Photodissociation spectroscopy of benzene cluster ions: (C6H6)+2 and (C6H6)+3

Ohashi, Kazuhiko; Nishi, Nobuyuki

doi:10.1063/1.460807

Cited by 59 publications

(58 citation statements)

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“…The results of (C 6 H 6 ) 3 + as well as (C 6 H 6 ) 2 + have already been reported and discussed in our previous publication. 8 When the (C 6 H 6 ) n + ions with n ) 4-6 were photodissociated in this wavelength region, both C 6 H 6 + and (C 6 H 6 ) 2 + were mainly detected as photofragment ions. We confirmed that the yield of each fragment ion showed almost linear dependence on the laser power.…”

Section: Resultsmentioning

confidence: 98%

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Electronic Structures and Photoevaporation Dynamics of Benzene Cluster Ions

1997

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The electronic spectra of benzene cluster ions, (C 6 H 6 ) n + with n ) 3-6, are measured through mass-selected photodissociation spectroscopy. The spectra in the 400-1100-nm region show three distinct absorption maxima centered around 430, 590-620, and 950 nm, which are analogous to the spectrum of (C 6 H 6 ) 2 + . The 950-nm band is assigned to a charge resonance (CR) band characteristic of the dimer ion, while the other two bands are attributed to local excitation bands. The position of the CR band is found to be almost independent of cluster size. The result suggests that the cluster ions have a charge-localized structure involving a strongly bound dimer ion core. In addition, the number and translational energy of neutral molecules ejected following photoexcitation are measured for (C 6 H 6 ) n + with n ) 3-8 in the photon energy range of 0.5-3.0 eV. The average number of ejected molecules increases linearly with increasing photon energy, suggesting that the fragmentation proceeds via the sequential ejection of neutral monomers. The average translational energy carried by one monomer is determined to be 50-70 meV, which is comparable with the calculated value according to a statistical theory. A large part of the imparted photon energy is partitioned into internal energies of the products. These results indicate that the photofragmentation of (C 6 H 6 ) n + can be regarded as a unimolecular decay of vibrationally hot clusters, despite the promotion of the chromophoric dimer core to the repulsive excited state.

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Section: Resultsmentioning

confidence: 98%

“…The sums of the normalized yields of fragment ions, C6H6 + and (C6H6)2 + , are plotted against the wavelengths of the dissociation laser. The spectra for n ) 2 and 3 are already reported in our previous work 8. Two local excitation (LE) bands are commonly observed for all the cluster ions.…”

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confidence: 90%

Electronic Structures and Photoevaporation Dynamics of Benzene Cluster Ions

1997

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“…[1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] The dimer ion form is kept as a dimer ion core in some homo-molecular cluster ions, such as (benzene) n + . 13,14 However, the charge distribution of cluster ions is not predictable so easily on the basis of IE, PA, or EA. One curious manner on the charge distribution occurs for (CO 2 ) n − cluster anions, 16,20,21 which show switching of the ion core between n = 6 and 7 and between 13 and 14.…”

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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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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“…46,47 Benzene clusters are the simplest prototype aromatic molecules for understanding the fundamental aspects of -interactions. An extensive amount of work has hitherto been devoted to the spectroscopy and structure of neutral and cationic clusters of benzene; 7,8,22,[57][58][59][60][61][62][63][64][65][66][67][68][69][70] however, there has been, to the best of our knowledge, no report on anionic clusters of benzene. As is well known, a benzene molecule has a negative electron affinity (EA); for example, vertical EA = À1:12 eV has been reported by electron transmission spectroscopy.…”

Section: Experimental Methodologymentioning

confidence: 99%

Formation of Large Molecular Cluster Anions and Elucidation of Their Electronic Structures

Mitsui¹,

Nakajima²

2007

Bulletin of the Chemical Society of Japan

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The present account describes our efforts to understand the microscopic aspects of condense phase phenomena, such as ion solvation in molecular liquids and charge carrier localization in molecular solids, by viewing finite-size molecular clusters as their embryonic forms. In this effort, we efficiently prepared supersonically cooled, isolated molecular cluster anions with up to more than 100 constituent molecules and size-selectively investigated their electronic structures using anion photoelectron spectroscopy. Large anionic clusters of two different types of organic molecule; acetonitrile and naphthalene reported as examples of the noteworthy results obtained in our studies. In these two systems, we found that energetically close anionic isomers coexist over a broad range in size, and their contribution in the photoelectron spectra could be separated using anion beam hole-burning technique. A detailed inspection into the electronic states and size-dependent energetics of each isomer has enabled us to establish a link from the large finite cluster to the infinite bulk system. Molecular clusters are finite aggregates consisting of 2-10 4 molecules and have been regarded as an excellent model system to use for gaining profound insights into weak noncovalent interactions, which play a predominant role in determining the structures and properties of molecular assemblies in chemistry, biology, and soft-material science. In molecular clusters, most of the properties originate from weakly perturbed, easily recognized, and well-defined units. Additionally, the finite number of molecules in the gas phase under collisionfree conditions makes a theoretical treatment much easier than that of bulk liquids and solids. Over the last two decades, therefore, intensive experimental and theoretical studies on molecular clusters have been performed, and a large number of review articles on the spectroscopic study of molecular clusters have been published in last twenty years.

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Photodissociation spectroscopy of benzene cluster ions: (C6H6)+2 and (C6H6)+3

Cited by 59 publications

References 45 publications

Electronic Structures and Photoevaporation Dynamics of Benzene Cluster Ions

Electronic Structures and Photoevaporation Dynamics of Benzene 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

Formation of Large Molecular Cluster Anions and Elucidation of Their Electronic Structures

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