The Synergy Between Qualitative Theory, Quantitative Calculations, and Direct Experiments in Understanding, Calculating, and Measuring the Energy Differences Between the Lowest Singlet and Triplet States of Organic Diradicals

Article discussing the synergy between qualitative theory, quantitative calculations, and direct experiments in understanding, calculating, and measuring the energy differences between the lowest singlet and triplet states of organic diradicals

Anion Photoelectron Spectroscopy of Deprotonated ortho-, meta-, and para-methylphenol

The anion photoelectron spectra of ortho-, meta-, and para-methylphenoxide, as well as methyl deprotonated meta-methylphenol, were measured. Using the Slow Electron Velocity Map Imaging technique, the Electron Affinities (EAs) of the o-, m-, and p-methylphenoxyl radicals were measured as follows: 2.1991±0.0014, 2.2177±0.0014, and 2.1199±0.0014 eV, respectively. The EA of m-methylenephenol was also obtained, 1.024±0.008 eV. In all four cases, the dominant vibrational progressions observed are due to several ring distortion vibrational normal modes that were activated upon photodetachment, leading to vibrational progressions spaced by ∼500 cm−1. Using the methylphenol O–H bond dissociation energies reported by King et al. and revised by Karsili et al., a thermodynamic cycle was constructed and the acidities of the methylphenol isomers were determined as follows: ΔacidH0298K=348.39±0.25, 348.82±0.25, 350.08±0.25, and 349.60±0.25 kcal/mol for cis-ortho-, trans-ortho-, m-, and p-methylphenol, respectively. The excitation energies for the ground doublet state to the lowest excited doublet state electronic transition in o-, m-, and p-methylphenoxyl were also measured as follows: 1.029±0.009, 0.962±0.002, and 1.029±0.009 eV, respectively. In the photoelectron spectra of the neutral excited states, C–O stretching modes were excited in addition to ring distortion modes. Electron autodetachment was observed in the cases of both m- and p-methylphenoxide, with the para isomer showing a lower photon energy onset for this phenomenon

Photoelectron spectroscopy of the hydroxymethoxide anion, H 2 C(OH)O −

We report the negative ion photoelectron spectroscopy of the hydroxymethoxide anion, H2C(OH)O − . The photoelectron spectra show that 3.49 eV photodetachment produces two distinct electronic states of the neutral hydroxymethoxy radical (H2C(OH)O · ). The H2C(OH)O · ground state (X˜ 2A) photoelectron spectrum exhibits a vibrational progression consisting primarily of the OCO symmetric and asymmetric stretches, the OCO bend, as well as combination bands involving these modes with other, lower frequency modes. A high-resolution photoelectron spectrum aids in the assignment of several vibrational frequencies of the neutral H2C(OH)O · radical, including an experimental determination of the H2C(OH)O · 2ν12 overtone of the H–OCO torsional vibration as 220(10) cm−1 . The electron affinity of H2C(OH)O · is determined to be 2.220(2) eV. The low-lying A˜ 2A excited state is also observed, with a spectrum that peaks ∼0.8 eV above the X˜ 2A state origin. The A˜ 2A state photoelectron spectrum is a broad, partially resolved band. Quantum chemical calculations and photoelectron simulations aid in the interpretation of the photoelectron spectra. In addition, the gas phase acidity of methanediol is calculated to be 366(2) kcal mol−1 , which results in an OH bond dissociation energy, D0(H2C(OH)O–H), of 104(2) kcal mol−1 , using the experimentally determined electron affinity of the hydroxymethoxy radical

Negative-Ion Photoelectron Spectroscopy, Gas-Phase Acidity, and Thermochemistry of the Peroxyl Radicals CH_3OO and CH_3CH_2OO

