A b i n i t i o effective core potentials including relativistic effects. II. Potential energy curves for Xe2, Xe+2, and Xe*2

Abstract

Articles you may be interested inA b i n i t i o effective core potentials including relativistic effects. V. SCF calculations with ω-ω coupling including results for Au2 +, TlH, PbS, and PbSe Relativistic effects in a b i n i t i o effective core potential studies of heavy metal compounds. Application to HgCl2, AuCl, and PtH A b i n i t i o effective core potentials including relativistic effects. IV. Potential energy curves for the ground and several excited states of Au2 A b i n i t i o effective core potentials including relativistic effects. I. Formalism and applications to the Xe and Au atoms Potential energy curves for the ground 1 I.: state of Xe2' the first four states of the Xei ions, and the eight Xe-2 excirner states corresponding to the addition of a 6su g Rydberg electron to these ion cores have been computed using averaged relativistic effective core potentials (AREP) and the self-consistent field approximation for the valence electrons. The calculations were carried out using the LS-coupling scheme with the effects of spin-<lrbit coupling included in the resulting potential energy curves using an empirical procedure. A comparison of nonrelativistic and averaged relativistic EP's and subsequent molecular calculations indicates that relativistic effects arising from the mass-velocity and Darwin terms are not important for these properties of X~ molecules. Spectroscopic constants for Xci are in good agreement with all electron CI calculations suggesting that the computed values for Xe-2 excirners should be reliable. The lifetime for the 0/ state of the Xe2-is computed to be 5.6 nsee which is in the range of the experimentally determined values.

A resonance enhanced multiphoton ionization study of the gerade excited states of Xe2 with a Xe 1S+Xe* 6s[3/2]1 dissociation limit

“…24,25 At large internuclear distances the results from those studies were in qualitative agreement. For the 1 g state some bound character was predicted with a minimum in the potential at about 8 bohr, whereas for the 0 g ϩ state a fully dissociative potential was obtained as long as the state is described as an ion core with a 6s g Rydberg electron.…”

“…The Rydberg electron of these molecular excited states is of 6s g symmetry. 24,25 In Fig. 5 a diagram is presented in which molecular states derived from dimer electronic configurations are correlated to molecular states derived from the appropriate dissociation limits.…”

“…The ordering of these excited states as well as that of the ionic states has been drawn schematically for an internuclear distance which is equal to the equilibrium distance of the ground state and has been obtained from the study of Ermler et al 25 On the right-hand side the molecular states are con- The energy scale on the x axis is relative to the dissociation limit. sidered in the separated atom limit.…”

“…26 In the Xe dimer only ⍀, the projection of the total electronic angular momentum on the internuclear axis, rather than ⌳ and ⌺ separately, is a well-defined quantum number. 24,25,27 In the diagram electronic states derived from electron configurations and dissociation limits are therefore adiabatically correlated using only ⍀ g/u . The diagram might seem to suggest that the excited states of the Xe dimer can be described by a single electron configuration.…”

UV emission from excited inert-gas molecules

“…Зачастую такой подход является вынуж денным, поскольку сведения о дипольных моментах переходов в димерах инер тных газов практически отсутствуют. Для интересующих нас переходов с учетом спин орбитального взаимодействия) нам известны данные только для Хе 2 [21] и Кr 2 [22].…”