title: CCSD(T) calculations of confined systems: in-crystal polarizabilities of F⁻, Cl⁻, O²⁻, and S²⁻.
abstract: We explore dipole polarizabilities of the singly and doubly charged anions F(-), Cl(-), O(2-), and S(2-) in an external, harmonic oscillator (HO) confining potential ∑(i)½ω(2)r(i)(2). We find that in contrast to F(-) and Cl(-) those for O(2-) and S(2-) are unrealistically high due to the instability of the corresponding restricted Hartree-Fock (RHF) solutions. Yet, already a relatively weak HO confining potential stabilizes their RHF solutions and eliminates any possible broken-symmetry solutions. The coupled-cluster theory with single, double and noniterative triple excitations (CCSD(T)) then yields considerably reduced polarizabilities for O(2-) and S(2-) relative to their unconfined values. We showed that polarizabilities of O(2-) and S(2-) are more sensitive to the strength of a confinement potential than are those for F(-) and Cl(-). This enables us to relate the confining parameter ω with the known experimental polarizabilities for selected crystals (our "training set") and to find a specific confining parameter ω for which the CCSD(T) polarizability equals the experimental in-crystal polarizability of an anion in the training set. The latter may then be used as an alternative approach for determining the in-crystal polarizabilities of anions by exploiting the fact that the characteristic ω values depend linearly on the ionic radius of a cation participating in specific crystals containing these anions. Using this method we then calculate the isotropic dipole polarizabilities for F(-), Cl(-), O(2-), and S(2-) embedded in the LiF, LiCl, NaF, NaCl, KF, KCl, ZnO, ZnS, MgO, MgS, CaO, CaS, SrO, SrS, BaO, BaS, and other crystals containing halogen, oxygen, or sulphur anions. We compare our results with those obtained via alternative models of the in-crystal anionic polarizabilities.
authors.affiliation: Faculty of Materials Science and Technology in Trnava, Institute of Materials Science, Slovak University of Technology in Bratislava, Paulínska 16, 917 24 Trnava, Slovakia.
authors.forename: F
authors.initials: F
authors.lastname: Holka
authors.affiliation: Faculty of Materials Science and Technology in Trnava, Institute of Materials Science, Slovak University of Technology in Bratislava, Paulínska 16, 917 24 Trnava, Slovakia.
authors.forename: M
authors.initials: M
authors.lastname: Urban
authors.affiliation: Department of Physical and Theoretical Chemistry, Faculty of Natural Sciences, Comenius University, Mlynská dolina, SK-842 15 Bratislava, Slovakia.
authors.forename: P
authors.initials: P
authors.lastname: Neogrády
authors.affiliation: Department of Applied Mathematics, University of Waterloo, Waterloo, Ontario N2L 3G1, Canada.
authors.forename: J
authors.initials: J
authors.lastname: Paldus