The Collision Of Ca Ion With The Rare-gas Atoms:Interaction Potential,Spectrum And Dynamics

The interaction potential of alkaline earth metal ions with rare gases has played a very important role in the calculation of non-resonant collision broadening and shifting coefficients.Therefore,it was particularly important to obtain information describing the interaction potentials between collision atoms.The potential energy and spectral information obtained through theoretical research can well explain the experimentally obtained spectral lines.In this paper,the multi-reference configuration interaction method was used to calculate the spectral constants and potential energy curves(PECs)of the Ca+-Rg(Rare gas,Rg=He,Ne,Ar,Kr)system.Then,based on the collision approximation and semi-empirical interatomic potential energy theory,the broadening and shifting coefficients of Ca+ spectral line collisions of rare gas disturbed atoms were calculated.The specific contents were as follows:(1)High-level ab initio method was used to calculate the three dissociation limits of the Ca+-Rg(He,Ne,Ar,Kr)system: Ca+(2S)+Rg(1S),Ca+(2D)+Rg(1S)and Ca+(2Po)+Rg(1S),these three dissociation limits correspond to the PECs of 6 ?-S electronic states.As shown in PECs,we found that the ground state X2?+ was the only state that correspond the first dissociation limit Ca+(2S)+Rg(1S),and the three states correspond to the second dissociation limit were A2(35),B2? and C2?+,and the third dissociation limit correspond to the D2? and E2?+ states.The spectroscopic constants of these electronic states were obtained by numerically solving the Schr?dinger equation.After comparing the data,we found that the results of this paper was in good agreement with the existing experimental and theoretical data.In the calculation of the Ca+-Rg system,the PECs shape of the systems were very similar due to the same valence electron structure.(2)The core valence correlation(CV)and spin-orbit coupling(SOC)effect have been investigated in calculation.After considering the SOC effect,the 6 ?-S states of Ca+-Rg(He,Ne,Ar,Kr)split to 9 ? states.The PECs,permanent dipole moments(PDMs),transition dipole moments(TDMs)and vibrational energy levels(VELs)of the ? state were obtained by calculation,and a graph was drawn to analyze its properties.The calculated PDMs decreases linearly with increasing the internuclear distance R,indicating that the dissociation limit of the system consists of ions and atoms.The spectral constants of the ? state were also calculated,and the changes in the spectral constants of Ca+-He,Ca+-Ne,Ca+-Ar,Ca+-Kr were compared and analyzed.Among them,the calculated values of the spectral constants for the ? state of the Ca+-Kr system were reported in the first time.(3)Using the obtained system potential energy curves,the Anderson-Talman theory was used to calculate the Ca+-Rg(He,Ne,Ar,Kr)system H line and K line broadening and shifting coefficients,and the existing experimental and theoretical data had a comparison.Taking the Ca+-He system as an example,the dependence of the line broadening and shifting coefficients on the temperature and the relationship between the line broadening and shifting coefficients and the pressure of the inert gases were analyzed.