Long-lived diatomic dications: Potential curves and radiative lifetimes for CaBr2+ and CaI2+ including relativistic effects

Relativistic effective core potential calculations have been employed in the framework of a spin-orbit configuration interaction to compute the lowest-lying electronic states of the CaBr2+ and CaI2+ dications, and the results are compared with the data for the isovalent CaCl2+ system studied earlier. The ground X 2H state in all three dications arises from a strong polarization of X(2Po)(X = Cl, Br or I) by the Ca2+(1S) ion and is bound by 0·96-1·55 eV with respect to the corresponding diabatic dissociation limits. It is split by the spin-orbit interaction into the X1 2Π3/2 and X2 2Π1/2 components, with the energy splittings calculated to be 647 cm-1 (CaCl2+), 2115 cm-1 (CaBr2+) and 3544cm-1 (CaI2+). The X1 and X2 states are found to be thermodynamically stable in CaCl2+ and CaBr2+, while in CaI2+ the lowest dissociation limit, Ca+(2S) + I+(3P2), lies 1700 and 5200 cm-1 lower than the X1 and X2 minima respectively. The X1 and X2 states in CaI2+ are extremely long-lived, however, owing to the high and very broad potential barriers to dissociation. The first electronic excited state, A2Σ+, is also bound in all the above systems, although it is pre-dissociated in CaBr2+ and CaI2+ at large internuclear distances. All other low-lying electronic states of CaX2+ are repulsive. Electric-dipole moments are calculated for the A → X1,X2 transitions. The corresponding radiative lifetimes are found to be very long in CaCl2+: τ(A → X1) = 19·3 ms and τ(A → X2) = 9·9 ms (the values are given for v′ = 0), and become very significantly shorter for CaBr2+ and CaI2+ because of the stronger spin-orbit interaction in the heavier systems. This effect is especially noticeable for the A → X2 transitions, for which the τ values are computed to be 364 μs in CaBr2+ and 50·3 us in CaI2+. The theoretical data obtained should aid in the future spectroscopic detection of these species. To data no experiment of this type has been successfully carried out for any of the thermodynamically stable diatomic dications

Dissociation of molecular chlorine in a Coulomb explosion: Potential curves, bound states, and deviation from Coulombic behavior for Cl2n+ (n = 2,3,4,6,8,10)

Highly charged molecular ions are generated in Coulomb explosion experiments involving multielectron dissociative ionization, but little is known about the precise mechanisms involved in their formation. To help improve the understanding of such experiments, potential energy curves are calculated in this paper for diatomic chlorine ( Cl 2 ) and its ions Cl n + 2 , where n = 1 , 2 , 3 , 4 , 6 , 8 , 10 . Bound vibrational states are obtained in three low-lying electronic states for Cl 2 + 2 and one state for Cl 3 + 2 . Vertical excitation energies are given for stepwise excitations up to Cl 1 0 + 2 . For all the ions examined there is a significant energy defect ( Δ ) from the corresponding Coulomb potential, in one case reaching magnitudes of over 20 eV. We analyze the origin of these energy defects in terms of residual chemical bonding, and discuss the contribution of strongly bonding configurations at short internuclear distance. Finally, we present a simple physical model which describes the qualitative behavior of Δ ( R , Q )

Long-lived diatomic+dications: Potential curves and radiative lifetimes for cabr2+ and cai2+ including relativistic effects

Relativistic effective core potential calculations have been employed in the framework of a spin-orbit configuration interaction to compute the lowest-lying electronic states of the CaBr2+ and CaI2+ dications, and the results are compared with the data for the isovalent 2+ 2 CaCl system studied earlier. The ground X n state in all three dications arises from a strong polarization of X(2Po)(X = C1, Br or i) by the Ca2+(1S) ion and is bound by 0 96 1.55 eV with respect to the corresponding diabatic dissociation limits. It is split by the spin- orbit interaction into the X1 2n 3/2 and (formula presented) components, with the energy splittings calculated to be 647cm-1(CaCl2+),2115cm-1(CaBr2+) anti 3544cm-1(CaI2+). The X1 and X2 states are found to be thermodynamically stable in CaCl2+ and CaBr2+, while in CaI + the lowest dissociation limit, Ca+(2S) + I+(3P2), lies 1700 and 5200 cm-1 lower than the X1 and X2 minima respectively. The X1 and X2 states in CaI2+ are extremely long-lived, however, owing to the high and very broad potential barriers to dissociation. The first electronic excited state, A  +, is also bound in all the above systems, although it is pre-dissociated in CaBr + and CaI2+ at large internuclear distances. All other low-lying electronic states of CaX2+ are repulsive. Electric-dipole moments are calculated for the A→X1X2 transitions. The corre­sponding radiative lifetimes are found to be very long in CaCl2+: t(A →X1) = 19-3 ms and t(a t, X2)=9 - 9 ms (the values are given for v = 0), and become very significantly shorter for CaBr2+ and CaI2+because of the stronger spin-orbit interaction in the heavier systems. This effect is especially noticeable for the A—»X2 transitions, for which the t values are computed to be 364 ns in CaBr2+ and 50.3 us in CaI2+. The theoretical data obtained should aid in the future spectroscopic detection of these species. To data no experiment of this type has been successfully carried out for any of the thermodynamically stable diatomic dications