title: Excited state dynamics in SO2. I. Bound state relaxation studied by time-resolved photoelectron-photoion coincidence spectroscopy.
abstract: The excited state dynamics of isolated sulfur dioxide molecules have been investigated using the time-resolved photoelectron spectroscopy and time-resolved photoelectron-photoion coincidence techniques. Excited state wavepackets were prepared in the spectroscopically complex, electronically mixed (B̃)(1)B1/(Ã)(1)A2, Clements manifold following broadband excitation at a range of photon energies between 4.03 eV and 4.28 eV (308 nm and 290 nm, respectively). The resulting wavepacket dynamics were monitored using a multiphoton ionisation probe. The extensive literature associated with the Clements bands has been summarised and a detailed time domain description of the ultrafast relaxation pathways occurring from the optically bright (B̃)(1)B1 diabatic state is presented. Signatures of the oscillatory motion on the (B̃)(1)B1/(Ã)(1)A2 lower adiabatic surface responsible for the Clements band structure were observed. The recorded spectra also indicate that a component of the excited state wavepacket undergoes intersystem crossing from the Clements manifold to the underlying triplet states on a sub-picosecond time scale. Photoelectron signal growth time constants have been predominantly associated with intersystem crossing to the (c̃)(3)B2 state and were measured to vary between 750 and 150 fs over the implemented pump photon energy range. Additionally, pump beam intensity studies were performed. These experiments highlighted parallel relaxation processes that occurred at the one- and two-pump-photon levels of excitation on similar time scales, obscuring the Clements band dynamics when high pump beam intensities were implemented. Hence, the Clements band dynamics may be difficult to disentangle from higher order processes when ultrashort laser pulses and less-differential probe techniques are implemented.
authors.affiliation: National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario K1A OR6, Canada.
authors.forename: Iain
authors.initials: I
authors.lastname: Wilkinson
authors.affiliation: National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario K1A OR6, Canada.
authors.forename: Andrey E
authors.initials: AE
authors.lastname: Boguslavskiy
authors.affiliation: National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario K1A OR6, Canada.
authors.forename: Jochen
authors.initials: J
authors.lastname: Mikosch
authors.affiliation: National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario K1A OR6, Canada.
authors.forename: Julien B
authors.initials: JB
authors.lastname: Bertrand
authors.affiliation: National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario K1A OR6, Canada.
authors.forename: Hans Jakob
authors.initials: HJ
authors.lastname: Wörner
authors.affiliation: National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario K1A OR6, Canada.
authors.forename: David M
authors.initials: DM
authors.lastname: Villeneuve
authors.affiliation: National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario K1A OR6, Canada.
authors.forename: Michael
authors.initials: M
authors.lastname: Spanner
authors.affiliation: National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario K1A OR6, Canada.
authors.forename: Serguei
authors.initials: S
authors.lastname: Patchkovskii
authors.affiliation: National Research Council of Canada, 100 Sussex Drive, Ottawa, Ontario K1A OR6, Canada.
authors.forename: Albert
authors.initials: A
authors.lastname: Stolow