A computational scheme for accurate spectroscopic constants was presented in this work and applied to the lowest two electronic states of sulfur dimer. A high-level ab initio calculation utilizing explicitly correlate...A computational scheme for accurate spectroscopic constants was presented in this work and applied to the lowest two electronic states of sulfur dimer. A high-level ab initio calculation utilizing explicitly correlated multireference con- figuration interaction method （MRCI-F12） was performed to compute the potential energy curves （PECs） of the ground triplet X3Eg and first excited singlet alAg states of sulfur dimer with cc-pCVXZ-F12（X = T, Q） basis sets. The effects of Davidson modification, core-valence correlation correction, and scalar relativistic correction on the spectroscopic con- stants were examined. The vibration-rotation spectra of the two electronic states were provided. Our computational results show excellent agreement with existing available experimental values, and the errors of main spectroscopic constants are within 0.1% order of magnitude. The present computational scheme is cheap and accurate, which is expected for extensive investigations on the potential energy curves or surfaces of other molecular systems.展开更多
High-level ab initio calculations of theΛ-S states for aluminum monoiodide(AlCl)molecule are performed by utilizing the explicitly correlated multireference configuration interaction(MRCI-F12)method.The Davidson corr...High-level ab initio calculations of theΛ-S states for aluminum monoiodide(AlCl)molecule are performed by utilizing the explicitly correlated multireference configuration interaction(MRCI-F12)method.The Davidson correction and scalar relativistic correction are investigated in the calculations.Based on the calculation by the MRCI-F12 method,the spin-orbit coupling(SOC)effect is investigated with the state-interacting technique.The adiabatic potential energy curves(PECs)of the 13Λ-S states and 24Ωstates are calculated.The spectroscopic constants of bound states are determined,which are in accordance with the results of the available experimental and theoretical studies.Finally,the transition properties of 0^(+)(2)-X0^(+),1(1)-X0^(+),and 1(2)-X0^(+)transitions are predicted,including the transition dipole moments(TDMs),Franck-Condon factors(FCFs),and the spontaneous radiative lifetimes.展开更多
基金supported by the National Natural Science Foundation of China(Grand No.11574114)the Natural Science Foundation of Jilin Province,China(Grand No.20150101003JC)
文摘A computational scheme for accurate spectroscopic constants was presented in this work and applied to the lowest two electronic states of sulfur dimer. A high-level ab initio calculation utilizing explicitly correlated multireference con- figuration interaction method （MRCI-F12） was performed to compute the potential energy curves （PECs） of the ground triplet X3Eg and first excited singlet alAg states of sulfur dimer with cc-pCVXZ-F12（X = T, Q） basis sets. The effects of Davidson modification, core-valence correlation correction, and scalar relativistic correction on the spectroscopic con- stants were examined. The vibration-rotation spectra of the two electronic states were provided. Our computational results show excellent agreement with existing available experimental values, and the errors of main spectroscopic constants are within 0.1% order of magnitude. The present computational scheme is cheap and accurate, which is expected for extensive investigations on the potential energy curves or surfaces of other molecular systems.
基金the National Key Research and Development Program of China(Grant No.2017YFA0403300)the National Natural Science Foundation of China(Grant Nos.11874177,11874179,and 11574114)+1 种基金the Natural Science Foundation of Jilin Province,China(Grant No.20180101289JC)the High Performance Computing Center of Jilin University and High Performance Computing Cluster Tiger@IAMP(Theoretical Simulation Laboratory of Generalized Atomic,Molecular,and Energy Researches at Institute of Atomic and Molecular Physics).
文摘High-level ab initio calculations of theΛ-S states for aluminum monoiodide(AlCl)molecule are performed by utilizing the explicitly correlated multireference configuration interaction(MRCI-F12)method.The Davidson correction and scalar relativistic correction are investigated in the calculations.Based on the calculation by the MRCI-F12 method,the spin-orbit coupling(SOC)effect is investigated with the state-interacting technique.The adiabatic potential energy curves(PECs)of the 13Λ-S states and 24Ωstates are calculated.The spectroscopic constants of bound states are determined,which are in accordance with the results of the available experimental and theoretical studies.Finally,the transition properties of 0^(+)(2)-X0^(+),1(1)-X0^(+),and 1(2)-X0^(+)transitions are predicted,including the transition dipole moments(TDMs),Franck-Condon factors(FCFs),and the spontaneous radiative lifetimes.
