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The anionic products following (H + H + ) abstraction from o -, m -, and p -methylphenol (cresol) are investigated using flowing afterglow-selected ion flow tube (FA-SIFT) mass spectrometry and anion photoelectron spectroscopy (PES). The PES of the multiple anion isomers formed in this reaction are reported, including those for the most abundant isomers, o -, m - and p -methylenephenoxide distonic radical anions. The electron affinity (EA) of the ground triplet electronic state of neutral m -methylenephenoxyl diradical was measured to be 2.227 ± 0.008 eV. However, the ground singlet electronic states of o - and p -methylenephenoxyl were found to be significantly stabilized by their resonance forms as a substituted cyclohexadienone, resulting in measured EAs of 1.217 ± 0.012 and 1.096 ± 0.007 eV, respectively. Upon electron photodetachment, the resulting neutral molecules were shown to have Franck–Condon active ring distortion vibrational modes with measured frequencies of 570 ± 180 and 450 ± 80 cm −1 for the ortho and para isomers, respectively. Photodetachment to excited electronic states was also investigated for all isomers, where similar vibrational modes were found to be Franck–Condon active, and singlet–triplet splittings are reported. The thermochemistry of these molecules was investigated using FA-SIFT combined with the acid bracketing technique to yield values of 341.4 ± 4.3, 349.1 ± 3.0, and 341.4 ± 4.3 kcal mol −1 for the o -, m -, and p -methylenephenol radicals, respectively. Construction of a thermodynamic cycle allowed for an experimental determination of the bond dissociation energy of the O–H bond of m -methylenephenol radical to be 86 ± 4 kcal mol −1 , while this bond is significantly weaker for the ortho and para isomers at 55 ± 5 and 52 ± 5 kcal mol −1 , respectively. Additional EAs and vibrational frequencies are reported for several methylphenyloxyl diradical isomers, the negative ions of which are also formed by the reaction of cresol with O − .
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Photoelectron Velocity Map Imaging Spectroscopy of the Beryllium Trimer and Tetramer
Computational studies of small beryllium clusters (BeN) predict dramatic, nonmonotonic changes in the bonding mechanisms and per-atom cohesion energies with increasing N. To date, experimental tests of these quantum chemistry models are lacking for all but the Be2 molecule. In the present study, we report spectroscopic data for Be3 and Be4 obtained via anion photodetachment spectroscopy. The trimer is predicted to have D3h symmetric equilibrium structures for both the neutral molecule and the anion. Photodetachment spectra reveal transitions that originate from the X2A2″ ground state and the (1)2A1′ electronically excited state. The state symmetries were assigned on the basis of anisotropic photoelectron angular distributions. The neutral and anionic forms of Be4 are predicted to be tetrahedral. Franck−Condon diagonal photodetachment was observed with a photoelectron angular distribution consistent with the expected Be4−X2A1 → Be4X1A1 transition. The electron affinities of Be3 and Be4 were determined to be 11363 ± 60 and 13052 ± 50 cm−1, respectively
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- Award ID(s):
- 2055579
- PAR ID:
- 10519936
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- The journal of physical chemistry letters
- ISSN:
- 1948-7185
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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