Slow photoelectron velocity-map imaging spectroscopy of the vinoxide anion

Yacovitch, Tara I.; Garand, Etienne; Neumark, Daniel M.

doi:10.1063/1.3157208

Cited by 22 publications

(81 citation statements)

References 47 publications

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“…The CCSD(T)/aug-cc-pVTZ adiabatic eBE of 1.49 eV including a small zero-point vibrational energy (ZPE) correction matches previous autodetachment 15 73 As for CH 2 CN − , we predict the eBE of CH 2 CHO − (1.77 eV) to lie within 0.06 eV of experiment, 62 and the ZPE correction affects this only slightly. The 1.77 eV excitation energy of the 1 1 A ← 1 1 A transition is predicted to be within 0.02 eV of the measured transition energy.…”

Section: Sisupporting

confidence: 73%

Theoretical prediction of new dipole-bound singlet states for anions of interstellar interest

Fortenberry

Crawford

2011

The Journal of Chemical Physics

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Anions that exhibit dipole-bound singlet states have been proposed as a potential class of molecules that may be identified in the interstellar medium. Using high-level coupled cluster theory, we have computed the dipole moments, electron binding energies, and excited states of 14 neutral radicals and their corresponding closed-shell anions. We have calibrated our methods against experimental data for CH(2)CN(-) and CH(2)CHO(-) and demonstrated that coupled cluster theory can closely reproduce experimental dipole moments, electron binding energies, and excitation energies. Using these same methods, we predict the existence of dipole-bound excited states for six of the 14 previously unknown anions, including CH(2)SiN(-), SiH(2)CN(-), CH(2)SiHO(-), SiN(-), CCOH(-), and HCCO(-). In addition, we predict the existence of a valence-bound excited state of CH(2)SiN(-) with an excitation wavelength near 589 nm.

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Section: Sisupporting

confidence: 73%

Theoretical prediction of new dipole-bound singlet states for anions of interstellar interest

Fortenberry

Crawford

2011

The Journal of Chemical Physics

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“…97 The corresponding CC stretching mode ofÃ 2 A 0 1-MVO radical (ν 5 ) is also active in the photoelectron spectrum of the 1-MVO ion 98 with a fundamental vibrational frequency of 1565 ( 25 cm -1 . The fundamental peak for the OCH (or CCH) bending mode ofÃ 2 A 0 VO radical is also present in the photoelectron imaging spectrum 97 with a vibrational frequency of 1218 cm -1 . The corresponding mode inÃ 2 A 0 1-MVO radical (ν 14 ) is the inplane CH 3 wagging mode, which is most active in theÃ state portion of the spectrum (Figure 10).…”

