Based on the first principles density functional theory,the equilibrium geometric structure and surface electronic properties of Cl and H2O co-adsorption on the Fe(100) surface are investigated.The results indicate th...Based on the first principles density functional theory,the equilibrium geometric structure and surface electronic properties of Cl and H2O co-adsorption on the Fe(100) surface are investigated.The results indicate that the optimal adsorption site for Cl and H2O co-adsorption on the Fe(100) surface is the location of Cl at the bridge site and H2O at the top site.Compared with the Fe(100)/H2O adsorption system,remarkable changes in geometric structure and electronic properties occur,owing to the presence of Cl in the Fe(100)/(H2O+Cl) adsorption system.The analysis of equilibrium geometric structure and surface electronic properties shows that the presence of Cl in the Fe(100)/(H2O+Cl) adsorption system unstablizes the Fe surface,making it easy to lose electrons.展开更多
The reaction mechanism and kinetics for the addition of hydroxyl radical （OH） to phenol have been investigated using the hybrid density functional （B3LYP） method with the 6-31＋＋G（2dp, 2dr） basis set and the co...The reaction mechanism and kinetics for the addition of hydroxyl radical （OH） to phenol have been investigated using the hybrid density functional （B3LYP） method with the 6-31＋＋G（2dp, 2dr） basis set and the complete basis set （CBS） method using APNO basis sets, respectively. The equilibrium geometries, energies, and thermodynamics properties of all the stationary points along the addition reaction pathway are calculated. The rate constants and the branching ratios of each channel are evaluated using classical transition state theory （TST） in the temperature range of 210 to 360 K, to simulate temperatures in all parts of the troposphere. The ortho addition pathway is dominant and accounts for 99.8%-96.7% of the overall adduct products from 210 to 360 K. The calculated rate constants are in good agreement with existing experimental values. The addition reaction is irreversible.展开更多
The equilibrium geometries, potential energy curves, spectroscopic dissociation energies of the ground and low-lying electronic states of He2, He2^＋ and He2^＋＋ are calculated using symmetry adapted cluster/symmetry...The equilibrium geometries, potential energy curves, spectroscopic dissociation energies of the ground and low-lying electronic states of He2, He2^＋ and He2^＋＋ are calculated using symmetry adapted cluster/symmetry adapted cluster-configuration interaction （SAC/SAC-CI） method with the basis sets CC-PV5Z. The corresponding dissociation limits for all states are derived based on atomic and molecular reaction statics. The analytical potential energy functions of these states are fitted with Murrell-Sorbie potential energy function from our calculation results. The spectroscopic constants Be, αe, ωe, and ωeχe of these states are calculated through the relationship between spectroscopic data and analytical energy function, which are in well agreement with the experimental data. In addition, the origin of the energy barrier in the ground state X^I∑9^＋ of He2^＋＋ energy curve are explained using the avoided crossing rules of valence bond model.展开更多
基金Supported by the National Natural Science Foundation of China (Grant Nos.50675112,50721004)Research Fund for the Doctoral Program of Higher Education (Grant No.20070003103)
文摘Based on the first principles density functional theory,the equilibrium geometric structure and surface electronic properties of Cl and H2O co-adsorption on the Fe(100) surface are investigated.The results indicate that the optimal adsorption site for Cl and H2O co-adsorption on the Fe(100) surface is the location of Cl at the bridge site and H2O at the top site.Compared with the Fe(100)/H2O adsorption system,remarkable changes in geometric structure and electronic properties occur,owing to the presence of Cl in the Fe(100)/(H2O+Cl) adsorption system.The analysis of equilibrium geometric structure and surface electronic properties shows that the presence of Cl in the Fe(100)/(H2O+Cl) adsorption system unstablizes the Fe surface,making it easy to lose electrons.
基金supported by the National Natural Science Foundation of China (20977064)
文摘The reaction mechanism and kinetics for the addition of hydroxyl radical （OH） to phenol have been investigated using the hybrid density functional （B3LYP） method with the 6-31＋＋G（2dp, 2dr） basis set and the complete basis set （CBS） method using APNO basis sets, respectively. The equilibrium geometries, energies, and thermodynamics properties of all the stationary points along the addition reaction pathway are calculated. The rate constants and the branching ratios of each channel are evaluated using classical transition state theory （TST） in the temperature range of 210 to 360 K, to simulate temperatures in all parts of the troposphere. The ortho addition pathway is dominant and accounts for 99.8%-96.7% of the overall adduct products from 210 to 360 K. The calculated rate constants are in good agreement with existing experimental values. The addition reaction is irreversible.
基金Supported by the Natural Science Foundation of Shaanxi Province of China under Grant No. 2009JM1007
文摘The equilibrium geometries, potential energy curves, spectroscopic dissociation energies of the ground and low-lying electronic states of He2, He2^＋ and He2^＋＋ are calculated using symmetry adapted cluster/symmetry adapted cluster-configuration interaction （SAC/SAC-CI） method with the basis sets CC-PV5Z. The corresponding dissociation limits for all states are derived based on atomic and molecular reaction statics. The analytical potential energy functions of these states are fitted with Murrell-Sorbie potential energy function from our calculation results. The spectroscopic constants Be, αe, ωe, and ωeχe of these states are calculated through the relationship between spectroscopic data and analytical energy function, which are in well agreement with the experimental data. In addition, the origin of the energy barrier in the ground state X^I∑9^＋ of He2^＋＋ energy curve are explained using the avoided crossing rules of valence bond model.
