Xác định hằng số tốc độ và một số đại lượng nhiệt động của phản ứng OH• + HCNO bằng phương pháp lý thuyết

Abstract

A theoretical investigation of the HCNO + ^·OH reaction, which is carried out by means of B3LYP/6-311++G(3df,2p) + ZPVE computational method to determine a set of reasonable pathways. The potential energy surface for this system shows that there are sixteen different product pathways: PR1 (H₂O + ^·CNO), PR2 (CH₂O + NO), PR3 (OCHNO + H), PR4 (CHOH: + NO), PR5 (CO₂ + ^·NH₂), PR6 (HOCN + ^·OH), PR7 (OCNOH + H), PR8 (HOCNO + H), PR9 (OCN^· + H₂O), PR10 (H₂ + OCNO), PR11 (CO + ^·NHOH), PR12(OCNH + ^·OH), PR13 (CO + NO + H₂), PR14 (^·CHO + HNO), PR15 (CO + NH₂O^·) and PR16 (HCN + HO₂^·). The results indicate that PR11 (CO + ^·NHOH) and PR14 (^·CHO + HNO) are the major product channels. The rate constants for these processes have been calculated using variational RRKM theory covering the temperature range 300-1000 K and compared with available experimental data. The total rate constant of HCNO + ^·OH reaction at 1atm, 300 K is 4.44´10^-11 (cm³molecule^-1s^-1).

Keywords: Kinetics, ^·OH radical, forming CO, fulminic acid HCNO, potential energy surface (PES).