Intracluster electron transfer from a metal atom/cluster followed by anionic oligomerization of vinyl molecules

科研費報告書収録論文(課題番号:13640498・基盤研究(C)(2) ・H13～H14/研究代表者:美齊津, 文典/アニオン重合初期反応系モデルとしての金属-分子クラスターの幾何・電子構造の研究

Electron distribution and intracluster reaction in [Nan(CS2)2]? negative ion clusters

科研費報告書収録論文(課題番号:15350003・基盤研究(B)(2)・15～16/研究代表者:美齊津, 文典/イオンドリフトチューブ法による異性体分離分光のクラスター内反応生物への適用

Studies on Solvation Structure and Intracluster Reaction of Aqueous Metal Ions by IR Photodissociation Spectroscopy

セミナー開催, 2005年7月22日, Buntine Group, at The University of Adelaide, in Adelaide, Australi

Negative-ion photoelectron spectroscopy of acrylonitrile clusters containing a sodium atom

Cluster anions of a sodium atom with acrylonitrile molecules, Na(AN)$_n^-$ ($n=0{-}6$), have been studied by negative-ion photoelectron spectroscopy. In addition, theoretical calculations by using density functional theory have been performed to obtain optimized structures and vertical detachment energies. For Na(AN)-, the spectrum can be explained by excitation of two different isomers of the anion. For Na(AN)$_3^-$, a broad band is found in the photoelectron spectrum, whose profile is almost identical with those of previously reported photoelectron spectra of (AN)$_3^-$ and a negative ion of chemically synthesized 1,3,5-cyclohexanetricarbonitrile (CHTCN) molecule. From this resemblance of band profiles, we conclude that oligomerization of (AN)3 takes place in Na(AN)$_3^-$ and the CHTCN is formed as the intracluster reaction product

Negative-ion photoelectron spectroscopy of acrylonitrile clusters containing a sodium atom

科研費報告書収録論文(課題番号:15350003・基盤研究(B)(2)・15～16/研究代表者:美齊津, 文典/イオンドリフトチューブ法による異性体分離分光のクラスター内反応生物への適用

Intracluster electron transfer from a metal atom/cluster followed by anionic oligomerization of vinyl molecules

Intracluster electron transfer and oligomerization reaction were investigated by mass spectrometry of clusters of alkali metal atom (M) with acrylonitrile (AN; CH2=CHCN). In the photoionization mass spectra of M(AN)n, magic numbers were clearly observed at n=3k (k=1-4 for M = Na and K, k=1 for M = Li). The results of photodissociation of neutral K(AN)n indicate that the n=3 cluster has an anomalous stability relative to other sizes of clusters. The C=C bond in vinyl molecules is also found to be necessary to form the magic numbers by measuring the photoionization mass spectrum of K atom with propionitrile. These results strongly support the intracluster anionic oligomerization reaction initiated by electron transfer from the alkali atom. The quantum chemical calculations have revealed that the evaporation induced by excess energy generated by intracluster oligomerization is important to form the magic numbers in the present clusters