Radiative and non-radiative decay of selected vibronic levels of the B state of alkoxy radicals

Gopalakrishnan, Sandhya; Zu, Lily; Miller, Terry A.

doi:10.1016/j.cplett.2003.08.124

Cited by 24 publications

(28 citation statements)

References 17 publications

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“…The experimental spectrum shows that the average vibrational band interval between the ν' C -O ＝ n and ν' C-O ＝n＋1 (0≤n≤6) levels is 521 cm -1 (6.23 kJ/mol) for the B state. 24,25 Obviously, our calculation agrees well with the result from the experiment.…”

Section: T-butoxy Isomersupporting

confidence: 92%

“…After the Davidson correction, they became 326, 333 and 326 kJ/mol, which agree well with the experimental results 320, 324 and 320 kJ/mol, 16,25 respectively (see Table 1). We also investigated the isomerization reactions between any two of the three conformers at the B state and the relative energies of the transition states were shown in Figure 5(b).…”

Section: -Butoxy Isomersupporting

confidence: 83%

“…This is consistent with the experimental lifetime measurements that the t-butoxy radical would not be strongly predissociated in the ν'＝0-7 levels. 24,25 Emission has not been observed from the higher vibrational levels, allowing for the possibility that they maybe shortly lived.…”

Section: T-butoxy Isomermentioning

confidence: 88%

“…For convenient comparison, the labeling of the different conformers is consistent with the previous experimental papers. 15,16,25 At the MP2/6-31＋G** level, the barriers for the isomerization were predicted to be between 8.8-14.6 kJ/mol, which are much lower than the 1,5-H transfer barriers (ca. 38 kJ/mol 17 ).…”

Section: -Butoxy Isomermentioning

confidence: 99%

“…The MR-CI/6-31＋G** calculations with the Davidson correction predicted that the adiabatic excitation energy values from the X to B state for the G 1 T 2 , T 1 T 2 and T 1 G 2 conformers were 351, 363 and 361 kJ/mol respectively, which agree well with the experimental results 343, 348 and 349 kJ/mol. 25 The relative energies of the B state with respect to X for the G 1 G 2 and G 1 ′G 2 conformers were predicted to be 351 and 352 kJ/mol, respectively, at the same calculation level. The experimental studies have not come out with the corresponding values for them so far.…”

Section: -Butoxy Isomermentioning

confidence: 99%

See 4 more Smart Citations

Theoretical Study of the Low‐Lying Excited States of Butoxy Radicals and Non‐Radiative Decay Routes

Lili

Fang

et al. 2007

Chin. J. Chem.

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The potential energy surfaces for the butoxy radical dissociation into R•＋O on the six low-lying electronic states have been determined with the combined CASSCF and MR-CI methods. The isomerization reactions between the different conformers of 1-and 2-butoxy radicals at the X and B states have been also investigated with the MP2, B3LYP, and CASSCF methods. The non-radiative decay mechanisms of butoxy radicals at the B state have been characterized with the computed potential energy surfaces and intersections. Supported by recent LIF experimental results, it was predicted that the t-butoxy radical would predissociate via the / B C intersection. As to 1-and 2-butoxy radicals, the relative energies of the transition states for the isomerization reactions between conformers at the B state are much lower than those of the / B C intersections, resulting in the predominance of the isomerization in the decay of the B state for 1-and 2-butoxy radicals.

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Section: T-butoxy Isomersupporting

confidence: 92%

Section: -Butoxy Isomersupporting

confidence: 83%

Section: T-butoxy Isomermentioning

confidence: 88%

Section: -Butoxy Isomermentioning

confidence: 99%

Section: -Butoxy Isomermentioning

confidence: 99%

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Theoretical Study of the Low‐Lying Excited States of Butoxy Radicals and Non‐Radiative Decay Routes

Lili

Fang

et al. 2007

Chin. J. Chem.

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Laser induced fluorescence study of the - transition of FCH2CH2O

Chhantyal-Pun¹,

Chen²,

Miller³

2013

Chemical Physics Letters

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Laser-Induced Fluorescence Spectroscopy of Large Secondary Alkoxy Radicals: Part I. Spectral Overviews and Vibronic Analysis

Liu

Miller

2021

J. Phys. Chem. A

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We report vibronically resolved laser-induced fluorescence (LIF) spectra of jet-cooled C5−C10 secondary alkoxy radicals. The LIF spectra demonstrate vibronic structures similar to smaller (C3−C4) secondary alkoxies. For 2-pentoxy and 2-hexoxy, rotationally resolved LIF spectra have also been recorded. Two types of rotational structures have been observed in vibronic bands of each molecule. Extensive quantum chemistry calculations have been performed on 2-pentoxy and 2-hexoxy. The computed results include the relative energies of conformers, their geometries, and the energy separations between the nearly degenerate A ̃and X ̃electronic states (ΔE A ̃−X ̃). Based on the similarity between the vibronic structures of different secondary alkoxies and calculated molecular parameters, including the relative energies of conformers, the B ̃← X ̃transition frequencies, and the vibrational frequencies, strong vibronic bands in the LIF spectra are assigned to the origin bands and CO stretch bands of the two lowest-energy conformers of each secondary alkoxy radical. The distinct rotational structures of the two different conformations of 2-pentoxy and 2-hexoxy will be simulated and analyzed in Part II of this series (J.

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Radiative and non-radiative decay of selected vibronic levels of the B state of alkoxy radicals

Cited by 24 publications

References 17 publications

Theoretical Study of the Low‐Lying Excited States of Butoxy Radicals and Non‐Radiative Decay Routes

Theoretical Study of the Low‐Lying Excited States of Butoxy Radicals and Non‐Radiative Decay Routes

Laser induced fluorescence study of the - transition of FCH2CH2O

Laser-Induced Fluorescence Spectroscopy of Large Secondary Alkoxy Radicals: Part I. Spectral Overviews and Vibronic Analysis

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