Mixing between Vibrationally Highly Excited Resonance States of DCO
نویسندگان
چکیده
Over the last years, state-resolved studies of unimolecular reactions of small and intermediate size molecules have provided considerable new insight into the dissociative dynamics of vibrationally highly excited molecules. In our laboratory, we use the technique of stimulated emission pumping (SEP) for preparing and probing selected highly excited states. In a case study of DCO ( X~ A’), we developed an effective polyad Hamiltonian for modeling the observed SEP spectra and the ensuing unimolecular dynamics. The model showed a high degree of mode specificity of the unimolecular dynamics. However, the decay rates of the individual resonance states were seen to exhibit extensive state-to-state fluctuations, which cannot easily be reconciled with a mode specific model.
منابع مشابه
Stimulated Emission Pumping Studies of Highly Vibrationally Excited Dco ( ): from Spectra to Unimolecular Dynamics
متن کامل
Spectroscopy of highly excited vibrational states of HCN in its ground electronic state.
An experimental technique based on a scheme of vibrationally mediated photodissociation has been developed and applied to the spectroscopic study of highly excited vibrational states in HCN, with energies between 29,000 and 30,000 cm(-1). The technique consists of four sequential steps: in the first one, a high power laser is used to vibrationally excite the sample to an intermediate state, typ...
متن کاملGeneration and characterization of highly vibrationally excited molecular beam.
A simple method to generate and characterize a pure highly vibrationally excited azulene molecular beam is demonstrated. Azulene molecules initially excited to the S4 state by 266-nm UV photons reach high vibrationally excited levels of the ground electronic state upon rapid internal conversion from the S4 electronically excited state. VUV laser beams at 157 and 118 nm, respectively, are used t...
متن کاملPhotodissociation dynamics of vibrationally excited CH2Cl2 molecules
Photodissociation of dichloromethane excited to the second C–H stretch overtone was performed by 235 nm photons that also tagged the Cl P3=2 [Cl] and spin–orbit excited Cl P1=2 [Cl ] photofragments via resonantly enhanced multiphoton ionization. The measured time-of-flight profiles together with the determined Cl /Cl branching ratio suggest fast dissociation and involvement of several upper sta...
متن کاملElectric Field Induced Dissociation of Molecules in Rydberg-like Highly Vibrationally Excited Ion-Pair States
The energetic thresholds for ion-pair photodissociation of diatomic oxygen fO2 1 hn ! O 1 OsP3y2, P1y2dg were measured using a novel technique. The technique depends on the production and selective detection of highly vibrationally excited ion-pair states which last for at least 5 ms following single photon excitation from the ground electronic state of O2. These ion-pair states are analogous t...
متن کامل