Photodissociation Spectroscopy and Dissociation Dynamics of TiO^+(CO_2)

Details Photodissociation Spectroscopy and Dissociation Dynamics of TiO^+(CO_2) Photodissociation Spectroscopy and Dissociation Dynamics of TiO^+(CO_2)

Jun 2009

adsabs.harvard.edu/cgi-bin/nph-data_query?bibcode=2009mss..conferf15p&link_type=abstract

"International Symposium On Molecular Spectroscopy, 64th Meeting, Held 22-26 June, 2009 at Ohio State University. http://molspec

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TiO^+(CO_2) is produced by reaction of laser-ablated titianium atoms with CO_2 and subsequent clustering, supersonically cooled and its electronic spectroscopy characterized by photofragment spectroscopy, monitoring loss of CO_2. The photodissociation spectrum consists of a vibrationally-resolved band in the visible, with extensive progressions in the covalent Ti-O stretch (952 cm^{-1} vibrational frequency and 5 cm^{-1} anharmonicity), and in the TiO^+-(CO_2) stretch (186 cm^{-1}) and rock (45 cm^{-1}). The band origin is at 13918 cm^{-1}, assigned using titanium isotope shifts, and the spectrum extends to 17350 cm^{-1}. The excited state lifetime decreases dramatically with increasing internal energy, from 1100 ns for the lowest energy band (v_{TiO}=0), to <50 ns for v_{TiO}=3. The long photodissociation lifetime substantially reduces the photodissociation quantum yield at low energy, likely due to competition with fluorescence. Electronic structure calculations help to assign the spectrum of TiO^+(CO_2) and predict allowed electronic transitions of TiO^+ in the visible, which have not been previously measured. Time-dependent density functional calculations predict that the observed transition is due to B, ^2Π← X, ^2Δ in the TiO^+ chromophore, and that binding to CO_2 red shifts the TiO^+ transition by 1508 cm^{-1}, and lowers the Ti-O stretch frequency by 16 cm^{-1}. Combining the computational and experimental results, the ^2Π state of TiO^+ is predicted to lie at T_0=15426 cm^{-1}, with frequency ωe = 968 cm^{-1} and anharmonicity ωexe = 5 cm^{-1}. The calculations also predict that there is only one low-lying ^2Σ state of TiO^+, contrary to conclusions derived from photoelectron spectroscopy of TiO. Prospects for astronomical observation of TiO^+ via the ^2Π-^2Δ transition are also discussed.

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