Quantum chemical calculations were used to estimate the bond dissociation energies （BDEs） for 13 substituted chlorobenzene compounds. These compounds were studied by the hybrid density functional theory （B3LYP, B3P...Quantum chemical calculations were used to estimate the bond dissociation energies （BDEs） for 13 substituted chlorobenzene compounds. These compounds were studied by the hybrid density functional theory （B3LYP, B3PW91, B3P86） methods together with 6-31G^＊＊ and 6-311G^＊＊ basis sets. The results show that B3P86/6-311G^＊＊ method is the best method to compute the reliable BDEs for substituted chlorobenzene compounds which contain the C-C1 bond. It is found that the C-C1 BDE depends strongly on the computational method and the basis sets used. Substituent effect on the C-C1 BDE of substituted chlorobenzene compounds is further discussed. It is noted that the effects of substitution on the C-C1 BDE of substituted chlorobenzene compounds are very insignificant. The energy gaps between the HOMO and LUMO of studied compounds estimate the relative thermal stability ordering are also investigated and from this data we of substituted chlorobenzene compounds.展开更多
We establish a general convergence theory of the Shift-Invert Residual Arnoldi(SIRA)method for computing a simple eigenvalue nearest to a given targetσand the associated eigenvector.In SIRA,a subspace expansion vecto...We establish a general convergence theory of the Shift-Invert Residual Arnoldi(SIRA)method for computing a simple eigenvalue nearest to a given targetσand the associated eigenvector.In SIRA,a subspace expansion vector at each step is obtained by solving a certain inner linear system.We prove that the inexact SIRA method mimics the exact SIRA well,i.e.,the former uses almost the same outer iterations to achieve the convergence as the latter does if all the inner linear systems are iteratively solved with low or modest accuracy during outer iterations.Based on the theory,we design practical stopping criteria for inner solves.Our analysis is on one step expansion of subspace and the approach applies to the Jacobi-Davidson(JD)method with the fixed targetσas well,and a similar general convergence theory is obtained for it.Numerical experiments confirm our theory and demonstrate that the inexact SIRA and JD are similarly effective and are considerably superior to the inexact SIA.展开更多
基金This work was supported by the National Natural Science Foundation of China （No.10774039）.
文摘Quantum chemical calculations were used to estimate the bond dissociation energies （BDEs） for 13 substituted chlorobenzene compounds. These compounds were studied by the hybrid density functional theory （B3LYP, B3PW91, B3P86） methods together with 6-31G^＊＊ and 6-311G^＊＊ basis sets. The results show that B3P86/6-311G^＊＊ method is the best method to compute the reliable BDEs for substituted chlorobenzene compounds which contain the C-C1 bond. It is found that the C-C1 BDE depends strongly on the computational method and the basis sets used. Substituent effect on the C-C1 BDE of substituted chlorobenzene compounds is further discussed. It is noted that the effects of substitution on the C-C1 BDE of substituted chlorobenzene compounds are very insignificant. The energy gaps between the HOMO and LUMO of studied compounds estimate the relative thermal stability ordering are also investigated and from this data we of substituted chlorobenzene compounds.
基金supported by National Basic Research Program of China(Grant No.2011CB302400)National Natural Science Foundation of China(Grant No.11071140)
文摘We establish a general convergence theory of the Shift-Invert Residual Arnoldi(SIRA)method for computing a simple eigenvalue nearest to a given targetσand the associated eigenvector.In SIRA,a subspace expansion vector at each step is obtained by solving a certain inner linear system.We prove that the inexact SIRA method mimics the exact SIRA well,i.e.,the former uses almost the same outer iterations to achieve the convergence as the latter does if all the inner linear systems are iteratively solved with low or modest accuracy during outer iterations.Based on the theory,we design practical stopping criteria for inner solves.Our analysis is on one step expansion of subspace and the approach applies to the Jacobi-Davidson(JD)method with the fixed targetσas well,and a similar general convergence theory is obtained for it.Numerical experiments confirm our theory and demonstrate that the inexact SIRA and JD are similarly effective and are considerably superior to the inexact SIA.
