Abstract
A detailed computational investigation is executed on the reaction between NO(3) and CH[triple bond, length as m-dash]CCH(2)OH at the CCSD(T)/cc-pVTZ//B3LYP/6-311++G(d,p) level. Addition/elimination and H-abstraction mechanisms are found for the NO(3) + CH[triple bond, length as m-dash]CCH(2)OH reaction, and they could compete with each other. The most feasible addition/elimination pathway through a series of central-C addition, 1,4-H migration to generate intermediates IM1 (CHCONO(2)CH(2)OH) and IM3 (CH(2)CONO(2)CH(2)O), and then IM3 directly decompose into product P2 (CH(2)CONO(2)CHO + H). The dominant H-abstraction pathway is abstracting the H atom of the -CH(2)- group to generate h-P1 (CHCCHOH + HNO(3)). RRKM-TST theory was used to compute the kinetics and product branching ratios of the NO(3) + CH[triple bond, length as m-dash]CCH(2)OH reaction at 200-3000 K. The rate constants at 298 K are consistent with the experimental values. The lifetime of CH[triple bond, length as m-dash]CCH(2)OH is estimated to be 59.72 days at 298 K. The implicit solvent model was used to examine the solvent effect on the total reaction. Based on the quantitative structure-activity relationship (QSAR) model, the toxicity during the degradation process is increased towards fish, and decreased towards daphnia and green algae.