Photoelectron spectroscopic detection of vinyl alcohol, CH2CHOH: evidence for the syn and anti rotamers

Matti, George Y.; Osman, Osman I.; Upham, J. E.; Suffolk, R. J.; Kroto, Harold W.

doi:10.1016/0368-2048(89)85008-x

Cited by 30 publications

(31 citation statements)

References 10 publications

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“…Except the origin band, the other signals of anti ‐vinyl alcohol are buried by the stronger peaks of the syn ‐rotamer. Our assignments are in consistent with those by Matti et al for the A and S bands,[36] but provide more details about the vibrational structures, since only the progressions of ν 5 (CC stretch) are identified by Matti et al[36]…”

Section: Resultssupporting

confidence: 90%

“…Taking both the adiabatic ionization energy and population into account, the photoelectron spectrum of vinyl alcohol with a Boltzmann distribution at 300 K is shown in Figure 4 (lower trace). The simulated photoelectron spectrum is in agreement with the experiment[36] (upper trace in Fig. 4).…”

Section: Resultssupporting

confidence: 84%

“… Comparison of the simulated (lower trace) to the experimental (upper trace, taken from Ref. 36) photoelectron spectra of vinyl alcohol. A and S are referred to the origin bands of anti ‐ and syn ‐vinyl alcohol, respectively.…”

Section: Resultsmentioning

confidence: 99%

“…In order to test the validity of our approach, we studied the photoelectron spectroscopy of two planar molecules, vinyl alcohol (C 2 H 3 OH)[34–45] and ovalene (C 32 H 14 ),[46–51] which had 15 and 132 normal modes, respectively. The planar molecules were chosen because they had a limited number of conformers.…”

Section: Introductionmentioning

confidence: 99%

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An analytical approach for computing Franck‐Condon integrals of harmonic oscillators with arbitrary dimensions

Chang¹,

Huang²,

Chen³

et al. 2012

J Comput Chem

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We have developed an analytical approach for computing Franck-Condon integrals (FCIs) of harmonic oscillators (HOs) with arbitrary dimensions in which the mode-mixing Duschinsky effect is taken into account. A general formula of FCIs of HOs was obtained and was applied to study the photoelectron spectroscopy of vinyl alcohol and ovalene (C(32)H(14)). The equilibrium geometries, harmonic vibrational frequencies and normal modes of vinyl alcohol, ovalene, and their cations were computed at the B3LYP/aug-cc-pVTZ or the B3LYP/6-31G(d) level, from which Franck-Condon factors were calculated and photoelectron spectra were simulated. The adiabatic ionization energies of vinyl alcohol were also computed by extrapolating the CCSD(T) energies to the complete basis set limit with aug-cc-pVXZ (X = D, T, Q, 5). The simulated photoelectron spectra of both vinyl alcohol and ovalene are in agreement with the experiments. The computed adiabatic ionization energies of syn- and anti-vinyl alcohol are in consistent with the experiment within 0.008 eV and 0.014 eV, respectively. We show, for the first time, that the analytical approach of computing FCIs is also efficient and promising for the studies of vibronic spectra of macrosystems.

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Section: Resultssupporting

confidence: 90%

Section: Resultssupporting

confidence: 84%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

An analytical approach for computing Franck‐Condon integrals of harmonic oscillators with arbitrary dimensions

Chang¹,

Huang²,

Chen³

et al. 2012

J Comput Chem

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“…Because n-butane can also be ionized under our experimental conditions, the C 4 H 10 + ion counts would interfere with those from the ionized C 3 H 6 O isomers (58 amu). Therefore, experiments were conducted with C 18 O instead of C 16 O to shift the masses by 2 amu to 60 amu (C 3 H 6 18 O) The ionization energies (IEs) of acetaldehyde (IE = 10.23 eV) (19) and of vinyl alcohol (IE syn = 9.17 eV; IE anti = 9.30 eV) (20) (23) and, hence, cannot contaminate the signal at m/z = 44. The TPD profile at 10.49 eV, which results from photoionization of both acetaldehyde and vinyl alcohol, exhibits a bimodal structure peaking at 117 and 147 K (Fig.…”

Section: Resultsmentioning

confidence: 99%

A study of interstellar aldehydes and enols as tracers of a cosmic ray-driven nonequilibrium synthesis of complex organic molecules

Abplanalp

Gozem

Krylov

et al. 2016

Proc. Natl. Acad. Sci. U.S.A.

