Imaging Studies of Excited and Dissociative States of Hydroxymethylene Produced in the Photodissociation of the Hydroxymethyl Radical

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2014-12, Vol.118 (51), p.11916-11925
• Main Authors: Rodrigo, Chirantha P, Sutradhar, Subhasish, Reisler, Hanna
• Format: Article
• Language: English
• Subjects: Deuteration; Excitation; Formaldehyde; Imaging; Photodissociation; Radicals; Rydberg states; Thresholds
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp505108k

Rotational, vibrational, and electronic states of formaldehyde and cis-hydroxymethylene products generated in the photodissociation of the hydroxymethyl radical are investigated by sliced velocity map imaging (SVMI) following excitation of the radical to its 3p x and 3p z Rydberg states. SVMI of H and D photofragments is essential in these studies because it allows zooming in on low-velocity regions of the images where small threshold signals can be identified. With CH2OD precursors, formaldehyde and hydroxymethylene products are examined separately by monitoring D and H, respectively. Whereas the main dissociation channels lead to formaldehyde and cis-hydroxymethylene in their ground electronic states, at higher excitation energies the kinetic energy distributions (KEDs) of H and D photofragments exhibit additional small peaks, which are assigned as triplet states of formaldehyde and hydroxymethylene. Results obtained with deuterated isotopologs of CH2OH demonstrate that the yield of the triplet state of formaldehyde decreases upon increasing deuteration, suggesting that the conical intersection seams that govern the dynamics depend on the degree of deuteration. The rotational excitation of cis-hydroxymethylene depends on the excited Rydberg state of CH2OD and is lower in dissociation via the 3p z state than via the lower lying 3p x and 3s states. Vibrational excitation of cis-HCOD, which spans the entire allowed internal energy range, consists mostly of the CO-stretch and in-plane bend modes. When the internal energy of cis-HCOD exceeds the dissociation threshold to D + HCO, slow D and H photofragments deriving from secondary dissociation are observed. The yields of these H and D fragments are comparable, and we propose that they are generated via prior isomerization of cis-HCOD to HDCO.