Formation of stable ionized complexes between coinage metal containing superhalogens and moderately reactive molecules: a DFT approach
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The possibility of ionization of six moderately reactive molecules (Y), namely silicon dioxide (SiO2), ammonia (NH3), water (H2O), carbon dioxide (CO2), chloroform (CHCl3) and dichlorodifluoromethane (CCl2F2) by two properly chosen superhalogens (SHs), gold tetrafluoride (AuF4), and gold hexafluoride (AuF6) denoted as AuXn (n = 4 and 6) has been explored at density functional theory (DFT) level. With increasing electron affinity (EA) of superhalogen, its capability to oxidize molecules with higher ionization potential also increases. We have demonstrated that this competition between the electron-binding energy of the superhalogen system and the ionization potential (IP) of the molecule with which the superhalogen combines is a key factor to predict the stability and nature of the formed complex. Binding energies have been evaluated to predict the stability of the formed complexes. The charge flow between Y and AuXn and localization of spin density distribution on the Y molecules have been estimated to verify the nature of interaction between the two. Atom in molecule (AIM) analysis has been performed to predict the nature of the bonds formed between the two interacting species. Overall, our study gives a comprehensive idea about the nature and stability of the complexes formed when moderately reactive (or inert) molecules interact with superhalogens containing coinage metal.
KeywordsSuperhalogen Moderately reactive molecule Geometrical parameter Binding energy DFT
S.S. is grateful to University Grant Commission (UGC), Government of India, T.A. and T.D. are grateful to Council of Scientific and Industrial Research (CSIR), Government of India, for providing them research fellowships.
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Conflict of interest
The authors declare that they have no conflict of interest.
Table S1 reports the EA and VDE of the superhalogens. Table S2 reports the BE, charge flow, and Mulliken spin density values evaluated at B3LYP level. Figure S1 depicts the optimized structures of the superhalogens. Cartesian coordinates for the optimized structures of the superhalogens, Y molecules, and all the Y-AuFn complexes are provided in the supplementary information.
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