Charge-Inverted Hydrogen-Bridged Bond in HCa(μ-H)₃E (E = Si, Ge, and Sn): Matrix Isolation Infrared Spectroscopic and Theoretical Studies

Abstract

Matrix isolation infrared spectroscopy combined with quantumchemical calculations were employed to study the reactions of calcium atoms with silane, germane, and stannane in a 4 K argon matrix. The ion pairs [HCa] + and [EH 3 ] − (E = Si, Ge, and Sn) in both the classical structure HCaEH 3 and the bridged structure HCa(μ-H) 3 E were identified based on the H/D isotopic substitution experiments and quantum-chemical calculations. The results show that the reaction between ground-state Ca and EH 4 proceeds inefficiently, and only after the photolytic activation of Ca atoms to the Ca( 1 P:4s4p) state does insertion occur to give HCaEH 3 , which rearranges to HCa(μ-H) 3 E upon photolysis. Topological analysis of the electronic structure suggests that the nonclassical structure HCa(μ-H) 3 E is formed by the electrostatic interaction with charge-inverted hydrogen bridge bond, while HCaEH 3 is dominated by (HCa) + (EH 3 ) − ion pair interactions.

Activation of H2S by Atomic Cr, Mn, and Fe: Matrix Infrared Spectra and Quantum Chemical Calculations

“…The experimental setup for laser ablation and matrix isolation infrared spectroscopy has been described in detail previously. , Briefly, a fundamental Nd:YAG laser (1064 nm, 10 Hz repetition rate with 10 ns pulse width) was focused on a rotating metal target. The laser-ablated Cr, Mn, or Fe metal atoms were co-deposited with hydrogen sulfide diluted in an argon matrix (typically 0.3%) on a 5 K CsI window for 1 h. After sample co-deposition, the Fourier transform infrared spectra were recorded between 400 and 4000 cm –1 at 0.5 cm –1 resolution using a Bruker 80 V spectrometer with a liquid nitrogen-cooled broadband MCT detector.…”

Theoretical Exploration of Peculiar Sandwich-Type Clusters Formed by the Coordination of E92– (E = Si, Ge, Sn) Zintl Clusters: Structural Properties, Active Sites, and Hydrogen Storage

“…Si, Ge, and Sn Zintl clusters show considerable potential for energy storage. For instance, Si, Ge, and Sn alloy anode materials have many applications in lithium ion batteries. − Second, Si and Ge Zintl clusters have been widely studied and used for hydrogen storage, in particular, − three main types: gaseous, liquid, and solid hydrogen storage. Owing to the large potential safety hazards of gaseous and liquid hydrogen storage, hydrogen storage is mainly realized by solid hydrogen storage via electrostatic forces, van der Waals interactions, ionic bonds, and covalent bonds .…”