Intact Four-atom Organic Tetracation Stabilized by Charge Localization in the Gas Phase.
Several features distinguish intact multiply charged molecular cations (MMCs) from other species such as monocations and polycations: high potential energy, high electron affinity, a high density of electronic states with various spin multiplicities, and charge-dependent reactions. However, repulsive Coulombic interactions make MMCs quite unstable, and hence small organic MMCs are currently not readily available. Herein, we report that the isolated four-atom molecule diiodoacetylene survives after the removal of four electrons via tunneling. We show that the tetracation remains metastable towards dissociation because of the localization (91-95 %) of the positive charges on the terminal iodine atoms, ensuring minimum Coulomb repulsion between adjacent atoms as well as maximum charge-induced attractive dipole interactions between iodine and carbon. Our approach making use of iodines as the positively charged sites enables small organic MMCs to remain intact.
Graduate School of Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi, Osaka, 558-8585, Japan. tomo@sci.osaka-cu.ac.jp.|PRESTO, Japan Science and Technology Agency, 4-1-8 Honcho Kawaguchi, Saitama, 332-0012, Japan. tomo@sci.osaka-cu.ac.jp.
Tomoyuki
http://orcid.org/0000-0002-6810-7774
T
Yatsuhashi
Graduate School of Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi, Osaka, 558-8585, Japan.
Kazuo
K
Toyota
Graduate School of Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi, Osaka, 558-8585, Japan.
Naoya
N
Mitsubayashi
Graduate School of Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi, Osaka, 558-8585, Japan.
Masatoshi
M
Kozaki
Graduate School of Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi, Osaka, 558-8585, Japan.
Keiji
K
Okada
Graduate School of Science, Osaka City University, 3-3-138 Sugimoto, Sumiyoshi, Osaka, 558-8585, Japan.
Nobuaki
N
Nakashima
active species; density functional calculations; laser chemistry; polycations; tunneling