Complex-forming reactions widely exist in gas-phase chemical reactions. Various complexforming bimolecular reactions have been investigated and interesting phenomena have been discovered. The complex-forming reactions...Complex-forming reactions widely exist in gas-phase chemical reactions. Various complexforming bimolecular reactions have been investigated and interesting phenomena have been discovered. The complex-forming reactions usually have small or no barrier in the entrance channel, which leads to obvious differences in kinetic and dynamic characteristics compared with direct reactions. Theoretically, quantum state-resolved reaction dynamics can provide the most detailed microscopic dynamic mechanisms and is now feasible for a direct reaction with only one potential barrier. However, it is of great challenge to construct accurate potential energy surfaces and perform accurate quantum dynamics calculations for a complex polyatomic reaction involving deep potential wells and multi-channels. This paper reviews the most recent progress in two prototypical oxyhydrogen complex-forming reaction systems, HO2 and HO3, which are significant in combustion, atmospheric, and interstellar chemistry. We will present a brief survey of both computational and experimental work and emphasize on some unsolved problems existing in these systems.展开更多
A new potential energy surface is presented for the triplet state 3At of the chemical reaction S(3P)+H2 from a set of accurate ab initio data. The single point energies are computed using highly correlated complete...A new potential energy surface is presented for the triplet state 3At of the chemical reaction S(3P)+H2 from a set of accurate ab initio data. The single point energies are computed using highly correlated complete active space self-consistent-field and multi-reference configuration interaction wave functions with a basis set of aug-cc-pV5Z. We have fitted the full set of energy values using many-body expansion method with an Aguado-Paniagua function. Based on the new potential energy surface, we carry out the time-dependent wave packet scattering calculations over the collision energy range of 0.8-2.2 eV. Both the centrifugalsudden approximation and Coriolis Coupling cross sections are obtained. In addition, the total reaction probabilities are calculated for the reactant H2 initially in the vibrational states v=0-3 (j=0). It is found that initial vibrational excitation enhances the title reaction.展开更多
Electrochimcal behaviors of rusticyanin (Rus.) isolated from Acidithiobacillus ferrooxidans were investigated through Rus.-ZnS-QDs/L-Cys/Au electrode. The cyclic voltammetric results indicate that rusticyanin immobi...Electrochimcal behaviors of rusticyanin (Rus.) isolated from Acidithiobacillus ferrooxidans were investigated through Rus.-ZnS-QDs/L-Cys/Au electrode. The cyclic voltammetric results indicate that rusticyanin immobilized on the surface of Rus.-ZnS-QDs/L-Cys/Au electrode can undergo a direct quasi-reversible electrochemical reaction. The immobilized rusticyanin is not denatured and still retains its activity in the temperature range of 19-43 ℃. The reduction ability of the protein increases and its oxidation ability becomes weak with the increase of pH from 6.0 to 7.8. Fe^2+ ions in the solution can promote the electron transfer kinetics of the immobilized rusticyanin and make its peak potentials (φp) markedly move negatively.展开更多
The energy utilization consistency method in process integration extracts the key component of process energy utilization, and simplifies the procedure of process analysis and integration. The method allows the conver...The energy utilization consistency method in process integration extracts the key component of process energy utilization, and simplifies the procedure of process analysis and integration. The method allows the conversion of the total process energy integration into a synthesis problem of a pseudo-heat exchanger network. The advantages of using the energy utilization consistency and the pseudo-temperature methods are presented by two examples of integration of large-scale complex processes. The improved genetic algorithm is proved to be an effective tool in the retrofitting procedures.展开更多
In this paper we give an appropriate energy equation considering the diffusion and the energy production contributions of species for a complex coupled system with chemical reaction. It is shown that the contribution ...In this paper we give an appropriate energy equation considering the diffusion and the energy production contributions of species for a complex coupled system with chemical reaction. It is shown that the contribution of the mass diffusion on the internal energy is the same whether it is introduced by the mass flow through the outer boundary or by the inner chemical reaction. In addition, the diffusion is a purely irreversible process and does not produce reversible entropy or entropy flow. Based on this theory a new entropy production rate equation is derived for the coupled thermal diffusive chemical heterogeneous system. The evolution equations of the heat conduction and the mass diffusion derived from this theory are fully consistent with the Fourier and Fick's laws.展开更多
Within the framework of the dynamical cluster decay model (DCM), the in evaporation cross-sections (σ1n) of cold fusion reactions (Pb and Bi targets) are calculated for ZCN = 104-113 superheavy nuclei. The calc...Within the framework of the dynamical cluster decay model (DCM), the in evaporation cross-sections (σ1n) of cold fusion reactions (Pb and Bi targets) are calculated for ZCN = 104-113 superheavy nuclei. The calculations are carried out in the fixed range of excitation energy ECN = 15 ± 1 MeV, so that the comparative analysis of reaction dynamics can be worked out. First of all, the fission barriers (Bf ) and neutron separation energies (S1n) are estimated to account the decreasing cross-sections of cold fusion reactions. In addition to this, the importance of hot optimum orientations of β24-deformed nuclei over cold one is explored at fixed angular momentum and neck-length parameters. The hot optimum orientations support all the target-projectile (t,p) combinations, which are explored experimentally in the cold fusion reactions. Some new target-projectile combinations are also predicted for future exploration. Further, the In cross-sections are addressed for ZCN = 104-113 superheavy nuclei at comparable excitation energies which show the decent agrement with experimental data upto ZCN = 109 nuclei. Finally, to understand the dynamics of higher-Z superheavy nuclei, the cross-sections are also calculated at maximum available energies around the Coulomb barrier and the effect of non-sticking moment of inertia (INS) is also investigated at these energies.展开更多
基金supported by the National Natural Science Foundation of China (No.91641104, No.21733006, and No.21590802)
文摘Complex-forming reactions widely exist in gas-phase chemical reactions. Various complexforming bimolecular reactions have been investigated and interesting phenomena have been discovered. The complex-forming reactions usually have small or no barrier in the entrance channel, which leads to obvious differences in kinetic and dynamic characteristics compared with direct reactions. Theoretically, quantum state-resolved reaction dynamics can provide the most detailed microscopic dynamic mechanisms and is now feasible for a direct reaction with only one potential barrier. However, it is of great challenge to construct accurate potential energy surfaces and perform accurate quantum dynamics calculations for a complex polyatomic reaction involving deep potential wells and multi-channels. This paper reviews the most recent progress in two prototypical oxyhydrogen complex-forming reaction systems, HO2 and HO3, which are significant in combustion, atmospheric, and interstellar chemistry. We will present a brief survey of both computational and experimental work and emphasize on some unsolved problems existing in these systems.
