Configuration interaction calculations of annihilation rates for positronic complexes of alkali hydrides

Ab initio multireference single- and double-excitation configuration interaction (MRD-CI) wave functions have been employed to compute the annihilation rates (AR) of positronic molecular complexes of four alkali hydrides. The first step in these calculations is the evaluation of integrals of the two-particle Dirac delta function delta(+-) over pairs of electronic and positronic basis functions. MRD-CI wave functions calculated with the same basis are then employed to obtain expectation values of the delta(+-) operator (Z(eff)), which in turn are proportional to the corresponding annihilation rates (AR) of the associated many-particle states. The importance of removing near-linear dependencies in the basis sets employed is stressed as well as the advisability of placing diffuse (small-exponent) functions in the basis only at the most electronegative center of the molecule. A tendency to underestimate the Z(eff) values is noted because of the impracticality of including sufficiently high-1 basis functions in the basis for general molecular systems. However, comparison with the relatively accurate values for the four-electron e(+)LiH complex obtained by Quantum Monte-Carlo (QMC) and other methods indicates that the fractional error is nearly constant over a large range of internuclear distance, consistent with the expectation that missing correlation effects in the MRD-CI treatment are predominantly atomic in nature. A scaling procedure based on the asymptotic delta(+-) value, which is the same for all four alkali hydrides, is then shown to produce good agreement with the QMC AR data for e(+)LiH. The same procedure has been applied to the delta(+-) values for the positronic complexes of the heavier alkali hydrides for which no other theoretical results are available. Trends in the variation of the AR results with bond distance are discussed. (C) 2009 Published by Elsevier B.V.