Infrared multiphoton dissociation of DN3 and HN3: Formation and reaction of electronically excited ND

✍ Scribed by Allen Hartford Jr.

• Publisher: Elsevier Science
• Year: 1978
• Tongue: English
• Weight: 450 KB
• Volume: 57
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(78)85524-9

✦ Synopsis

ChemZiZescence is observed from DN3 at pressures beIov3 100 mtorr fonowing irradiation with the focused output of a Co? TJZA laser. Emission is attributed to ND2 (2A1) formed in the reaction ND@ :a) + DN3 -c ND2 (*Al) i N3. The ND(a i a) is produced ia the primary photolysis. Tiie resolved studies of the fluorescence permit determination of the rate constant for the chemiiumiuescent reaction (2.09 f: 0.31 w-r torr-I)_ Multiphoton dissociation of H&l3 by use of a laser wav&engtlx coincident with a hot baud absomtion is also demonstrated I. Itltmduction The vapor phase photolysis of hydrazoic acid in the ultraviolet and near ~2cuum ultraviolet spectral R@OIXS has been studied by several iIW%tigttOrS [I--31. The primary dissociation charmer involves the formation of NH and N2. As a fimction of the phOtO&sis wavelength the NH may be produced in several different eIectronicalJy excited states. In the most recent study [4f, Iaser photo@sis of H?J; at 266 run was found to produce NH almost excInsiveIy in the a 'A, V' = 0 state -9.8%). Jn addition, the rate constant for the secondary reaction NH@ IA, V' = 0) + Ii& -+ NHz(2Ar) f NS has been determined by monitoriug the time resolved chemiluminescence from the electronically excited NH2 [S] _ The infrared m~ti~hoton dissociation [6] of both DN3 and E_IN3 is reported. This study was undertaken for a number of reasons, one being the existence of infrared absorption bands in both molecules in the vicinity of CO2 laser emission, Furrhermore, *&e baud in DNI, corresponds to a strong vibrational fundamental (D--N bending mode), while iu HN3 the absorption feature is due to a much weaker hot band. The disparate intensities of these bands, together with the possiiility of scavenging the reactive ND hiradical, suggest the potential for deuterium enrichment.