文摘A new potential energy surface is presented for the triplet state 3At of the chemical reaction S(3P)+H2 from a set of accurate ab initio data. The single point energies are computed using highly correlated complete active space self-consistent-field and multi-reference configuration interaction wave functions with a basis set of aug-cc-pV5Z. We have fitted the full set of energy values using many-body expansion method with an Aguado-Paniagua function. Based on the new potential energy surface, we carry out the time-dependent wave packet scattering calculations over the collision energy range of 0.8-2.2 eV. Both the centrifugalsudden approximation and Coriolis Coupling cross sections are obtained. In addition, the total reaction probabilities are calculated for the reactant H2 initially in the vibrational states v=0-3 (j=0). It is found that initial vibrational excitation enhances the title reaction.
基金Project(2010CB630903) supported by the National Basic Research Program of ChinaProject(50621063) supported by the National Natural Science Foundation of China
文摘Electrochimcal behaviors of rusticyanin (Rus.) isolated from Acidithiobacillus ferrooxidans were investigated through Rus.-ZnS-QDs/L-Cys/Au electrode. The cyclic voltammetric results indicate that rusticyanin immobilized on the surface of Rus.-ZnS-QDs/L-Cys/Au electrode can undergo a direct quasi-reversible electrochemical reaction. The immobilized rusticyanin is not denatured and still retains its activity in the temperature range of 19-43 ℃. The reduction ability of the protein increases and its oxidation ability becomes weak with the increase of pH from 6.0 to 7.8. Fe^2+ ions in the solution can promote the electron transfer kinetics of the immobilized rusticyanin and make its peak potentials (φp) markedly move negatively.
文摘The energy utilization consistency method in process integration extracts the key component of process energy utilization, and simplifies the procedure of process analysis and integration. The method allows the conversion of the total process energy integration into a synthesis problem of a pseudo-heat exchanger network. The advantages of using the energy utilization consistency and the pseudo-temperature methods are presented by two examples of integration of large-scale complex processes. The improved genetic algorithm is proved to be an effective tool in the retrofitting procedures.
文摘In this paper we give an appropriate energy equation considering the diffusion and the energy production contributions of species for a complex coupled system with chemical reaction. It is shown that the contribution of the mass diffusion on the internal energy is the same whether it is introduced by the mass flow through the outer boundary or by the inner chemical reaction. In addition, the diffusion is a purely irreversible process and does not produce reversible entropy or entropy flow. Based on this theory a new entropy production rate equation is derived for the coupled thermal diffusive chemical heterogeneous system. The evolution equations of the heat conduction and the mass diffusion derived from this theory are fully consistent with the Fourier and Fick's laws.
基金Supported by the Council of Scientific and Industrial Research(CSIR),in the Form of Research Project Grant No.03(1341)/15/EMR-Ⅱ and to DST,New DelhiINSPIRE-Fellowship Grant No.DST/INSPIRE/03/2015/000199
文摘Within the framework of the dynamical cluster decay model (DCM), the in evaporation cross-sections (σ1n) of cold fusion reactions (Pb and Bi targets) are calculated for ZCN = 104-113 superheavy nuclei. The calculations are carried out in the fixed range of excitation energy ECN = 15 ± 1 MeV, so that the comparative analysis of reaction dynamics can be worked out. First of all, the fission barriers (Bf ) and neutron separation energies (S1n) are estimated to account the decreasing cross-sections of cold fusion reactions. In addition to this, the importance of hot optimum orientations of β24-deformed nuclei over cold one is explored at fixed angular momentum and neck-length parameters. The hot optimum orientations support all the target-projectile (t,p) combinations, which are explored experimentally in the cold fusion reactions. Some new target-projectile combinations are also predicted for future exploration. Further, the In cross-sections are addressed for ZCN = 104-113 superheavy nuclei at comparable excitation energies which show the decent agrement with experimental data upto ZCN = 109 nuclei. Finally, to understand the dynamics of higher-Z superheavy nuclei, the cross-sections are also calculated at maximum available energies around the Coulomb barrier and the effect of non-sticking moment of inertia (INS) is also investigated at these energies.