Section: Vibronic Structure Of the 1-methylvinoxy Radicalmentioning

confidence: 99%

Photoelectron Spectroscopic Study of the Oxyallyl Diradical

et al. 2011

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ABSTRACT:The photoelectron spectrum of the oxyallyl (OXA) radical anion has been measured. The radical anion has been generated in the reaction of the atomic oxygen radical anion (O •-) with acetone. Three low-lying electronic states of OXA have been observed in the spectrum. Electronic structure calculations have been performed for the triplet states ( 3 B 2 and 3 B 1 ) of OXA and the ground doublet state ( 2 A 2 ) of the radical anion using density functional theory (DFT). Spectral simulations have been carried out for the triplet states based on the results of the DFT calculations. The simulation identifies a vibrational progression of the CCC bending mode of the 3 B 2 state of OXA in the lower electron binding energy (eBE) portion of the spectrum. On top of the 3 B 2 feature, however, the experimental spectrum exhibits additional photoelectron peaks whose angular distribution is distinct from that for the vibronic peaks of the 3 B 2 state. Complete active space selfconsistent field (CASSCF) method and second-order perturbation theory based on the CASSCF wave function (CASPT2) have been employed to study the lowest singlet state ( 1 A 1 ) of OXA. The simulation based on the results of these electronic structure calculations establishes that the overlapping peaks represent the vibrational ground level of the 1 A 1 state and its vibrational progression of the CO stretching mode. The 1 A 1 state is the lowest electronic state of OXA, and the electron affinity (EA) of OXA is 1.940 ( 0.010 eV. The 3 B 2 state is the first excited state with an electronic term energy of 55 ( 2 meV. The widths of the vibronic peaks of theX 1 A 1 state are much broader than those of theã 3 B 2 state, implying that the 1 A 1 state is indeed a transition state. The CASSCF and CASPT2 calculations suggest that the 1 A 1 state is at a potential maximum along the nuclear coordinate representing disrotatory motion of the two methylene groups, which leads to three-membered-ring formation, i.e., cyclopropanone. The simulation ofb 3 B 1 OXA reproduces the higher eBE portion of the spectrum very well. The term energy of the 3 B 1 state is 0.883 ( 0.012 eV. Photoelectron spectroscopic measurements have also been conducted for the other ion products of the O •-reaction with acetone. The photoelectron imaging spectrum of the acetylcarbene (AC) radical anion exhibits a broad, structureless feature, which is assigned to theX 3 A 00 state of AC. The ground ( 2 A 00 ) and first excited ( 2 A 0 ) states of the 1-methylvinoxy (1-MVO) radical have been observed in the photoelectron spectrum of the 1-MVO ion, and their vibronic structure has been analyzed.

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“…The SEVI spectrum of vinoxide, CH 2 CHO -, illustrated Duschinsky mixing of normal modes between the anion and the vinoxy radical and underlined the importance of including this effect in simulated spectra. 11 Our recent SEVI spectrum of the i-methylvinoxide anion revealed fine structure on top of each vibrational transition to theX 2 A state of the i-methylvinoxy radical that was attributed to hindered rotor levels of the methyl substituent accessed upon photodetachment. 9 The subject of this paper, the n-methylvinoxy radical, n-C 3 H 5 O, (Fig.…”

Section: Introductionmentioning

confidence: 94%

“…This paper is the third in a series of SEVI studies on the vinoxide and substituted vinoxide anions. 9,11 The corresponding vinoxy-based radicals are intermediates in combustion chemistry, 12,13 as well as in atmospheric reactions such as the tropospheric ozonolysis of alkenes. 14,15 The family of vinoxy radicals also represents an important model system in electronic spectroscopy, and as such has been investigated extensively in many laboratories.…”

Section: Introductionmentioning

confidence: 99%

Slow photoelectron velocity-map imaging spectroscopy of the n-methylvinoxide anion

Yacovitch

Kim

Garand

et al. 2011

The Journal of Chemical Physics

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High resolution photoelectron spectra of the n-methylvinoxide anion and its deuterated isotopologue are obtained by slow electron velocity-map imaging. Transitions between the X̃(1)A' anion ground electronic state and the radical X̃(2)A" and Ã(2)A' states are observed. The major features in the spectra are attributed to transitions involving the lower energy cis conformers of the anion and neutral, while the higher energy trans conformers contribute only a single small peak. Franck-Condon simulations of the X̃(2)A" ← X̃(1)A' and Ã(2)A' ← X̃(1)A' transitions are performed to assign vibrational structure in the spectrum and to aid in identifying peaks in the cis-n-methylvinoxy X̃ (2)A" band that occur only through vibronic coupling. The experimental electron affinity and Ã state term energy are found to be EA = 1.6106 ± 0.0008 eV and T(0) = 1.167 ± 0.002 eV for cis-n-methylvinoxy.

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Slow photoelectron velocity-map imaging spectroscopy of the vinoxide anion

Cited by 22 publications

References 47 publications

Theoretical prediction of new dipole-bound singlet states for anions of interstellar interest

Theoretical prediction of new dipole-bound singlet states for anions of interstellar interest

Photoelectron Spectroscopic Study of the Oxyallyl Diradical

Slow photoelectron velocity-map imaging spectroscopy of the n-methylvinoxide anion

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