Theoretical study on atmospheric reactions of fluoranthene and pyrene with N2O5/NO3/NO2

It is complex to assign the products obtained from the gas-phase reactions of PAHs with NO3/NO2 and N2O5. For this purpose, theoretical calculations are performed. Results show that 2-nitrofluoranthene and 2-nitropyrene are the dominant products for reactions of fluoranthene and pyrene with NO3/NO2, while 3-nitrofluoranthene and 1-nitropyrene are the major nitration products of N2O5. S(N)2 reaction mechanisms are elucidated and homolytic mechanisms are calculated for the first time. Rate constants for reactions of fluoranthene and pyrene with N2O5 are deduced for the first time, which are 2.50 x 10(-27) and 2.16 x 10(-24) cm(3) molecule(-1) s(-1), respectively at 298 K. (C) 2015 Elsevier B.V. All rights reserved.