistance abilities were evaluated.Information was obtained on the relation between molecular structures and properties of 1a,1b,2a and 2b.
