The equilibrium structures, the charge population, and the spectroscopic properties of UO, UO2, UO3, and U2O3 molecules are systematically investigated using the density functional theory （DFT） with the method of ge...The equilibrium structures, the charge population, and the spectroscopic properties of UO, UO2, UO3, and U2O3 molecules are systematically investigated using the density functional theory （DFT） with the method of generalized gradient approximation （GGA）. The bond lengths and the vibrational frequencies of the ground states of UO, UO2, and UO3 molecules are all in agreement with available experimental data. For U2O3 molecules, our calculations indicate that the ground state of the U203 molecule is an XTA1 state with Dah （trigonal bipyramid） symmetry （R1 （U O）=0.2113 nm, R2（U1 U2）=0.2921 nm, ZU1OU2 = 87.5° , dihedral angle O（U,O1,O2,O3）=62.40°）. The harmonic frequency, the IR intensity and the spin density of the U2Oa molecule are all obtained for the first time in theory. For the ground state of U203 molecules, the vibrational frequencies are 178.46 （Ai）, 276.79 （E1＇＇）, 310.77 （EL）, 396.63 （AS＇）, 579.15 （El）, and 614.98 （A1＇） cm-1. The vibrational modes corresponding to the IR maximum peaks are worked out for UO3 and U203 molecules. Besides, the results of Gophinatan-Jng bond order indicate that UO, UO2, and UO3 molecules possess U=O double bonds and that the U203 molecule possesses U O single bonds and a U-U single bond.展开更多
Compared chemical bonds change situation of coal surface and oxygen mole- cules before and after coal surface adsorption to three oxygen molecules,after adsorption each oxygen molecule's chemical bond got longer,b...Compared chemical bonds change situation of coal surface and oxygen mole- cules before and after coal surface adsorption to three oxygen molecules,after adsorption each oxygen molecule's chemical bond got longer,but had not broken,the coal surface's chemical bonds changed a little.It proves that the coal surface adsorption to five oxygen molecules is the physical adsorption and is the multilayer adsorption according to the op- timized geometry structure.The oxygen molecule's bond length that adsorbed by the side chain of coal surface changes most from 1.258 2×10^(-10) m to 1.316 8×10^(-10) m,which indi- cates this oxygen molecular to be the liveliest.The analysis of charge population reveals that how many electrons shift in the atom is directly proportional to the change of chemical bonds.The more electrons shift in the atom,the more molecule chemical bond changes. In the adsorption state,which is composed of coal surface and five oxygen molecules,the vibration frequency of oxygen molecules drops off,and the adsorption energy reached by calculation is 202.11 kJ/mol.展开更多
文摘The equilibrium structures, the charge population, and the spectroscopic properties of UO, UO2, UO3, and U2O3 molecules are systematically investigated using the density functional theory （DFT） with the method of generalized gradient approximation （GGA）. The bond lengths and the vibrational frequencies of the ground states of UO, UO2, and UO3 molecules are all in agreement with available experimental data. For U2O3 molecules, our calculations indicate that the ground state of the U203 molecule is an XTA1 state with Dah （trigonal bipyramid） symmetry （R1 （U O）=0.2113 nm, R2（U1 U2）=0.2921 nm, ZU1OU2 = 87.5° , dihedral angle O（U,O1,O2,O3）=62.40°）. The harmonic frequency, the IR intensity and the spin density of the U2Oa molecule are all obtained for the first time in theory. For the ground state of U203 molecules, the vibrational frequencies are 178.46 （Ai）, 276.79 （E1＇＇）, 310.77 （EL）, 396.63 （AS＇）, 579.15 （El）, and 614.98 （A1＇） cm-1. The vibrational modes corresponding to the IR maximum peaks are worked out for UO3 and U203 molecules. Besides, the results of Gophinatan-Jng bond order indicate that UO, UO2, and UO3 molecules possess U=O double bonds and that the U203 molecule possesses U O single bonds and a U-U single bond.
基金National Natural Science Foundation(50474010)Eleventh Five Year Key Technologies(2006BAK03B05)
文摘Compared chemical bonds change situation of coal surface and oxygen mole- cules before and after coal surface adsorption to three oxygen molecules,after adsorption each oxygen molecule's chemical bond got longer,but had not broken,the coal surface's chemical bonds changed a little.It proves that the coal surface adsorption to five oxygen molecules is the physical adsorption and is the multilayer adsorption according to the op- timized geometry structure.The oxygen molecule's bond length that adsorbed by the side chain of coal surface changes most from 1.258 2×10^(-10) m to 1.316 8×10^(-10) m,which indi- cates this oxygen molecular to be the liveliest.The analysis of charge population reveals that how many electrons shift in the atom is directly proportional to the change of chemical bonds.The more electrons shift in the atom,the more molecule chemical bond changes. In the adsorption state,which is composed of coal surface and five oxygen molecules,the vibration frequency of oxygen molecules drops off,and the adsorption energy reached by calculation is 202.11 kJ/mol.