105

132

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Complex organic molecules such as sugars and amides are ubiquitous in star-and planet-forming regions, but their formation mechanisms have remained largely elusive until now. Here we show in a combined experimental, computational, and astrochemical modeling study that interstellar aldehydes and enols like acetaldehyde (CH 3 CHO) and vinyl alcohol (C 2 H 3 OH) act as key tracers of a cosmic-ray-driven nonequilibrium chemistry leading to complex organics even deep within low-temperature interstellar ices at 10 K. Our findings challenge conventional wisdom and define a hitherto poorly characterized reaction class forming complex organic molecules inside interstellar ices before their sublimation in star-forming regions such as SgrB2(N). These processes are of vital importance in initiating a chain of chemical reactions leading eventually to the molecular precursors of biorelevant molecules as planets form in their interstellar nurseries.astrochemistry | suprathermal chemistry | photoionization | organics | low-temperature kinetics

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Interstellar Enolization‐Acetaldehyde (CH₃CHO) and Vinyl Alcohol (H₂CCH(OH)) as a Case Study

Kleimeier

Kaiser

2021

ChemPhysChem

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Owing to the unique conditions in cold molecular clouds, enols—the thermodynamically less stable tautomers of aldehydes and ketones—do not undergo tautomerization to their more stable tautomers in the gas phase because they cannot overcome tautomerization barriers at the low temperatures. Laboratory studies of interstellar analog ices have demonstrated the formation of several keto–enol tautomer pairs in astrochemically relevant ice mixtures over the last years. However, so far only one of them, acetaldehyde−vinyl alcohol, has been detected in deep space. Due to their reactivity with electrophiles, enols can play a crucial role in our understanding of the molecular complexity in the interstellar medium and in comets and meteorites. To study the enolization of aldehydes in interstellar ices by interaction with galactic cosmic rays (GCRs), we irradiated acetaldehyde ices with energetic electrons as proxies of secondary electrons generated in the track of GCRs while penetrating interstellar ices. The results indicate that GCRs can induce enolization of acetaldehyde and that intra‐ as well as intermolecular processes are relevant. Therefore, enols should be ubiquitous in the interstellar medium and could be searched for using radio telescopes such as ALMA. Once enols are detected and abundances are established, they can serve as tracers for the non‐equilibrium chemistry in interstellar ices thus eventually constraining fundamental reaction mechanisms deep inside interstellar ices.

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Photoelectron spectroscopic detection of vinyl alcohol, CH2CHOH: evidence for the syn and anti rotamers

Cited by 30 publications

References 10 publications

An analytical approach for computing Franck‐Condon integrals of harmonic oscillators with arbitrary dimensions

An analytical approach for computing Franck‐Condon integrals of harmonic oscillators with arbitrary dimensions

A study of interstellar aldehydes and enols as tracers of a cosmic ray-driven nonequilibrium synthesis of complex organic molecules

Interstellar Enolization‐Acetaldehyde (CH₃CHO) and Vinyl Alcohol (H₂CCH(OH)) as a Case Study

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Photoelectron spectroscopic detection of vinyl alcohol, CH2CHOH: evidence for the syn and anti rotamers

Cited by 30 publications

References 10 publications

An analytical approach for computing Franck‐Condon integrals of harmonic oscillators with arbitrary dimensions

An analytical approach for computing Franck‐Condon integrals of harmonic oscillators with arbitrary dimensions

A study of interstellar aldehydes and enols as tracers of a cosmic ray-driven nonequilibrium synthesis of complex organic molecules

Interstellar Enolization‐Acetaldehyde (CH3CHO) and Vinyl Alcohol (H2CCH(OH)) as a Case Study

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Product

Resources

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Interstellar Enolization‐Acetaldehyde (CH₃CHO) and Vinyl Alcohol (H₂CCH(OH)) as a Case Study