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Sergey V. Kozlov, Elena
A. Pazyuk, Andrey V. Stolyarov
Undulating potentials of
rydberg Σ+-states of Me–Rg molecules: non-empirical treatment
of Na–He exciplex
Abstract
Abstract. The
multi-reference configuration interaction method based on single and double
excitations (MR–CISD), l-independent core polarization potential (CPP)
and diffuse function-saturated cc-pVQZ and
aug-cc-pV5Z basis sets for Na and He atoms, respectively, have been used to
perform non-relativistic calculations of potential energy curves and permanent
dipole moment functions for the ground and excited electronic states of the
exciplex Na–He molecule up to the Na(62S) state. The ab initio
results obtained in a wide range of internuclear distances R [1.7, 20.0]
(Å) have quantitatively claimed the undulating behavior of interatomic
potentials, predicted within the framework of the inelastic scattering theory.
It has been established that at large R the interatomic potentials and dipole
moments of highly excited (3,6,10)2Σ+ states, converging to Na (n = 4, 5, 62S)+He(22S)
atomic limits, are modulated by the nodal structure of the radial Rydberg wave
function (n > 3) s-electron of Na atom during its scattering
on the remote He atom.
Key words: Rydberg
states, Fermi pseudopotential, ab initio calculations, electronic structure of
molecules.
Copyright (C) Chemistry Dept., Moscow State University, 2002
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