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We designed novel alkalides such as FLi2-M-OLi3 and FLi2-M-NLi4 (M = Li, Na, K), along with OLi3-M-NLi4 (M = Li, Na) by interacting alkali metal atoms with heterogeneous superalkali clusters in anionic, neutral and cationic configurations. The stability of these superalkali based alkalides are confirmed by its binding energy (Eb). Utilising QTAIM method, the bond strength and nature of bond have been analysed. NPA charge analysis is conducted to forecast charge transfer and also to confirm the alkalide character of the complex along with the electron localisation function (ELF) analysis. The HOMO–LUMO gap analysis is performed to analyse electrical conductivity and chemical reactivity. The nonlinear optical (NLO) properties have been investigated by polarisability and first-order static hyperpolarizibilty (β0), which is found to be as high as 2.77 × 107 a. u. for (OLi3-Li-NLi4)+ complex. The UV-Vis spectra and electronic transitions are used to explain the enhanced NLO responses. The study not only identifies new alkalide candidates but also presents strategies to significantly improve their NLO properties, which may be useful in nonlinear optics and optoelectronics. [ABSTRACT FROM AUTHOR]

Superalkalis (SAs) are exotic clusters having lower ionization energy than alkali atoms, which makes them strong reducing agents. In the quest for the reduction of diatomic molecules (X2) such as N2, O2, and H2 using Møller‐Plesset perturbation theory (MP2), we have studied their interaction with typical superalkalis such as FLi2, OLi3, and NLi4 and calculated various parameters of the resulting SA−X2 complexes. We noticed that the SA−O2 complex and its isomers possess strong ionic interaction, which leads to the reduction of O2 to O2− anion. On the contrary, there are both ionic and covalent interactions in SA−N2 complexes such that the lowest energy isomers are covalently bonded with no charge transfer from SA. Further, the interaction between SA and H2 leads to weakly bound complexes, which results in the adsorption of H2 molecules. The nature of interaction is found to be closely related to the electron affinity of diatomic molecules. These findings might be useful in the study of the activation, reduction, and adsorption of small molecules, which can be further explored for their possible applications. [ABSTRACT FROM AUTHOR]

Piperine (a naturally occurring alkaloid), is a biologically active natural product belonging to the alkaloid series of compounds. In this study, the spectral characterization of piperine isolated from black pepper has been performed using FT-IR, 1H-NMR, and 13C-NMR. To explain spectral features, we have calculated the vibrational frequencies of the optimized structure of piperine using the B3LYP/6-311 + G(d,p) level of theory and NMR spectra using the GIAO method. All vibrational modes of the title molecule have been assigned based on potential energy distribution. The calculated scaled wavenumbers and NMR chemical shifts show good agreement with the experimental FT-IR and NMR data, respectively. To assess the bioactivity of piperine, we have first performed molecular docking using the ITK receptor and subsequently, the molecular dynamics simulation of the resulting complex for 100 ns. The results suggest the potential of piperine for possible anti-inflammatory action. [ABSTRACT FROM AUTHOR]

Superalkalis are known for their lower ionization energy than alkali atoms. In the last four decades, a lot of exploration has been done to enrich the superalkali series. In this work, we report the superalkali behavior of XH4-x(CH3)x series of molecules for X = N, P, As, and x = 0⎼4. We have systematically studied neutral and cationic NH4-x(CH3)x and PH4-x(CH3)x as well as AsH4-x(CH3)x species using MP2/6⎼311 ++ G(d,p) level by successive substitutions of methyl (CH3) groups. We have also analyzed the effect of substitutions as well as the role of central atom on the ionization energy (IE) of XH4-x(CH3)x. As we move from x = 1 to x = 4, the IE decreases in NH4-x(CH3)x, PH4-x(CH3)x, and AsH4-x(CH3)x, being in the range 3.97–2.77 eV, 4.10–2.76 eV, and 4.40–2.78 eV, respectively. Consequently, these molecules go to superalkalis. Their superalkali behavior has been explained on the basis of charge (de)localization in these species. These findings will provide new way to design superalkali molecules with even lower ionization energies. [ABSTRACT FROM AUTHOR]

Superalkalis (SAs) are exotic clusters having lower ionization energy than alkali atoms, which makes them strong reducing agents. In the quest for the reduction of diatomic molecules (X 2 ) such as N 2 , O 2 , and H 2 using Møller-Plesset perturbation theory (MP2), we have studied their interaction with typical superalkalis such as FLi 2 , OLi 3 , and NLi 4 and calculated various parameters of the resulting SA-X 2 complexes. We noticed that the SA-O 2 complex and its isomers possess strong ionic interaction, which leads to the reduction of O 2 to O 2 - anion. On the contrary, there are both ionic and covalent interactions in SA-N 2 complexes such that the lowest energy isomers are covalently bonded with no charge transfer from SA. Further, the interaction between SA and H 2 leads to weakly bound complexes, which results in the adsorption of H 2 molecules. The nature of interaction is found to be closely related to the electron affinity of diatomic molecules. These findings might be useful in the study of the activation, reduction, and adsorption of small molecules, which can be further explored for their possible applications., (© 2023 The Authors. ChemistryOpen published by Wiley-VCH GmbH.)