
doi: 10.1039/b602825j
pmid: 16880904
Time-resolved photoion and photoelectron velocity mapped images from NO(2) excited close to its first dissociation limit [to NO(X(2)Pi) + O((3)P(2))] have been recorded in a two colour pump-probe experiment, using the frequency-doubled and frequency-tripled output of a regeneratively amplified titanium-sapphire laser. At least three processes are responsible for the observed transient signals; a negative pump-probe signal (corresponding to a 266 nm pump), a very short-lived transient close to the cross-correlation of the pump and probe pulses but on the 400 nm pump side, and a longer-lived positive pump-probe signal that exhibits a signature of wavepacket motion (oscillations). These transients have two main origins; multiphoton excitation of the Rydberg states of NO(2) by both 266 and 400 nm light, and electronic relaxation in the 1(2)B(2) state of NO(2), which leads to a quasi-dissociated NO(2) high in the 1(2)A(1) electronic ground state and just below the dissociation threshold. The wavepacket motion that we observe is ascribed to states exhibiting free rotation of the O atom about the NO moiety. These states, which are common for loosely bound systems such as a van der Waals complex but unusual for a chemically-bound molecule, have previously been observed in the frequency domain by optical double resonance spectroscopy but never before in the time domain.
Models, Molecular, Time Factors, Photochemistry, Lasers, Electrons, Nitric Oxide, Mass Spectrometry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, Models, Chemical, Computer Simulation, Algorithms
Models, Molecular, Time Factors, Photochemistry, Lasers, Electrons, Nitric Oxide, Mass Spectrometry, [CHIM.THEO] Chemical Sciences/Theoretical and/or physical chemistry, Models, Chemical, Computer Simulation, Algorithms
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