Product channels in the 193-nm photodissociation of HCNO (fulminic acid)

Abstract

IR diode laser spectroscopy was used to detect the products of HCNO (fulminic acid) photolysis at 193 nm. Six product channels are energetically possible at this photolysis wavelength: O + HCN, H + NCO/CNO, CN + OH, CO + NH, NO + CH and HNCO. In some experiments, isotopically labeled 15 N 18 O, C 2 D 6 or C 6 H 12 reagents were included into the photolysis mixture in order to suppress and/or redirect possible secondary reactions. HCN, OC 18 O, 15 N 15 NO, CO, DCN and HNCO molecules were detected upon laser photolysis of HCNO/reagents/buffer gas mixtures. Analysis of the yields of product molecules leads to the following photolysis quantum yields: φ 1a (O+HCN) = 0.38 ± 0.04, φ 1b (H + (NCO)) = 0.07 ± 0.02, φ 1c (CN + OH) = 0.24 ± 0.03, φ 1d (CO + NH(a 1 ∆)) < 0.22 ± 0.1, φ 1e (HNCO) = 0.02 ± 0.01 and φ 1f (CH + NO) = 0.21 ± 0.1, respectively.

Mechanism and kinetics for the reaction of fulminic acid, HCNO, with an amino radical, NH2

“…Later, Grußdorf et al [16] reported that the dominant channel is HCNO + H, accounting for about 84%. The physicochemical properties of HCNO, and its reactions with various species present in hydrocarbon combustion such as H-and O-atoms, HO x radicals, and other reactive species have been investigated [3,[17][18][19][20][21][22][23][24][25][26][27][28][29]. Theoretical studies showed that there are two main mechanisms for the reactions of HCNO, i.e.…”

Photoelectron spectroscopy and dissociative photoionization of fulminic acid, HCNO

“…19 Particularly relevant for the present work are studies by Mondal et al 20 on the appearance of Jahn-Teller and Renner-Teller interactions in HCNO + as well as the work by Luna et al who published the global potential energy surface of the [H,C,N,O] + system using density functional theory. 21 Experimentally the microwave [22][23][24] and IR-spectra [24][25][26][27][28][29][30][31][32] have been reported, the photodissociation has been investigated at 248 nm 33 and 193 nm 34 and the kinetics of the HCNO + OH reaction has been studied 35 . In the soft X-ray regime, we recently reported normal and resonant Auger spectra of HCNO at all three K-edges.…”

Auger electron spectroscopy of fulminic acid, HCNO: an experimental and theoretical study

“…12,13 Additionally, Feng et al studied the reaction kinetics with OH 14 and the photodissociation of HCNO at 248 nm and 193 nm. 15,16 In contrast, no studies in the X-ray regime have been reported yet. Because HCNO consists of only 4 atoms and 22 electrons it has also been attractive for theoretical chemists early on.…”