Slow photoelectron imaging spectroscopy of CCO− and CCS−

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

doi:10.1063/1.2969819

Cited by 16 publications

(26 citation statements)

References 53 publications

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“…Even though all partial waves are allowed by symmetry from such an orbital, in practice s + d wave detachment is often dominant. 9,52 In a more strongly bent species such as C 3 O − , the propensity rules for detachment are expected to be less strict, so one might expect p-wave detachment to become increasingly more important at higher eKE. The C 3 O − and C 3 S − PADs thus most likely reflect the difference in geometry between the two anions predicted by our DFT calculations.…”

Section: Analysis and Discussionmentioning

confidence: 99%

“…[1][2][3][4][5][6][7][8] In this paper, we continue our investigation of these two isovalent series of clusters via negative ion photodetachment. 9 The high resolution photoelectron ͑PE͒ spectra of the C 3 O − and C 3 S − anions are reported, providing a detailed probe of the neutral and anionic ground electronic states of these species.…”

Section: Introductionmentioning

confidence: 99%

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Slow photoelectron velocity-map imaging spectroscopy of C3O− and C3S−

Garand

Yacovitch

Neumark

2009

The Journal of Chemical Physics

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High-resolution photodetachment spectra of C(3)O(-) and C(3)S(-) using slow photoelectron velocity-map imaging spectroscopy are reported. Well-resolved transitions to the neutral X (1)Sigma(+) state are seen for both species. The electron affinities of C(3)O and C(3)S are determined to be EA(C(3)O) = 1.237+/-0.003 eV and EA(C(3)S) = 1.5957+/-0.0010 eV, respectively. Several vibrational frequencies for gas phase C(3)O and C(3)S are determined for the first time. The long progression of bending modes observed in the spectra is consistent with electronic structure calculations predicting that the C(3)O(-) and C(3)S(-) have bent equilibrium geometries.

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Section: Analysis and Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Slow photoelectron velocity-map imaging spectroscopy of C3O− and C3S−

Garand

Yacovitch

Neumark

2009

The Journal of Chemical Physics

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“…However, mode v 18 has b 1 symmetry and its activity must be due to vibronic couplings, as observed recently in high-resolution PE imaging of other small polyatomic anions. [36] The angular distributions of all the vibrational peaks because of the a 1 modes display s-plus dorbital characters, [31] consistent with the p-type orbital from which the electron is detached. The angular distributions of the vibrational peaks because of the v 18 mode are different, displaying distinct p-orbital character (Figure 1).…”

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confidence: 84%

Observation of Mode‐Specific Vibrational Autodetachment from Dipole‐Bound States of Cold Anions

Liu¹,

Ning²,

Huang³

et al. 2013

Angew Chem Int Ed

111

191

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Molecules with sufficiently large dipole moments were predicted to form weakly bound negative ions in the dipolar field [1][2][3][4] and such dipole-bound anions have been observed and characterized experimentally. [5][6][7][8][9][10] Negative ions with dipolar molecular cores can have excited dipole-bound states (DBSs) near the detachment threshold, analogous to Rydberg states in neutral molecules. DBSs in excited anions were first observed as resonances in photodetachment crosssections. [11][12][13] Ultrahigh resolution spectroscopy has been reported on excited DBSs of a number of anions near their detachment threshold by autodetachment. [14][15][16] The theory for autoionization from Rydberg states was first developed by Berry, [17] who predicted a Dv = À1 vibrational propensity rule, that is, the Rydberg state undergoes a vibrational relaxation by one vibrational quantum in the molecular core during autoionization, in which the vibrational energy is transferred to the Rydberg electron. The Dv = À1 propensity rule has been observed in autoionization of numerous molecules [18][19][20] and mode-specific autoionization has been observed by photoelectron spectroscopy, [21] in which the kinetic energies of the outgoing electrons are measured. The same Dv = À1 propensity rule should apply in autodetachment from DBSs of excited anions [22] and has been inferred in previous studies.[ 13,16] However, the electron kinetic energies of the outgoing autodetached electrons from the excited DBSs have not been measured by electron spectroscopy.All prior studies of DBSs in excited anions are dominated by rotational effects [23,24] and pure vibrational autodetachment from DBSs has not been reported, even though vibrational autodetachment has been observed in weakly bound anions and has been used effectively as a spectroscopic tool for anions. [25][26][27] Here we report the direct observation of pure vibrational autodetachment from DBSs of cryogenically cooled phenoxide anions using high-resolution photoelectron imaging. Autodetachment from eight vibrational levels of the DBS in optically exited phenoxide anions are observed and the Dv = À1 propensity rule is found to be strictly obeyed.

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“…The C 2 (X 1 Σ + ) + OCS(X 1 Σ + ) reaction may lead to the exothermic and spin‐allowed CCS (a 1 Δ, b 1 Σ + ) + CO (X 1 Σ + ) products (−163/−136 kJ mol −1 ) (Garand, Yacovitch & Neumark 2008). However, it is difficult to determine whether this reaction presents a barrier.…”

Section: Ocs Consumptionmentioning

confidence: 99%

Review of OCS gas-phase reactions in dark cloud chemical models

Loison

Halvick

Bergeat

et al. 2012

Monthly Notices of the Royal Astronomical Society

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The association reaction S + CO {\to} OCS + hnu has been identified as being particularly important for the prediction of gas-phase OCS abundances by chemical models of dark clouds. We performed detailed ab-initio calculations for this process in addition to undertaking an extensive review of the neutral-neutral reactions involving this species which might be important in such environments. The rate constant for this association reaction was estimated to be several orders of magnitude smaller than the one present in current astrochemical databases. The new rate for this reaction and the introduction of other processes, notably OH + CS {\to} OCS + H and C + OCS {\to} CO + CS, dramatically changes the OCS gas-phase abundance predicted by chemical models for dark clouds. The disagreement with observations in TMC-1 (CP) and L134N (N), suggests that OCS may be formed on grain surfaces as is the case for methanol. The observation of solid OCS on interstellar ices supports this hypothesis.Comment: Accepted for publication in MNRA

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Slow photoelectron imaging spectroscopy of CCO− and CCS−

Cited by 16 publications

References 53 publications

Slow photoelectron velocity-map imaging spectroscopy of C3O− and C3S−

Slow photoelectron velocity-map imaging spectroscopy of C3O− and C3S−

Observation of Mode‐Specific Vibrational Autodetachment from Dipole‐Bound States of Cold Anions

Review of OCS gas-phase reactions in dark cloud chemical models

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