State-resolved predissociation dynamics of the formyloxyl radical

State-Resolved Quantum Dynamics of Photodetachment of HCO2−/DCO2− on an Accurate Global Potential Energy Surface

“…Third, the propagation time (roughly equivalent to 2 ps) may be too short to completely capture the long-lived tunneling feature for low-lying peaks. Nonetheless, these rovibrational state distributions of the CO 2 product represent a huge improvement over our previous work 22 on the LTSH PES in comparing with the experimental observations of Ray et al 14 To understand the CO 2 internal excitation, we rely on the recently proposed sudden vector projection (SVP) model. 63−66 Assuming an instantaneous dissociation, the extent of vibrational excitation in the product of the unimolecular reaction is related to the coupling of the product vibrational mode with the reaction coordinate at the transition state (TS3 in Figure 2).…”

Photoelectron photofragment coincidence spectroscopy of carboxylates

“…One example of this is studying the dissociation dynamics of HCO 2 to probe the transition state region of H + CO 2 / OH + CO, a fundamental gas-phase reaction that plays a role in combustion and the atmosphere. 4,5 Another is probing the competing channels that follow photodetachment of pcoumarate, to investigate the role of the protein environment and the chromophore in the photoactive yellow protein by establishing gas-phase benchmarks for the isolated chromophores. 6 Solution-phase decarboxylation has been investigated using experimental and theoretical approaches, and comparison to gas-phase dynamics studies allows the role of solvation to be understood.…”

“…The dominant DPD channel for carboxylate anions following photodetachment is decarboxylation, driven by the thermodynamic stability of CO 2 . [4][5][6]10,11 Ionic photodissociation, again thermodynamically driven by the formation of neutral CO 2 , has also been observed for a handful of carboxylates. 6,12 In some cases photodetachment may result in a stable radical with a lifetime longer than the ight time of the neutral fragments (typically z10 ms).…”

“…Therefore, PPC spectroscopy is able to study the decarboxylation dynamics of carboxyl radicals in detail. [4][5][6]10,11 2 Experimental methods…”

An investigation into low-lying electronic states of HCS2 via threshold photoelectron imaging

“…[1][2][3][4][5][6][7][8][9] Fine electronic states of HCO 2 have been reported in gas phase via slow electron velocity-map imaging method by Neumark group. 6 Their study unambiguously identified that 2 A 1 state was the ground state and 2 B 2 state was a very lowlying excited state with term energy of T 0 = 0.039(1) eV.…”