Negative-ion photoelectron spectroscopy of (CS2)−: coexistence of electronic isomers

Tsukuda, Tatsuya; Hirose, Takayuki; Nagata, Takashi

doi:10.1016/s0009-2614(97)01021-x

Cited by 42 publications

(67 citation statements)

References 13 publications

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“…Photoelectron and photodissociation spectroscopy of the (CS 2 ) n − cluster anions suggested the coexistence of electronic isomers with a CS 2 − monomer or (CS 2 ) 2 − dimer ion core. [39][40][41][42]44,45 In contrast, our IRPD study of the (CS 2 ) 3-8 − clusters suggested a CS 2 − monomer ion core form. 27 Very recently, Sanov and coworkers clearly showed the definitive evidence of the electronic and geometric structure of (CS 2 ) 2 − by IRPD spectroscopy with a temperature-controlled ion trap and a free electron laser.…”

Section: Experimental and Computationalcontrasting

confidence: 72%

“…34 The OCS anion clusters have been much more investigated than the cation clusters, because the (OCS) n − clusters are homologous systems of (CO 2 ) n − and (CS 2 ) n − , which have complicated but interesting natures of the electronic structure. 16,20,21,33,[35][36][37][38][39][40][41][42][43][44][45] Sanov and coworkers have extensively studied photochemistry and electronic structure of (OCS) n − using photodissociation and photoelectron imaging techniques. [36][37][38] They suggested the coexistence of isomers having the OCS − monomer core and the (OCS) 2 − dimer one.…”

Section: Introductionmentioning

confidence: 99%

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IR photodissociation spectroscopy of (OCS)n+ and (OCS)n− cluster ions: Similarity and dissimilarity in the structure of CO2, OCS, and CS2 cluster ions

Inokuchi

Ebata

2015

The Journal of Chemical Physics

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Infrared photodissociation (IRPD) spectra of (OCS)n(+) and (OCS)n(-) (n = 2-6) cluster ions are measured in the 1000-2300 cm(-1) region; these clusters show strong CO stretching vibrations in this region. For (OCS)2 +) and (OCS)2(-), we utilize the messenger technique by attaching an Ar atom to measure their IR spectra. The IRPD spectrum of (OCS)2 (+)Ar shows two bands at 2095 and 2120 cm(-1). On the basis of quantum chemical calculations, these bands are assigned to a C2 isomer of (OCS)2 (+), in which an intermolecular semi-covalent bond is formed between the sulfur ends of the two OCS components by the charge resonance interaction, and the positive charge is delocalized over the dimer. The (OCS)n(+) (n = 3-6) cluster ions show a few bands assignable to "solvent" OCS molecules in the 2000-2080 cm(-1) region, in addition to the bands due to the (OCS)2(+) ion core at ∼2090 and ∼2120 cm(-1), suggesting that the dimer ion core is kept in (OCS)3-6(+). For the (OCS)n(-) cluster anions, the IRPD spectra indicate the coexistence of a few isomers with an OCS(-) or (OCS)2(-) anion core over the cluster range of n = 2-6. The (OCS)2(-)Ar anion displays two strong bands at 1674 and 1994 cm(-1). These bands can be assigned to a Cs isomer with an OCS(-) anion core. For the n = 2-4 anions, this OCS(-) anion core form is dominant. In addition to the bands of the OCS(-) core isomer, we found another band at ∼1740 cm(-1), which can be assigned to isomers having an (OCS)2(-) ion core; this dimer core has C2 symmetry and (2)A electronic state. The IRPD spectra of the n = 3-6 anions show two IR bands at ∼1660 and ∼2020 cm(-1). The intensity of the latter component relative to that of the former one becomes stronger and stronger with increasing the size from n = 2 to 4, which corresponds to the increase of "solvent" OCS molecules attached to the OCS(-) ion core, but it suddenly decreases at n = 5 and 6. These IR spectral features of the n = 5 and 6 anions are ascribed to the formation of another (OCS)2(-) ion core having C2v symmetry with (2)B2 electronic state.

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Section: Experimental and Computationalcontrasting

confidence: 72%

Section: Introductionmentioning

confidence: 99%

IR photodissociation spectroscopy of (OCS)n+ and (OCS)n− cluster ions: Similarity and dissimilarity in the structure of CO2, OCS, and CS2 cluster ions

Inokuchi

Ebata

2015

The Journal of Chemical Physics

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“…As with AD, no analog of this band is seen in OCS ÿ H 2 O and thus it cannot be attributed to OCS ÿ OCS. Note that a 2.7 eV band in the photoelectron spectrum of CS 2 ÿ 2 was also assigned to a similar covalent isomer [22].…”

mentioning

confidence: 89%

Imaging of Direct Photodetachment and Autodetachment of(OCS)2−: Excited-State Dynamics of the Covalent Dimer Anion

Surber

Sanov

2003

Phys. Rev. Lett.

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We report a photoelectron imaging study of (OCS)-2 and compare the results to OCS-.H2O. Two electron-emission mechanisms are observed for the dimer anion: direct photodetachment and autodetachment, while OCS-.H2O exhibits only the direct mechanism. The results provide evidence of covalent (OCS)-2 coexisting with the OCS-.OCS cluster anion. The autodetachment originating from the covalent species is modeled as thermionic emission transpiring in the regime of fragmentation. The bulk statistical model is found applicable to the small anion due to the availability of low-lying excited states.

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“…(C-C bound) or C 2v symmetry (C-C and S-S bound) rather than the D 2d symmetry of the C-C bound C 2 O 4 -anion [36,37,38]. It is almost certain that the S-S bound structure is energetically preferable, because the UV-vis photoexcitation of C 2 S 4 -(CS 2 ) n-2 anions results in the fragmentation of the dimer core to C 2 S 2 -and S 2 [37].…”

Section: /12/04mentioning

confidence: 99%

Multimer Radical Ions and Electron/Hole Localization in Polyatomic Molecular Liquids: A Critical Review

Shkrob

Sauer

2004

ChemInform

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Abstract.While ionization of some polyatomic molecular liquids (such as water and aliphatic alcohols) yields so-called "solvated electrons" in which the excess electron density is localized in the interstices between the solvent molecules, most organic and inorganic liquids yield radical anions and cations in which the electron and spin densities reside on the solvent molecule or, more commonly, a group of such molecules. The resulting multimer ions have many unusual properties, such as high rates of diffusive hopping. The "solvated electron" can be regarded as a variant of a multimer radical anion in which the charge, while perturbing the solvent molecules, mainly resides in the space between these molecules. We give several examples of less known modes for electron localization in liquids that yield multimer radical anions (such as C 6 F 6 , benzene, acetonitrile, carbon disulfide and dioxide, etc.) and holes localization in liquids that yield multimer radical cations (such as cycloalkanes). Current understanding of the reaction properties for these high-mobility solvent radical anions and cations is discussed.

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Negative-ion photoelectron spectroscopy of (CS2)−: coexistence of electronic isomers

Cited by 42 publications

References 13 publications

IR photodissociation spectroscopy of (OCS)n+ and (OCS)n− cluster ions: Similarity and dissimilarity in the structure of CO2, OCS, and CS2 cluster ions

IR photodissociation spectroscopy of (OCS)n+ and (OCS)n− cluster ions: Similarity and dissimilarity in the structure of CO2, OCS, and CS2 cluster ions

Imaging of Direct Photodetachment and Autodetachment of(OCS)2−: Excited-State Dynamics of the Covalent Dimer Anion

Multimer Radical Ions and Electron/Hole Localization in Polyatomic Molecular Liquids: A Critical Review

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