Information about electronic excited states of molecular anions plays an important role in investigating electron attachment and detachment processes.Here we present a high-level theoretical study of the electronic st...Information about electronic excited states of molecular anions plays an important role in investigating electron attachment and detachment processes.Here we present a high-level theoretical study of the electronic structures of 12 alkali-metal-containing diatomic anions MX-(MX = LiH,LiF,LiCl,NaF,NaCl,NaBr,RbCl,KCl,KBr,RbI,KI and CsI).The equation-of-motion electron-attachment coupled-cluster singles and doubles(EOM-EA-CCSD) method is used to calculate the electron binding energies(EBEs) of 10 electronic excited states of each of the 12 molecule anions.With addition of different s-/p-/d-type diffusion functions in the basis set,we have identified possible excited dipole bound states(DBSs) of each anion.With the investigation of EBEs on the 12 MXs with dipole moment(DM) up to 12.1 D,we evaluate the dependence of the number of anionic excited DBSs on molecular DM.The results indicate that there are at least two or three DBSs of anions with a molecular DM larger than 7 D and a molecule with DM > 10 D can sustain a π-DBS of the anion.Our study has some implications for the excited DBS electronic states of alkali-metal-containing diatomic molecules.展开更多
Calculations on the spectroscopic constants and transition properties of the first three states(a^(1)△,b^(1)Σ^(+),and X3Σ-)of the Sb H molecule were performed under the relativistic framework using the exact two-co...Calculations on the spectroscopic constants and transition properties of the first three states(a^(1)△,b^(1)Σ^(+),and X3Σ-)of the Sb H molecule were performed under the relativistic framework using the exact two-component Hamiltonian(X2C).The potential energy curves in the Franck-Condon region were computed and compared with the previous values.Furthermore,the transition dipole moments for the weak spin-forbidden transitions(b0^(+)-X10^(+),b0^(+)-X_(2)1,X10^(+)-X_(2)1,and X_(2)1-a2)were reported.The spontaneous radiative lifetime of the b1Σ^(+)(υ′=0)state was calculated as 163.5±7.5μs,which is in reasonable agreement with the latest experimental value of 173±3μs.The spontaneous radiative lifetimes of the X_(2)1(υ′=0)state and the a2(υ′=0)state were calculated to be 48.6 s and~8 ms,respectively.Our study is expected to be a benchmark transition property computation for comparison with other theoretical and experimental results.The datasets presented in this paper,including the transition dipole moments,are openly available at https://dx.doi.org/10.11922/sciencedb.j00113.00018.展开更多
基金Project supported by the National Natural Science Foundation of China(Grant Nos.12274178 and 12174148)Support of High Performance Computing Center of Jilin Universitythe high-performance computing cluster Tiger@IAMP。
文摘Information about electronic excited states of molecular anions plays an important role in investigating electron attachment and detachment processes.Here we present a high-level theoretical study of the electronic structures of 12 alkali-metal-containing diatomic anions MX-(MX = LiH,LiF,LiCl,NaF,NaCl,NaBr,RbCl,KCl,KBr,RbI,KI and CsI).The equation-of-motion electron-attachment coupled-cluster singles and doubles(EOM-EA-CCSD) method is used to calculate the electron binding energies(EBEs) of 10 electronic excited states of each of the 12 molecule anions.With addition of different s-/p-/d-type diffusion functions in the basis set,we have identified possible excited dipole bound states(DBSs) of each anion.With the investigation of EBEs on the 12 MXs with dipole moment(DM) up to 12.1 D,we evaluate the dependence of the number of anionic excited DBSs on molecular DM.The results indicate that there are at least two or three DBSs of anions with a molecular DM larger than 7 D and a molecule with DM > 10 D can sustain a π-DBS of the anion.Our study has some implications for the excited DBS electronic states of alkali-metal-containing diatomic molecules.
基金Project supported by the National Natural Science Foundation of China(Grant No.11874177)。
文摘Calculations on the spectroscopic constants and transition properties of the first three states(a^(1)△,b^(1)Σ^(+),and X3Σ-)of the Sb H molecule were performed under the relativistic framework using the exact two-component Hamiltonian(X2C).The potential energy curves in the Franck-Condon region were computed and compared with the previous values.Furthermore,the transition dipole moments for the weak spin-forbidden transitions(b0^(+)-X10^(+),b0^(+)-X_(2)1,X10^(+)-X_(2)1,and X_(2)1-a2)were reported.The spontaneous radiative lifetime of the b1Σ^(+)(υ′=0)state was calculated as 163.5±7.5μs,which is in reasonable agreement with the latest experimental value of 173±3μs.The spontaneous radiative lifetimes of the X_(2)1(υ′=0)state and the a2(υ′=0)state were calculated to be 48.6 s and~8 ms,respectively.Our study is expected to be a benchmark transition property computation for comparison with other theoretical and experimental results.The datasets presented in this paper,including the transition dipole moments,are openly available at https://dx.doi.org/10.11922/sciencedb.j00113.00018.
