Reply to “Comment on ‘Does Tetrahydrofuran (THF) Behave like a Solvent or a Reactant in the Photolysis of Thionyl Chloride (Cl2SO) in Cyclohexane? A Transient Infrared Difference Study’”

We would like to clarify two important issues that are not thoroughly considered and addressed in the Comment. (1)

Dr. Korth proposed the mechanisms regarding the reaction of the chlorine radical with both cyclohexane (cHex) and tetrahydrofuran (THF). However, the concentration of cHex (9.3 M) is much higher than that of THF (0.082 M). Assuming that the bimolecular rate coefficients of the chlorine radical with cHex and THF are similar, the reactions of the chlorine radical with THF and the cascading steps, after eq 7, would be very minor. The proposed generation of the secondary and cascading products will be less possible. On the contrary, if the proposed mechanisms by Dr. Korth are important, there will be more vibrational features in the time-resolved infrared difference spectra. (2) Therefore, the THF in a very small portion in cHex might not be greatly involved in the secondary reactions.

In addition, some predicted vibrational wavenumbers of relevant species are not reasonable. Taking Cl–THF for example, its vibrational wavenumbers did largely shift toward high wavenumbers after accounting for the solvent effect, whereas other X–THF species did not manifest the same trend. However, 100 cm^–1 is a big difference. The wavenumbers in the Supporting Information of ref (1) should be sorted in terms of the vibrational modes. On the basis of the predicted vibrational features in the Supporting Information, we are not able to confirm the correctness.