(x = 1–5): a unique series of organic superalkali cations. (16th February 2020)

• Record Type: Journal Article
• Authors: Srivastava, Ambrish Kumar
• Is Part Of: Molecular physics. Volume 118:Number 4(2020)
• Publication Date: 2020-02-16
• Subjects: Protonated methane clusters -- superalkali -- vertical electron affinity -- dihydrogen bonds -- density function calculations; Molecules -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Molécules -- Périodiques; Chimie physique et théorique -- Périodiques; 539.6.05
• DOI: 10.1080/00268976.2019.1615648
• Languages: English
• ISSNs: 0026-8976

Abstract

Abstract : Superalkalis, having lower ionisation energy (electron affinity) than alkali atom (cation), form a very important class of clusters with several applications. With an aim to enrich the superalkali series, we have studied C x H 4 x \ +\ 1 + clusters ( x = 1–5) at dispersion-corrected density functional ωB97xD/6-311++G(d, p) level of calculations and the quantum theory of atoms in molecules (QTAIM). We notice that these C x H 4 x \ +\ 1 + cations appear as ( x \ -\ 1 ) C H 4 {--}CH 5 + complexes, which are stabilised by some weak and electrostatic H-bonds. Furthermore, their stability increases with the increase in x, due to the presence of dihydrogen bonds. Moreover, C x H 4 x \ +\ 1 + clusters belong to a unique series of purely hydrocarbon based organic superalkali cations as their vertical electron affinities range 4.35–2.96 eV for x = 1–5, which is in accordance with the increase in their stability. Nevertheless, the deprotonation energy and free-energy of deprotonation of C x H 4 x \ +\ 1 + clusters not only suggest their stability but also provide a suitable path of their synthesis by protonation of CH4 clusters at least in the gas phase. We believe that this unique series of non-metallic organic superalkalis will get further attention of the researchers worldwide as well as their possible applications will be explored. GRAPHICAL ABSTRACT: