A new contracted CI scheme—adjustable contracted CI scheme—is presented and programed. The efficiency of this scheme is tested by some example calculations. The result shows that the application of the new scheme is...A new contracted CI scheme—adjustable contracted CI scheme—is presented and programed. The efficiency of this scheme is tested by some example calculations. The result shows that the application of the new scheme is flexible and the correlation energy loss is lower than that of the original externally contracted CI method. Keywords: configuration interaction, contracted CI method, correlation energy.展开更多
Potential energy curves （PECs） for the ground state （X2∑＋） and the four excited electronic states （A2∏, B2∏, C2∑＋, 4∏） of a Bell molecule are calculated using the multi-configuration reference single and ...Potential energy curves （PECs） for the ground state （X2∑＋） and the four excited electronic states （A2∏, B2∏, C2∑＋, 4∏） of a Bell molecule are calculated using the multi-configuration reference single and double excited configuration interaction （MRCI） approach in combination with the aug-cc-pVTZ basis sets. The calculation covers the internuclear distance ranging from 0.07 nm to 0.70 nm, and the equilibrium bond length Re and the vertical excited energy Te are determined directly. It is evident that the X2∑＋, A2∏, B2∏, C2∑＋ states are bound and 4∏ is a repulsive excited state. With the potentials, all of the vibrational levels and inertial rotation constants are predicted when the rotational quantum number J is set to be equal to zero （J = 0） by numerically solving the radial SchrSdinger equation of nuclear motion. Then the spectroscopic data are obtained including the rotation coupling constant w e, the anharmonic constant WeXe, the equilibrium rotation constant Be, and the vibration-rotation coupling constant ae. These values are compared with the theoretical and experimental results currently available, showing that they are in agreement with each other.展开更多
The electronic structure of nitrogen trifluoride was investigated by combining the high-resolution electron momentum spectroscopy with the high-level calculations. The experimental binding energy spectra and the momen...The electronic structure of nitrogen trifluoride was investigated by combining the high-resolution electron momentum spectroscopy with the high-level calculations. The experimental binding energy spectra and the momentum distributions of each orbital were compared with the results of Hartree-Fock, density functional theory （DFT）, and symmetry-adapted- cluster configuration-interaction （SAC-CI） methods. SAC-CI and DFT-B3LYP with the aug-cc-pVTZ basis set can well reproduce the binding energy spectra and the observed momentum distributions of the valence orbitals except 1 a2 and 4e orbitals. It was found that the calculated momentum distributions using DFT-B3LYP are even better than those using the high-level SAC-CI method.展开更多
Potential energy curves(PECs) for the ground state(X 2 Σ +) and the four excited electronic states(A 2 Π,B 2 Π,C 2 Σ +,4 Π) of a BeH molecule are calculated using the multi-configuration reference single and doub...Potential energy curves(PECs) for the ground state(X 2 Σ +) and the four excited electronic states(A 2 Π,B 2 Π,C 2 Σ +,4 Π) of a BeH molecule are calculated using the multi-configuration reference single and double excited configuration interaction(MRCI) approach in combination with the aug-cc-pVTZ basis sets.The calculation covers the internuclear distance ranging from 0.07 nm to 0.70 nm,and the equilibrium bond length R e and the vertical excited energy T e are determined directly.It is evident that the X2Σ+,A2Π,B2Π,C2Σ+ states are