Photodissociation Spectroscopy of

Ohashi, Kazuhiko; Nakai, Yasuhiro; Shibata, Takeshi; Nishi, Nobuyuki

doi:10.1155/1994/52450

Cited by 46 publications

(72 citation statements)

References 2 publications

(2 reference statements)

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“…Figure 3 shows the photodepletion spectra of (C 6 H 6 ) n + with n ) 3-6 in the range of 800-1100 nm, together with the fragment-yield spectrum of (C 6 H 6 ) 2 + . 10 We have already reported the fragment-yield spectra of (C 6 H 6 ) 3 + , 11 which are consistent with the depletion spectrum of (C 6 H 6 ) 3 + shown in Figure 3. The absorption bands of (C 6 H 6 ) n + with n ) 3-6 exhibit essentially the same features with that of (C 6 H 6 ) 2 + , although small shifts are found from the trimer (940 nm) to the hexamer (960 nm).…”

Section: Resultssupporting

confidence: 87%

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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: Resultssupporting

confidence: 87%

“…Fragmentyield spectrum of (C6H6)2 + is also shown in the top panel. 10 Charge resonance (CR) band characteristic of (C6H6)2 + remains almost intact in the larger cluster ions.…”

Section: Resultsmentioning

confidence: 99%

Electronic Structures and Photoevaporation Dynamics of Benzene Cluster Ions

1997

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“…These states are described as The upper charge resonance state has a repulsive potential surface along the intermolecular distance. 18 The excitation to the LE state will be followed by the internal conversion to the lower dissociative state, resulting in a dissociation yield close to unity. The resemblance of the gas-phase dissociation spectrum to the condensed-phase absorption spectrum in a Freon mixture is thus well understood by assuming approximately the same dissociation yield for the photon energies in the visible and near-IR region.…”

Section: Resultsmentioning

confidence: 99%

Photodissociation Spectrum of Naphthalene Dimer Cation

Inokuchi

Ohashi²,

Matsumoto

et al. 1995

J. Phys. Chem.

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The electronic spectrum of (CloH8)2+ is obtained in the 455-1400 nm region by applying photodissociation spectroscopy to the ion produced by the laser-induced plasma technique. The spectrum shows a local excitation band at 580 nm and a charge resonance band at 1180 nm. The locations of these bands coincide with those reported for intramolecular dimer cations of dinaphthylpropanes with a partially overlapped conformation, suggesting that (ClOHg)2+ has a similar conformation in the gas phase.

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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

Cited by 46 publications

References 2 publications

Electronic Structures and Photoevaporation Dynamics of Benzene Cluster Ions

Electronic Structures and Photoevaporation Dynamics of Benzene Cluster Ions

Photodissociation Spectrum of Naphthalene Dimer Cation

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

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