- Utilizing vibrationally mediated photodissociation of jet-cooled CH3CFCl2 enabled monitoring of the second (3νCH) and third (4νCH) overtones of the methyl in the ground electronic state. The excited molecules are photodissociated by ∼235 or 243.135 nm photons that further tag Cl(2P3/2)[Cl] and Cl(2P1/2)[Cl∗] isotopes or H photofragments via mass selective (2+1) resonantly enhanced multiphoton ionization. The vibrational spectra are characterized by a multiple peak structure related to C–H stretches and to Fermi resonating levels involving the CH3 deformation. The cooling in the expansion reduces the rotational and vibrational congestion and affords a determination of the splittings and the upper limits for homogeneous broadening of the transitions. The highest-frequency peak of 4νCH exhibits an additional splitting, related to coupling of the mixed stretch–deformation states with other modes of the molecule. The yield of all three photofragments increases as a result of preexcitation, demonstrating that the energy is not preserved in the excited bond but rather flows to the C–Cl bond. The initial vibrational state preparation not only enhances C–Cl and C–H bond cleavage but also affects the Cl∗/Cl branching ratio, as compared to the nearly isoenergetic one-photon 193 nm photolysis of vibrationless ground state CH3CFCl2, implying that it alters the photodissociation dynamics. © 2000 American Institute of Physics.