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Benjamin J Whitaker

Publications and source records attributed to Benjamin J Whitaker.

5 recordsLinked to original sources
PubMed2006

Time-resolved photoion and photoelectron imaging of NO(2).

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.

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PubMed2004

Dissociative multiphoton ionization of NO2 studied by time-resolved imaging.

We have studied dissociative multiphoton ionization of NO2 by time-resolved velocity map imaging in a two-color pump-probe experiment using the 400 and 266 nm harmonics of a regeneratively amplified titanium-sapphire laser. We observe that most of the ion signal appears as NO+ with approximately 0.28 eV peak kinetic energy. Approximately 600 fs period oscillations indicative of wave packet motion are also observed in the NO+ decay. We attribute the signal to two competitive mechanisms. The first involving three-photon 400 nm absorption followed by dissociative ionization of the pumped state by a subsequent 266 nm photon. The second involving one-photon 400 nm absorption to the 2B2 state of NO2 followed by two-photon dissociative ionization at 266 nm. This interpretation is derived from the observation that the total NO+ ion signal exhibits biexponential decay, 0.72 exp(-t/90+/-10)+0.28 exp(-t/4000+/-400), where t is the 266 nm delay in femtoseconds. The fast decay of the majority of the NO+ signal suggests a direct dissociation via the bending mode of the pumped state. .

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PubMed2003

Excited state dynamics and rapid internal conversion in a stable dipole molecule.

The excited singlet state of an azomethine ylide or 'stable dipole' exhibits an ultrafast radiationless relaxation after femtosecond laser excitation. These transients are observed before the excited state decays in an almost activationless manner, the barrier is 440 cm-1, to the ground state with a 1.5 ps lifetime. Cooling of the hot ground state is also apparent in the transient absorption data and in methanol decays with a 5.7 ps lifetime. The viscosity dependence of the fluorescence yield and lifetime in different solvents is small and far less pronounced than in triphenylmethane dyes. Surprisingly, the excited state decay is not due to twisting about the C-N bond of the ylide but it is caused by buckling of one of the rings as the nitrogen atom changes character from sp2 to sp3 hybridisation.

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