Hydrogenated Superalkalis and Their Possible Applications

Overview

Journal J Mol Model

Publisher Springer

Specialty Molecular Biology

Date 2016 May 12

PMID 27168197

Authors

Ambrish Kumar Srivastava

Neeraj Misra

Affiliations

Soon will be listed here.

Abstract

Superalkali species possess lower ionization energy than alkali metals, which allow them to form a variety of unusual compounds with interesting properties. Herein, we report the structures and properties of hydrogenated superalkalis (SAHs) such as FLi2H, OLi3H, and NLi4H using ab initio MP2/6-311++G(d,p) level of theory. All SAH species are found to be thermodynamically stable, which can be considered as a salt between SA cation and H‾ anion. The gas phase basicity and nonlinear optical properties (NLO) of SAH have been explored. The larger proton affinity of NLi4H isomers 1187-1226 kJ mol(-1) and significant mean hyperpolarizability 1.5 × 10(3)-3.7 × 10(3) a.u. suggest their strong basic nature and enhanced NLO properties, respectively. We have also demonstrated some possible applications of hydrogenated superalkalis, as reducing agent as well as building block of supersalts. Graphical abstract The gas phase basicity and nonlinear optical properties of hydogenated superalkalis increase with the increase in the size of superalkalis, FLi2 < OLi3 < NLi4.

References

Tong J, Li Y, Wu D, Li Z, Huang X . Ab initio investigation on a new class of binuclear superalkali cations M2Li(2k+1)+ (F2Li3+, O2Li5+, N2Li7+, and C2Li9+). J Phys Chem A. 2011; 115(10):2041-6. DOI: 10.1021/jp110417z. View

Wang F, Li Z, Wu D, Sun X, Chen W, Li Y . Novel superalkali superhalogen compounds (Li3)+(SH)- (SH=LiF2, BeF3, and BF4) with aromaticity: new electrides and alkalides. Chemphyschem. 2006; 7(5):1136-41. DOI: 10.1002/cphc.200600014. View

Bera P, Sattelmeyer K, Saunders M, Schaefer 3rd H, Schleyer P . Mindless chemistry. J Phys Chem A. 2006; 110(13):4287-90. DOI: 10.1021/jp057107z. View

Tian Z, Chan B, Sullivan M, Radom L, Kass S . Lithium monoxide anion: a ground-state triplet with the strongest base to date. Proc Natl Acad Sci U S A. 2008; 105(22):7647-51. PMC: 2409378. DOI: 10.1073/pnas.0801393105. View

Hoffmann R, Schleyer P, Schaefer 3rd H . Predicting molecules--more realism, please!. Angew Chem Int Ed Engl. 2008; 47(38):7164-7. DOI: 10.1002/anie.200801206. View

Li Y, Wu D, Li Z . Compounds of superatom clusters: preferred structures and significant nonlinear optical properties of the BLi6-X (X = F, LiF2, BeF3, BF4) motifs. Inorg Chem. 2008; 47(21):9773-8. DOI: 10.1021/ic800184z. View

Hou N, Wu D, Li Y, Li Z . Lower the electron affinity by halogenation: an unusual strategy to design superalkali cations. J Am Chem Soc. 2014; 136(7):2921-7. DOI: 10.1021/ja411755t. View

Sun W, Fan L, Li Y, Liu J, Wu D, Li Z . On the potential application of superalkali clusters in designing novel alkalides with large nonlinear optical properties. Inorg Chem. 2014; 53(12):6170-8. DOI: 10.1021/ic500655s. View

Elliott B, Koyle E, Boldyrev A, Wang X, Wang L . MX3(-) superhalogens (M = Be, Mg, Ca; X = Cl, Br): a photoelectron spectroscopic and ab initio theoretical study. J Phys Chem A. 2005; 109(50):11560-7. DOI: 10.1021/jp054036v. View

10.

Sun W, Wu D, Li Y, Li Z . Theoretical study on superalkali (Li3) in ammonia: novel alkalides with considerably large first hyperpolarizabilities. Dalton Trans. 2013; 43(2):486-94. DOI: 10.1039/c3dt51559a. View

11.

Tong J, Li Y, Wu D, Wu Z . Theoretical study on polynuclear superalkali cations with various functional groups as the central core. Inorg Chem. 2012; 51(11):6081-8. DOI: 10.1021/ic202675j. View

12.

Tong J, Wu Z, Li Y, Wu D . Prediction and characterization of novel polynuclear superalkali cations. Dalton Trans. 2012; 42(2):577-84. DOI: 10.1039/c2dt31429k. View