bound and 4Π is a repulsive excited state.With the potentials,all of the vibrational levels and inertial rotation constants are predicted when the rotational quantum number J is set to be equal to zero(J = 0) by numerically solving the radial Schr¨odinger equation of nuclear motion.Then the spectroscopic data are obtained including the rotation coupling constant ω e,the anharmonic constant ωexe,the equilibrium rotation constant Be,and the vibration-rotation coupling constant αe.These values are compared with the theoretical and experimental results currently available,showing that they are in agreement with each other.展开更多
应用多参考组态相互作用方法计算了GeO分子的第一解离极限(Ge(3Pg)+O(3Pg))对应的18个-S电子态的电子结构.计算中纳入了Ge原子的3d轨道电子的内壳层-价壳层电子关联效应、标量相对论效应和Davidson修正.基于计算的电子态的电子结构,通...应用多参考组态相互作用方法计算了GeO分子的第一解离极限(Ge(3Pg)+O(3Pg))对应的18个-S电子态的电子结构.计算中纳入了Ge原子的3d轨道电子的内壳层-价壳层电子关联效应、标量相对论效应和Davidson修正.基于计算的电子态的电子结构,通过求解径向Schrdinger方程获得了束缚电子态的光谱常数Re,Te,ωe,ωeχe,B e,理论计算给出的这些电子态的光谱常数与之前的实验结果符合得很好.计算了电子态的电偶极矩随核间距的变化,分析了电子态的组态成分的变化对电偶极矩的影响.计算的势能曲线表明,激发态A1∏,11,D1Σ,a3∏,a′3Σ+,d3△和e3Σ的绝热激发能密集地分布于26000—37000 cm 1范围内,这些密集分布的电子态之间的相互作用对振动波函数有明显扰动作用.借助于激发态之间的自旋-轨道耦合矩阵元,阐明了邻近的激发态对A1和a3的扰动作用.基于计算的A1∏—X1Σ+和A′1Σ+—X1Σ+跃迁的电偶极跃迁矩和Franck-Condon因子,给出了A1和A′1Σ+态的最低的六个振动能级的辐射寿命.展开更多
传统的利用变分原理求解Schrfidinger方程获得原子激发态波函数的方法是基于HUM理论(HylleraasUndheim and MacDonald theorem),在有限的N维Hilbert空间中,通过求解久期方程的高阶根获得激发态的近似波函数.在我们前期的工作中已指出,由...传统的利用变分原理求解Schrfidinger方程获得原子激发态波函数的方法是基于HUM理论(HylleraasUndheim and MacDonald theorem),在有限的N维Hilbert空间中,通过求解久期方程的高阶根获得激发态的近似波函数.在我们前期的工作中已指出,由于HUM方法的几个内禀缺陷限制,它将导致在相同的函数空间中,由传统变分法得到的激发态波函数的‘质量’远差于足够好的基态波函数.进一步地,为了避免基于HUM方法的变分缺陷,本文提出了新的变分函数,并证明其试探激发态波函数在其本征态处具有局域极小值,因而可以通过变分极小无限制的逼近该本征态.在此基础上,利用广义的Laguerre类型轨道(GLTO)在组态相互作用的框架下,分别编写了基于传统HUM理论和新变分函数的关于求解原子近似波函数的计算程序,并且利用该程序计算了氦原子(He)在1S(e),1P(o)态下相应的基态及激发态近似波函数及对应的能量值和径向平均值,并与已有文献中结果进行比较,计算结果显示了HUM理论的缺陷及新变分函数优越性,并就进一步提高激发态的精度指明了方向.展开更多
基金supported by the Scientific Foundation of Education Department in Yunnan Province, China (07Z11621)Innovation Foundationfor New Researchers in Dali University, China (KY421040)~~
基金Project supported by the National Natural Science Foundation of China (Grant No. 29773035).
文摘A new contracted CI scheme—adjustable contracted CI scheme—is presented and programed. The efficiency of this scheme is tested by some example calculations. The result shows that the application of the new scheme is flexible and the correlation energy loss is lower than that of the original externally contracted CI method. Keywords: configuration interaction, contracted CI method, correlation energy.
文摘Potential energy curves （PECs） for the ground state （X2∑＋） and the four excited electronic states （A2∏, B2∏, C2∑＋, 4∏） of a Bell molecule are calculated using the multi-configuration reference single and double excited configuration interaction （MRCI） approach in combination with the aug-cc-pVTZ basis sets. The calculation covers the internuclear distance ranging from 0.07 nm to 0.70 nm, and the equilibrium bond length Re and the vertical excited energy Te are determined directly. It is evident that the X2∑＋, A2∏, B2∏, C2∑＋ states are bound and 4∏ is a repulsive excited state. With the potentials, all of the vibrational levels and inertial rotation constants are predicted when the rotational quantum number J is set to be equal to zero （J = 0） by numerically solving the radial SchrSdinger equation of nuclear motion. Then the spectroscopic data are obtained including the rotation coupling constant w e, the anharmonic constant WeXe, the equilibrium rotation constant Be, and the vibration-rotation coupling constant ae. These values are compared with the theoretical and experimental results currently available, showing that they are in agreement with each other.
