Wydział Chemii

Sławomir Berski

Grzegorz Gajewski

Zdzisław Latajka

2007

Journal of Molecular Structure

844-845

278-285

10.1016/j.molstruc.2007.05.024

Naukowa

Angielski

Artykuł

A nature of the chemical bond and delocalization of the electron density in the H₂X, H₂C@X and XO₂(X = O, S, Se and Te) mol-ecules is systematically studied by means of the topological analysis of the electron localization function (ELF). The covariance param-eter cov[XI,Xj], which reveals a correlation between the electron density distributions in basinsXIandXjis analyzed. Going from theoxygen to tellurium atom one observes gradual decrease of the electron delocalization between the lone pairs of chalcogen:V1(X)MV2(X) and increase of delocalization between the lone pairs and core basin V1(X)MC(X)MV2(X). In H2O, H2S andH2C@O, H2C@S dominates an exchange between lone electron pairs: cov[V1(X),V2(X)] > cov[Vi= 1,2(X),C(X)], meanwhile for Seand Te containing molecules prevails a delocalization with core region: cov[Vi= 1,2(X),C(X)] > cov[V1(X),V2(X)]. It is proposed that thiseffect is associated with not negligible penetration of d electrons from the outermost shell of the atomic core into valence shell. A study onthe O3molecule reveals dominating delocalization between the lone pair V(O) and electron density of the O–Oi= 1,2bonds:V(O,Oi=1)MV(O)MV(O, Oi=2), meanwhile an exchange between the chalcogen core C(X) and lone pair V(X): C(X)MV(X) prevailsin SO2, SeO₂and TeO₂.

Electron localisation function, Ab initiocalculations, Selenium compounds, Sulphur compounds, Tellurium compounds, Chemical bond

https://doi.org/10.1016/j.molstruc.2007.05.024

http://www.elsevier.com