Quantum chemical investigation of HCN/Cu and HNC/Cu gas-phase complexes

Defense against chemical warfare agents and toxic industrial chemicals

“…Possible complexation of HCN and ClCN to the transition metal ions was tested for a variety of possible configurations. Stable complexation was found to occur only for the linear nitrogen end-on structure that was found previously both theoretically [3] , and experimentally [16] for neutral copper. The transition metal-nitrogen distance is markedly smaller than in the neutral atom system.…”

“…Table 3 presents a partial list of reaction energetics and bond distances for the complexation of TICs (HCN, ClCN, and HCl) with Zn 2+ , Cu 2+ , and the organic dopant (TEDA). Previous theoretical studies on HCN/Cu(0) gas phase complexation wisely eschewed strict analysis of energetics and limited themselves to an analysis of geometries and orbital population [3] . We give energetics with the dual purpose of assessing feasibility for reactions that may be occurring in this complicated medium, and for placing results within the framework of experimentally validated behavior.…”

“…For this preliminary work, we follow the example of prior work [2][3] and focus on gas phase reactions of various combinations of transition metal ions, TEDA, water, and cyanide compounds. Calculations have been performed at a variety of method levels and basis set size.…”

“…From this perspective, an atomistic level understanding of the chemical reactions occurring between the media and the TIC will provide insight into tailoring more effective protection, promoting useful reactions while hopefully mitigating side reactions producing harmful products. Prior work has been performed by Fattal and Carter on zinc and phosgene systems [2] and by Hunstock, Muller, Stach, and Reinhold for the HCN/Cu system [3] .…”