基金supported by the National Natural Science Foundation of China(Grant No.11174175)the Tsinghua University Initiative Scientific Research Program,China
文摘The electronic structure of nitrogen trifluoride was investigated by combining the high-resolution electron momentum spectroscopy with the high-level calculations. The experimental binding energy spectra and the momentum distributions of each orbital were compared with the results of Hartree-Fock, density functional theory （DFT）, and symmetry-adapted- cluster configuration-interaction （SAC-CI） methods. SAC-CI and DFT-B3LYP with the aug-cc-pVTZ basis set can well reproduce the binding energy spectra and the observed momentum distributions of the valence orbitals except 1 a2 and 4e orbitals. It was found that the calculated momentum distributions using DFT-B3LYP are even better than those using the high-level SAC-CI method.
文摘Potential energy curves(PECs) for the ground state(X 2 Σ +) and the four excited electronic states(A 2 Π,B 2 Π,C 2 Σ +,4 Π) of a BeH molecule are calculated using the multi-configuration reference single and double excited configuration interaction(MRCI) approach in combination with the aug-cc-pVTZ basis sets.The calculation covers the internuclear distance ranging from 0.07 nm to 0.70 nm,and the equilibrium bond length R e and the vertical excited energy T e are determined directly.It is evident that the X2Σ+,A2Π,B2Π,C2Σ+ states are bound and 4Π is a repulsive excited state.With the potentials,all of the vibrational levels and inertial rotation constants are predicted when the rotational quantum number J is set to be equal to zero(J = 0) by numerically solving the radial Schr¨odinger equation of nuclear motion.Then the spectroscopic data are obtained including the rotation coupling constant ω e,the anharmonic constant ωexe,the equilibrium rotation constant Be,and the vibration-rotation coupling constant αe.These values are compared with the theoretical and experimental results currently available,showing that they are in agreement with each other.
文摘应用多参考组态相互作用方法计算了GeO分子的第一解离极限(Ge(3Pg)+O(3Pg))对应的18个-S电子态的电子结构.计算中纳入了Ge原子的3d轨道电子的内壳层-价壳层电子关联效应、标量相对论效应和Davidson修正.基于计算的电子态的电子结构,通过求解径向Schrdinger方程获得了束缚电子态的光谱常数Re,Te,ωe,ωeχe,B e,理论计算给出的这些电子态的光谱常数与之前的实验结果符合得很好.计算了电子态的电偶极矩随核间距的变化,分析了电子态的组态成分的变化对电偶极矩的影响.计算的势能曲线表明,激发态A1∏,11,D1Σ,a3∏,a′3Σ+,d3△和e3Σ的绝热激发能密集地分布于26000—37000 cm 1范围内,这些密集分布的电子态之间的相互作用对振动波函数有明显扰动作用.借助于激发态之间的自旋-轨道耦合矩阵元,阐明了邻近的激发态对A1和a3的扰动作用.基于计算的A1∏—X1Σ+和A′1Σ+—X1Σ+跃迁的电偶极跃迁矩和Franck-Condon因子,给出了A1和A′1Σ+态的最低的六个振动能级的辐射寿命.
文摘传统的利用变分原理求解Schrfidinger方程获得原子激发态波函数的方法是基于HUM理论(HylleraasUndheim and MacDonald theorem),在有限的N维Hilbert空间中,通过求解久期方程的高阶根获得激发态的近似波函数.在我们前期的工作中已指出,由于HUM方法的几个内禀缺陷限制,它将导致在相同的函数空间中,由传统变分法得到的激发态波函数的‘质量’远差于足够好的基态波函数.进一步地,为了避免基于HUM方法的变分缺陷,本文提出了新的变分函数,并证明其试探激发态波函数在其本征态处具有局域极小值,因而可以通过变分极小无限制的逼近该本征态.在此基础上,利用广义的Laguerre类型轨道(GLTO)在组态相互作用的框架下,分别编写了基于传统HUM理论和新变分函数的关于求解原子近似波函数的计算程序,并且利用该程序计算了氦原子(He)在1S(e),1P(o)态下相应的基态及激发态近似波函数及对应的能量值和径向平均值,并与已有文献中结果进行比较,计算结果显示了HUM理论的缺陷及新变分函数优越性,并就进一步提高激发态的精度指明了方向.
