The low-lying singlet and triplet states of HCB and HBC, and doublet states of HCB- and HBC- are examined using ab initio molecular orbital theory at the HF/TZP, FOCI/MCSCF level. For the neutral molecules, several ne...The low-lying singlet and triplet states of HCB and HBC, and doublet states of HCB- and HBC- are examined using ab initio molecular orbital theory at the HF/TZP, FOCI/MCSCF level. For the neutral molecules, several new low-lying electroinc states are found, and the linear triplet structures are found to have the lowest energy. For the anions, the 2 ∑+ states are lower in energy than the 2Π states. For HCB, the 3Π state is 15.38kcal·mol-1 more stable than the 3∑- state, and for HBC the 3Π is 2.51kcal·mol-1 below the 3∑- state at the first order configuration interaction (FOCI) level. The barriers of the conversion of HBC(3Π) to HCB(3Π), HBC(1△(1A1)) to HCB(1A’C3) and HBC(1△(1A2)) to HCB(1A"C3) are 23.21, 12.97 and 21.09kcal·mol-1,respectively. The activation energies of the conversion of HBC-(2∑+) to HCB(2∑+) and HCB-(2Π) to HBC-(2Π) are 18.13 and 25.88kcal·mol-1, respectively. A symmetry breaking phenomenon is observed in several states. The harmonic vibrational frequencies of the neutral molecules and the anions are also reported to provide information for the possible experimental observation of these species.展开更多
Effects of natural organic matters(NOM) and hydrated metal oxides(HMO) in sediments on the anaerobic degradation of γ 666, p,p' DDT and HCB were investigated by means of removing NOM and HMO in Liaohe R...Effects of natural organic matters(NOM) and hydrated metal oxides(HMO) in sediments on the anaerobic degradation of γ 666, p,p' DDT and HCB were investigated by means of removing NOM and HMO in Liaohe River sediments sequentially. The results showed that the anaerobic degradation of γ 666, p,p' DDT and HCB followed pseudo first order kinetics in different sediments. But, the extents and rates of degradation were different, even the other conditions remained the same. Anaerobic degradation rates of γ 666, p,p' DDT and HCB were 0 020 d -1 , 0 009 d -1 and 0 035 month -1 respectively for the sediments without additional carbon resources. However, with addition of carbon resources, the anaerobic degradation rates of γ 666, p, p ' DDT and HCB were 0 071 d -1 , 0 054 d -1 and 0 088 month -1 in the original sediments respectively. After removing NOM, the rates were decreased to 0 047 d -1 , 0 037 d -1 and 0 066 month -1 ; in the sediments removed NOM and HMO, the rates were increased to 0 067 d -1 , 0 059 d -1 and 0 086 month -1 . These results indicated that NOM in the sediments accelerated the anaerobic degradation of γ 666, p,p' DDT and HCB; the HMO inhibited the anaerobic degradation of γ 666, p,p' DDT and HCB.展开更多
文摘The low-lying singlet and triplet states of HCB and HBC, and doublet states of HCB- and HBC- are examined using ab initio molecular orbital theory at the HF/TZP, FOCI/MCSCF level. For the neutral molecules, several new low-lying electroinc states are found, and the linear triplet structures are found to have the lowest energy. For the anions, the 2 ∑+ states are lower in energy than the 2Π states. For HCB, the 3Π state is 15.38kcal·mol-1 more stable than the 3∑- state, and for HBC the 3Π is 2.51kcal·mol-1 below the 3∑- state at the first order configuration interaction (FOCI) level. The barriers of the conversion of HBC(3Π) to HCB(3Π), HBC(1△(1A1)) to HCB(1A’C3) and HBC(1△(1A2)) to HCB(1A"C3) are 23.21, 12.97 and 21.09kcal·mol-1,respectively. The activation energies of the conversion of HBC-(2∑+) to HCB(2∑+) and HCB-(2Π) to HBC-(2Π) are 18.13 and 25.88kcal·mol-1, respectively. A symmetry breaking phenomenon is observed in several states. The harmonic vibrational frequencies of the neutral molecules and the anions are also reported to provide information for the possible experimental observation of these species.
文摘Effects of natural organic matters(NOM) and hydrated metal oxides(HMO) in sediments on the anaerobic degradation of γ 666, p,p' DDT and HCB were investigated by means of removing NOM and HMO in Liaohe River sediments sequentially. The results showed that the anaerobic degradation of γ 666, p,p' DDT and HCB followed pseudo first order kinetics in different sediments. But, the extents and rates of degradation were different, even the other conditions remained the same. Anaerobic degradation rates of γ 666, p,p' DDT and HCB were 0 020 d -1 , 0 009 d -1 and 0 035 month -1 respectively for the sediments without additional carbon resources. However, with addition of carbon resources, the anaerobic degradation rates of γ 666, p, p ' DDT and HCB were 0 071 d -1 , 0 054 d -1 and 0 088 month -1 in the original sediments respectively. After removing NOM, the rates were decreased to 0 047 d -1 , 0 037 d -1 and 0 066 month -1 ; in the sediments removed NOM and HMO, the rates were increased to 0 067 d -1 , 0 059 d -1 and 0 086 month -1 . These results indicated that NOM in the sediments accelerated the anaerobic degradation of γ 666, p,p' DDT and HCB; the HMO inhibited the anaerobic degradation of γ 666, p,p' DDT and HCB.
