Correlationbound anions of NaCl clusters
Abstract
In the past a variety of electron binding motifs has been identified for sodium chloride cluster anions. As for all of these clusters the excess electron is predicted to be bound in selfconsistentfield calculations, the different binding mechanisms can be understood in terms of a oneelectron potential largely due to the permanent multipole moments of the neutral cluster. Here we investigate a new class of (NaCl)N anion that is predicted to be bound only after electron correlation has been taken into account. Correlationbound states of the trimer, (NaCl)3, and tetramer, (NaCl)4, are characterized using Green's function and an equationofmotion coupledcluster method, and the computed electron binding energies as well as the distributions of the excess electrons as inferred from natural orbitals of the coupledcluster calculations are compared with that of dipolebound, quadrupolebound, and defectlike (NaCl)N anions. For the (NaCl)4 tetramer anion the correlationbound state is predicted to represent the most stable isomer. Our results provide a sensitive test case for the development of improved oneelectron model potentials for excess electrons bound to alkali halide clusters, and suggest that cluster abundance as inferred from peak intensities of photoelectron spectra is not directly related to the relative stability of the clusters.
 Publication:

Journal of Chemical Physics
 Pub Date:
 September 2010
 DOI:
 10.1063/1.3488228
 Bibcode:
 2010JChPh.133k4301S
 Keywords:

 binding energy;
 coupled cluster calculations;
 electron correlations;
 Green's function methods;
 molecular clusters;
 molecular moments;
 photoelectron spectra;
 SCF calculations;
 sodium compounds;
 36.40.Mr;
 31.15.bw;
 33.15.Ry;
 31.15.V;
 31.30.jp;
 31.15.xr;
 Spectroscopy and geometrical structure of clusters;
 Clusters: electronic properties equilibrium geometries coupledcluster theory;
 Ionization potentials electron affinities molecular core binding energy;
 Electron correlation calculations for atoms ions and molecules;
 Electron electric dipole moment;
 Selfconsistentfield methods