Methyl, methyl-d3, and ethyl hydroperoxide anions (CH_3OO-, CD_3OO-, and CH_3CH_2OO-) have been prepared by deprotonation of their respective hydroperoxides in a stream of helium buffer gas. Photodetachment with 364 nm (3.408 eV) radiation was used to measure the adiabatic electron affinities:  EA[CH_3OO, X̃^2A‘‘] = 1.161 ± 0.005 eV, EA[CD_3OO, X̃^2A‘‘] = 1.154 ± 0.004 eV, and EA[CH_3CH_2OO, X̃^2A‘‘] = 1.186 ± 0.004 eV. The photoelectron spectra yield values for the term energies:  ΔE(X̃^2A‘‘−Ã^2A‘)[CH_3OO] = 0.914 ± 0.005 eV, ΔE(X̃^2A‘‘−Ã^2A‘)[CD_3OO] = 0.913 ± 0.004 eV, and ΔE(X̃^2A‘‘−Ã^2A‘)[CH_3CH_2OO] = 0.938 ± 0.004 eV. A localized RO−O stretching mode was observed near 1100 cm^(-1) for the ground state of all three radicals, and low-frequency R−O−O bending modes are also reported. Proton-transfer kinetics of the hydroperoxides have been measured in a tandem flowing afterglow−selected ion flow tube (FA-SIFT) to determine the gas-phase acidity of the parent hydroperoxides: Δ_(acid)G_(298)(CH_3OOH) = 367.6 ± 0.7 kcal mol^(-1), Δ_(acid)G_(298)(CD_3OOH) = 367.9 ± 0.9 kcal mol^(-1), and Δ_(acid)G_(298)(CH_3CH_2OOH) = 363.9 ± 2.0 kcal mol^(-1). From these acidities we have derived the enthalpies of deprotonation: Δ_(acid)H_(298)(CH_3OOH) = 374.6 ± 1.0 kcal mol^(-1), Δ_(acid)H_(298)(CD_3OOH) = 374.9 ± 1.1 kcal mol^(-1), and Δ_(acid)H_(298)(CH_3CH_2OOH) = 371.0 ± 2.2 kcal mol^(-1). Use of the negative-ion acidity/EA cycle provides the ROO−H bond enthalpies: DH_(298)(CH_3OO−H) = 87.8 ± 1.0 kcal mol^(-1), DH_(298)(CD_3OO−H) = 87.9 ± 1.1 kcal mol^(-1), and DH_(298)(CH_3CH_2OO−H) = 84.8 ± 2.2 kcal mol^(-1). We review the thermochemistry of the peroxyl radicals, CH_3OO and CH_3CH_2OO. Using experimental bond enthalpies, DH_(298)(ROO−H), and CBS/APNO ab initio electronic structure calculations for the energies of the corresponding hydroperoxides, we derive the heats of formation of the peroxyl radicals. The “electron affinity/acidity/CBS” cycle yields Δ_fH_(298)[CH_3OO] = 4.8 ± 1.2 kcal mol^(-1) and Δ_fH_(298)[CH_3CH_2OO] = −6.8 ± 2.3 kcal mol^(-1)

PHOTODETACHMENT ELECTRON SFECTROSCOPY OF FeO−FeO^{-}: DETERMINATION OF THE NEUTRAL MOLECULAR GROUND STATE

Author Institution: Department of Chemistry and Joint Institute of Laboratory Astrophysics, University of ColoradoThe energy spectrum of electrons photodetached from $FeO^{-}$ anions was obtained in a crossed ion-beam/laser-beam apparatus. From this spectrum the electron affinity of FeO could be determined and, additionally, the vibrational frequencies of the ground states of both the anion (760 $cm^{-1})$ and the neutral (970 $cm^{-1})$ were obtained. These FeO studies not only provide an EA(FeO) = 1.497 eV but also show that the state of FeO which has been considered the ground state for thirty years is in fact an excited state lying some 4000 $cm^{-1}$ above the true ground state

A DIRECT DETERMINATION OF THE 1Δ−X3Σ^{1}\Delta-X^{3}\Sigma SEPARATION IN NH BY PHOTOELECTRON SPECTROMETRY OF NH−NH^{-}

$^{1}$A. Gilles, J. Masanet, and C. Vermeil, Chem. Phys. Lett. 25, 346 (1974). $^{2}$C. Zetsch and F. Stahl, Chem. Phys. Lett. 33, 375 (1975).Author Institution: Department of Chemistry and Joint Institute of Laboratory Astrophysics, The University of ColoradoThe energy spectrum of electrons photodetached from $NH^{-}$ anions was obtained in a crossed ion-beam/laser-beam apparatus. This spectrum not only confirms the electron affinity of NH, but also provides a direct measurement of the $A^{1}\Delta -X^{3}\Sigma^{-}$ separation, confirming the postulated assignment of an intercombination transition ($^{1}\Sigma^{+} -^{3}\Sigma^{-}$) recently observed by several $groups.^{1,2}