A Theoretical Investigation of the Decomposition Reactions of Ethyl Formate in the S1 and T1 States

This study investigates the decomposition reactions of ethyl formate in the S₁ and T₁ states. The dissociation channels leading to HCOOH + C₂H₄, CH₃CH₂O + HCO, CH₃CH₂OCO + H, and CH₃CH₂ + HCO₂ were studied. The major reactions of ethyl formate in the S₁ and T₁ states are isomerization to the biradical CH₂CH₂OC(OH)H and dissociation to CH₃CH₂O + HCO. All the stationary and intersection points were optimized at the CAS(10,8) level of theory with the 6‐31G(d,p) and 6‐311G(2df,2pd) basis sets. Single‐point CASPT3 energy was calculated for each of the stationary and intersection points. Microcanonical rate constants were also calculated for each of the reactions by using the RRKM theory.