Observation of Dipole-Bound States of Negative Ions

Lykke, Keith R.; Mead, Roy D.; Lineberger, W. C.

doi:10.1103/physrevlett.52.2221

Cited by 150 publications

(101 citation statements)

References 23 publications

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“…Lineberger and co-workers had performed high-resolution autodetachment spectroscopy via DBS. [143][144][145][146][147][148] The phenoxy radical has a sufficiently large dipole moment (∼4 D) (see inset of Fig. 8(b)) and it was plausible that phenoxide could have excited DBS near its detachment threshold.…”

Section: A Pes Of Phenoxide At Room Temperature and Observation Of Dmentioning

confidence: 99%

“…150 to probe vibrational properties of interesting neutral radicals using optical excitation. Lineberger and co-workers used autodetachment to perform rotational spectroscopy using a highresolution laser, [143][144][145][146][147][148] but with narrow wavelength ranges. Furthermore, the limited cooling capacity often yielded quite congested autodetachment spectra even for relatively simple anions.…”

Section: Photodetachment Spectroscopy Of Cold Anions Via Autodetacmentioning

confidence: 99%

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Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions

Wang

2015

The Journal of Chemical Physics

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Electrospray ionization (ESI) has become an essential tool in chemical physics and physical chemistry for the production of novel molecular ions from solution samples for a variety of spectroscopic experiments. ESI was used to produce free multiply-charged anions (MCAs) for photoelectron spectroscopy (PES) in the late 1990 s, allowing many interesting properties of this class of exotic species to be investigated. Free MCAs are characterized by strong intramolecular Coulomb repulsions, which create a repulsive Coulomb barrier (RCB) for electron emission. The RCB endows many fascinating properties to MCAs, giving rise to meta-stable anions with negative electron binding energies. Recent development in the PES of MCAs includes photoelectron imaging to examine the influence of the RCB on the electron emission dynamics, pump-probe experiments to examine electron tunneling through the RCB, and isomer-specific experiments by coupling PES with ion mobility for biological MCAs. The development of a cryogenically cooled Paul trap has led to much better resolved PE spectra for MCAs by creating vibrationally cold anions from the room temperature ESI source. Recent advances in coupling the cryogenic Paul trap with PE imaging have allowed high-resolution PE spectra to be obtained for singly charged anions produced by ESI. In particular, the observation of dipole-bound excited states has made it possible to conduct vibrational autodetachment spectroscopy and resonant PES, which yield much richer vibrational spectroscopic information for dipolar free radicals than traditional PES.

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Section: A Pes Of Phenoxide At Room Temperature and Observation Of Dmentioning

confidence: 99%

Section: Photodetachment Spectroscopy Of Cold Anions Via Autodetacmentioning

confidence: 99%

Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions

Wang

2015

The Journal of Chemical Physics

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“…[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.…”

mentioning

confidence: 99%

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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“…quoted therein. Resonance energies of dipolar anions have been determined experimentally by low energy electron scattering off the dipolar molecules [25,26,29,31,33].…”

Section: Introductionmentioning

confidence: 99%

Bound states of dipolar molecules studied with the Berggren expansion method

et al. 2013

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Bound states of dipole-bound negative anions are studied by using a non-adiabatic pseudopotential method and the Berggren expansion involving bound states, decaying resonant states, and nonresonant scattering continuum. The method is benchmarked by using the traditional technique of direct integration of coupled channel equations. A good agreement between the two methods has been found for well-bound states. For weakly-bound subthreshold states with binding energies comparable with rotational energies of the anion, the direct integration approach breaks down and the Berggren expansion method becomes the tool of choice.PACS numbers: 03.65. Nk, 33.15.Ry

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Observation of Dipole-Bound States of Negative Ions

Cited by 150 publications

References 23 publications

Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions

Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions

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

Bound states of dipolar molecules studied with the Berggren expansion method

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