Spectroscopic Characterization of Peroxynitrous Acid in cis-perp Configurations

Abstract

This paper presents experimental evidence, supported by two-dimensional theoretical calculations, that HOONO can be observed in cis-perp (cp) configurations in a pulsed supersonic expansion. The spectral properties (transition frequency, rotational constants, and transition type) of OH overtone transitions originating from a state with predominately cp character are predicted theoretically and compared with those associated with a weak feature at 6996.2 cm(-1) observed experimentally using infrared action spectroscopy. This spectral feature is attributed to HOONO in cp configurations based on its vibrational frequency, rotational band contour, and resultant OH product state distribution.

Sunlight‐Initiated Photochemistry: Excited Vibrational States of Atmospheric Chromophores

“…Slight differences in the product distribution of OH were seen when the combination band of the O-H stretch overtone and the torsion mode was excited compared to the excitation via pure O-H stretch overtone. Following their work, overtone-induced photodissociation reactions have been investigated in several molecules with the O-O-H bond, such as peroxynitric acid (O 2 NOOH) [28,32], peroxynitrous acid (ONOOH) [20,[64][65][66], methyl hydroperoxide (CH 3 OOH) [27,67], as well as hydrogen trioxy radical (OOOH) [68,69]. Furthermore, systems with weak bonds adjacent to the O-H bond, such as N-O (De∼55 kcal/mol) in nitric acid (O 2 NOH) [70,71] and O-Cl (De∼43 kcal) in ClOH [72][73][74][75], have also been investigated as possible candidates to dissociate following O-H stretching overtone excitation.…”

Visible Light-Driven Chemistry of Oxalic Acid in Solid Argon, Probed by Raman Spectroscopy

“…Molecules containing an OH-chromophore are the most convenient targets for these experimental studies, because the OH stretching vibrational transitions are characterized by higher frequencies and larger cross sections than C–H, S–H, and N–H vibrational transitions. − In turn, the ν(OH) combination modes have been observed with equally significant absorption intensities in the NIR as ν(OH) overtones . High-overtone-driven photodecomposition reactions have been successfully demonstrated for both organic ,, and inorganic − compounds, and a number of isomerization processes initiated by high-overtone pumping have also been reported. ,,, …”

Dynamics and spectroscopy of vibrational overtone excited glyoxylic acid and 2,2-dihydroxyacetic acid in the gas-phase

“…Light initiated processes provide attractive systems for studying state specific unimolecular reactions since photon absorption generates activated complexes with a narrow distribution of internal energy. [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20] Unimolecular reactions are traditionally treated with statistical approaches such as Rice-Ramsperger-Kassel-Marcus Theory ͑RRKM͒, which assumes that coupling within the activated complex is sufficiently strong to distribute excitation energy between all vibrational modes on a fast time scale compared with reaction. 19,[21][22][23][24][25] Several classic studies using reactions initiated by excitation of vibrational overtone transitions near a chemical threshold were performed in a search for control over these reactions.…”

“…20,40,41 In spite of the much lower photoabsorption cross sections for vibrational overtone transitions when compared with electronic transitions, [42][43][44] this chemistry initiated by vibrational overtone pumping in ground electronic states is important in the atmosphere. [6][7][8]20,40,41, Fast reactions, where energy dissipation is comparatively slow, are of considerable interest in environmental applications. 1,20,73 In this spirit, we present results of a study on the early time dynamics of the concerted reactions initiated by excitation of the OH vibrational overtone transition of GA and its monohydrate, 2,2-dihydroxyacetic acid ͑GAM͒.…”