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Gas Phase Photofragmentation Dynamics of Hnco/Dnco After Laser Excitation At 222 nM

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Using the laser photolysis/laser-induced fluorescence (LP/LIF) pump-probe technique, the gas phase photofragmentation dynamics of HNCO and DNCO at room temperature was studied at photolysis wavelength of 222 nm. H/D atoms produced via HNCO/DNCO (X1A) + hv → H/D(2S) + NCO (X2P) were detected by (2p2P → 1s2S) LIF. The quantum yield for photofragmentation into H atom channel has been measured to be ΦH(222 nm) = (0.33±0.04) for HNCO. For the isotopomer DNCO the quantum yield value was (ΦD(222 nm) = (0.42±0.09). From H/D atom Doppler profiles measured under single collision conditions, the fraction fT of the available energy released as product translational energy was determined to be ft (H+NCO) =(0.37±0.03) and fT (D+NCO) =(0.36±0.03) at 222 nm. The experimental results suggest that isomerisation from the optically excited trans HNCO to cis HNCO followed by dissociation on S1 surface is the prevalent mechanism at this wavelength.

Affiliations: 1: Physikalisch-Chemisches Institut der Universitat Heidelberg, Im Neuenheimer Feld 253, D-69120 Heidelberg, Germany; 2: Chemistry Division, Bhabha Atomic Research Center, Mumbai 400 085, India


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