Theoretical Study on Polynuclear Superalkali Cations with Various Functional Groups as the Central Core

Abstract

A new series of polynuclear superalkali cations YLi(3)(+) (Y = CO(3), SO(3), SO(4), O(4), and O(5)) has been created when the central group is surrounded by alkali atoms. The structural characteristics and stabilities of these systems are provided on the basis of ab initio methods. In the lowest-energy structure of the CO(3)Li(3)(+), SO(3)Li(3)(+), and SO(4)Li(3)(+) cations, the central Y (Y = CO(3), SO(3), and SO(4)) group features a slight distortion. The global minima of O(4)Li(3)(+) and O(5)Li(3)(+) are of the forms O(2)(-)(Li(+))(3)O(2)(-) and O(2)(-)(Li(+))(3)O(3)(-), respectively, both of which contain two monovalent ion units. The structural integrity of the central Y group and the arrangement of the lithium ligands are two influencing factors on the vertical electron affinities (EA(vert)) for the YLi(3)(+) species. The YLi(3)(+) cation, with its lithium ligands being distributed evenly or far from each other, tends to exhibit a low EA(vert) value, whereas a greater extent of cleavage of the central Y group leads to a higher EA(vert) value and even makes some species lose their superalkali nature.

Do nonmetallic superalkali cations exist?

“…Subsequent investigation on M 2 Li þ 2kþ1 (M = F, O, N, C) indicates that these species with low vertical electron affinities (vEA) also belong to the class of binuclear superalkali cations [11]. Afterwards, we considered the species containing various central cores and theoretically predicted the polynuclear superalkali cations YLi [12,13]. It can be noticed that all the hitherto investigated superalkalies have been alkali metal compounds, while the species with other ligands attract little attention.…”

Superalkali atoms bonding to the phenalenyl radical: structures, intermolecular interaction and nonlinear optical properties

“…According to the above expression, β 0 is proportional to Δμ and f 0 but inversely proportional to ΔE [11][12][13][14][15][16]. The physical quantities in the two-level model may be helpful to qualitatively understand the variation in β 0 values.…”

“…The phenalenyl radical consists of three adjacent benzene rings that share a central carbon atom with a highly symmetrical structure. (see Scheme 1) On the other hand, superatom families have generated a great deal of theoretical [11][12][13][14][15][16] and experimental [17,18]interest. Particularly, an important class of superatoms are superalkalis, which act as potential building blocks for nanostructural materials [19,20].…”

Trivalent acid radical-centered YLi4+(Y = PO4, AsO4, VO4) cations: new polynuclear species designed to enrich the superalkali family

“…7,8,[23][24][25][26][27] Firstly, all atoms were placed at a common point in the geometrical space and then were tossed randomly within a sphere with a radius between R min and R max . We set the R min = 1.5 Å and R max = 6.0 Å.…”