Photoelectron spectroscopy of (C6F6)− and (Au-C6F6)− clusters

Nakajima, Atsushi; Taguwa, Tetsuya; Hoshino, Kuniyoshi; Sugioka, Tsuneyoshi; Naganuma, Takashi; Oho, F.; Watanabe, Keiji; Nakao, Kojiro; Konishi, Yasuo; Kishi, Reiko; Kaya, Kunimitsu

doi:10.1016/0009-2614(93)85449-x

Cited by 114 publications

(69 citation statements)

References 19 publications

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“…As depicted in Fig. 1, we employed two anion production methods: 56 (a) injection of slow photoelectrons (kinetic energy: %0.3 eV), produced by irradiating the surface of a Y 2 O 3 disk with the second harmonics of a Nd 3þ :YAG laser, and (b) high-energy electron impact ionization method (typically 300 eV, %5 mA), where the formation of cluster anions results from attachment of slow secondary electrons (kinetic energy: <1 eV) generated by ionization of the carrier gas. In both methods, electrons were injected into the dense area of the supersonic expansion with the distance (z) between ionization region and nozzle orifice variable from 1 to 50 mm.…”

Section: Experimental Methodologymentioning

confidence: 99%

“…13,[85][86][87][88][89] In particular, the ''dark'' optically forbidden electronic states (e.g., excited triplet states) of neutral molecules are accessible via a one-electron photodetachment transition from the corresponding anion ground state. Figure 5 illustrates a schematic diagram of our anion photoelectron spectroscopy apparatus 56,91 which consists of three parts: a cluster anion source, an in-line Wiley-McLaren TOF-MS (M=ÁM % 200), and a magnetic-bottle-type electron energy analyzer. 92 On the left side, the anion source containing a pulsed Even-Lavie valve and electron gun (or Y 2 O 3 disk) is displayed, the details of which have been already mentioned above.…”

Section: Experimental Methodologymentioning

confidence: 99%

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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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Section: Experimental Methodologymentioning

confidence: 99%

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 apparatus used in the present work is a negative ion photoelectron spectrometer that has been described in detail previously [32]. Here we give only a brief description.…”

Section: Methodsmentioning

confidence: 99%

Photoelectron spectroscopy of transition metal-sulfur cluster anions

Nakajima¹,

Kawamata²,

Hayase³

et al. 1997

Z Phys D - Atoms, Molecules and Clusters

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Metal (M)-sulfur cluster anions (M = Ag, Fe and Mn) have been studied using photoelectron spectroscopy (PES) with a magnetic-bottle type time-of-flight electron spectrometer. The M n S − m cluster anions were formed in a laser vaporization cluster source. For Ag-S, the largest coordination number of Ag atoms (n max ) is generally expressed as n max = 2m − 1 in each series of the number of S atoms (m). For Fe-S and Mn-S, it was found that the stable cluster ions are the ones with compositions of n = m and n = m ± 1. Their electron affinities were measured from the onset of the PES spectrum. For Ag-S, the EAs of Ag 1 S m are small and around 1 eV, whereas those of Ag n S m (n ≥ 2) become large above 2 eV. The features in the mass distribution and PES suggest that Ag 2 S unit is preferentially formed with increasing the number of Ag atoms. For Fe-S and Mn-S, the PES spectra of Fe n S − m /Mn n S − m show a unique similarity at n ≥ m, indicating that the Fe/Mn atom addition to Fe n S − n /Mn n S − n has little effect on the electronic property of Fe n S n /Mn n S n . The PES spectra imply that the Fe n S n cluster is the structural framework of these clusters, as similarly as the determined structure of the Fe n S n cluster in nitrogenase enzyme. PACS: 79.60.Eq; 33.60.Cv; 36.40.In I IntroductionRecently, photoelectron spectroscopy has been proven to be a powerful tool to study the electronic and geometric structures of atomic and molecular clusters [1, 2], due to its ability to combine size selectivity with spectral sensitivity. Ever since the pioneering work of Smalley et al. [3] and Lutz et al. [4], there have been significant recent advances in this field. A variety of work have been done on the PES of pure metal cluster anions [5], semi-conductor clusters anions [3, 6] and solvated anions (cluster as the solvent) [7].Among them, Lineberger and co-workers [8] have studied a number of small heavy metal cluster anions with a high energy resolution electron spectrometer. In a very recent work, Handschuh et al. [9] have improved the energy resolution of a magnetic-bottle type electron spectrometer to about 6 meV, and thus vibrationally resolved photoelectron spectra can be studied in this type of electron spectromer. Since photodetachment is a process of transition from the ground state of anions into the ground state or electronic excited states of the corresponding neutrals, therefore, the electronic properties of the neutral clusters are readily observed from the photoelectron spectra. While the most works on anion PES have been reported for pure elemental and molecular clusters [7], and for solvated anions of the type of A − (X) n (X is solvent molecules) [10,11], there is an increasingly recent interest on the study of binary cluster anions of the type of A n B − m [12,13], in which A and B can be a metal or nonmetal element or both.Among the binary clusters, the study of transition-metal sulfides has attracted broad attention over the past decades because of their solids exhibiting a variety of electronic and st...

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“…:O.03 eV. 6 On the basis of these data, there is no doubt that two low lying bound electronic states of C 6 F(; exist as postulated earlier. 4 The data discussed above can be combined with data for the rate constant for thermal electron attachment and electron beam data 8 to provide three data points on the pseudo "two dimensional" Morse potential energy curves for the two low lying bound negative ion states of C 6 F 6 .…”

mentioning

confidence: 88%

Comment on ‘‘Temperature-enhanced electron detachment from C6F−6 negative ions’’ [J. Chem. Phys. 98, 7875 (1993)]

Chen

Wentworth

1994

The Journal of Chemical Physics

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The results of three recent, independent measurements of the electron affinity of C6F6 are discussed. These utilize an electron capture detector (ECD), an atmospheric pressure ionization mass spectrometer (APIMS), and a photoelectron spectrometer (PES). Seven independent measurements of the temperature dependence of the ECD response of C6F6 give an average value of 0.86±0.02 eV for the electron affinity of C6F6 in agreement with an earlier published value. The APIMS and PES studies have been recently published and support the ECD value. On this basis, it is suggested that the value of the electron affinity of about 0.5 eV presented in the subject article refers to an excited electronic state of the anion of C6F6. Morse potential energy curves are calculated for four negative ions states of C6F6 using experimental data.

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Photoelectron spectroscopy of (C6F6)− and (Au-C6F6)− clusters

Cited by 114 publications

References 19 publications

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

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

Photoelectron spectroscopy of transition metal-sulfur cluster anions

Comment on ‘‘Temperature-enhanced electron detachment from C6F−6 negative ions’’ [J. Chem. Phys. 98, 7875 (1993)]

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