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CHCl·- activates oxygen-containing gases: Uncovering intrinsic reaction nature from a multiscale theoretical
Junxi Liang1, Jie Gao1,2, Xinjie Wang1
1Key Laboratory of Environment-Friendly Composite Materials of the State Ethnic Affairs Commission, Gansu Province Engineering Research Center for Biomass Functional Composite Materials, Key Laboratory for the Utilization of Environment-Friendly Composite Materials and Biomass in Universities of Gansu Province, Gansu Province Research Center for Basic Sciences of Surface and Interface Chemistry, College of Chemical Engineering, Northwest Minzu University, Lanzhou, Gansu 730030, China.
Abstract:
Understanding the ionic reactivity of CHCl˙- anions is essential for modeling chemical processes in interstellar media, plasmas, and planetary atmospheres. Using multiscale computational simulations, this work examines the adsorption and reaction behaviors of eight oxygen-containing gases (O2, CO, CO2, NO, N2O, NO2, COS, SO2) on CHCl˙- clusters. Our findings reveal that electrostatic interactions dominate system stabilization over dispersion forces. The O2 environment strongly induces activation of the CHCl˙- anion, while COS exhibits minimal reactivity. Bond activation occurs across O-O, C-O, C-S, N-O, N-N, and S-O linkages, with binding strengths following O2 > NO2 > SO2 > CO. Although CO2, NO, and N2O interactions are thermodynamically limited at room temperature, they become accessible upon heating. These results demonstrate that anion-molecule reactivity emerges from coupled mass transport, electrostatic compatibility, and bond lability, thereby advancing predictive frameworks for radical-mediated chemistry.
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