The potential energy surface for the [C₂H₂O]^+˙ system: The ketene radical cation [CH₂CO]^+˙ and its isomers

Gas-Phase Ion Chemistry of Oxalyl Chloride: An Electron Bombardment Matrix Isolation FTIR Spectroscopic Study

“…We believe that this technique may find use in the isolation and spectroscopic characterization of some important molecules that have eluded direct spectroscopic observation to date. These include molecules such as OCCO, , oxirene, oxywater, and the tautomers of formamide 39a,b and N -methylformamide, 39a,c All except oxywater have been observed in NRMS experiments, and all are proposed to be obtainable through the corresponding radical cations. The correct choice of precursors, charge exchange agent, and quenching agent may result in the matrix isolation and direct observation of these very important and interesting molecules.…”

Selenoketene (H2CCSe)+• and selenoketyl cumulene (HCCSe)+ ions and their neutral counterparts: a tandem mass spectrometric and computational study

“…Ion 1b +• (selenirene) is the second most stable structure, followed by 1c +• (ethyne selenol), 1d +• , and 1e +• , which are less stable than 1a +• by 51.3 kJ mol −1 , 99.6 kJ mol −1 , 292 kJ mol −1 , and 402 kJ mol −1 respectively. This is in contrast to the stability order of oxygen analogues wherein ethynol radical cation (HCCOH) +• is second most stable isomer followed by oxirene ($\catcode`@=11 \def\overlsqmatrix#1{\null\vbox{\normalbaselines\m@th \ialign{\hfil$##$\hfil&&\quad\hfil$##$\hfil\crcr \mathstrut\crcr\noalign{\kern-\baselineskip} #1\crcr\mathstrut\crcr\noalign{\kern-\baselineskip}}}} \newdimen\rulwidth \def\downsqbrace#1{\setbox1=\hbox{#1} \rulwidth=\wd1\advance \rulwidth by -6pt \raise3pt\hbox{$\overlsqmatrix{\vrule height5pt\kern-0.5pt\raise5pt\hbox to \rulwidth{\hrulefill}\kern-0.5pt\vrule height5pt\cr\noalign{\vskip-3pt}\hbox{#1}\cr\noalign{\vskip-5pt}}$}} \catcode`@=12 \def\bond{\hbox{--}} \def\dbond{\hbox{=}} \downsqbrace{CH\dbond CH{\bond}O}$ ) +• , which are reported to be less stable than the ketene (CH 2 CO) +• ion by 189 kJ mol −1 and 257 kJ mol −1 , respectively 36. Ion 1d +• has both syn ‐ and anti ‐ isomers, which have a difference of only 12 kJ mol −1 .…”

“…4). This is similar to the stability of neutral oxygen analogues, that is, isomers of ketene 36. The energy barriers for isomerization from 1a → 1b is 321.5 kJ mol −1 , 1a → 1c , 355 kJ mol −1 , 1b → 1d , 271 kJ mol −1 , 1c → 1d , 253.1 kJ mol −1 and 1d → 1e , 487.5 kJ mol −1 .…”

“…Very recently, we have shown that a polycarbon selenocumulene HC 3 Se, is a stable species in the gas phase, by using a combination of NRMS and computational study 33. While the ketene has been well characterized by NRMS34 and theoretical calculations,35, 36 there is no report in the literature on characterization of selenoketene. In continuation of our studies on selenium‐containing molecules, we report here the successful characterization of ionic and neutral selenoketene H 2 CCSe +•/o and a selenoketyl radical, HC 2 Se +/• by NRMS in combination with theoretical calculations.…”

Anharmonic Franck–Condon Factors for the X̃2B1 ← X̃1A1 Photoionization of Ketene

“…For example, Hall et al 7 studied the electronic states of the radical cation of ketene. Bouma et al 8 investigated the potential energy surface of H 2 CCO +• , and Orlova et al 9 were interested in the water-catalyzed hydrolysis of the radical cation of ketene, whereas Heinrich et al 10 had a detailed look at the reaction of H 2 CCO +• with ethylene. For sure, this list is not comprehensive.…”