Electron autodetachment from isolated nickel and copper phthalocyanine-tetrasulfonate tetraanions: Isomer specific rates

被引:48
作者
Arnold, K
Balaban, TS
Blom, MN
Ehrler, OT
Gilb, S
Hampe, O
van Lier, JE
Weber, JM
Kappes, MM
机构
[1] Forschungszentrum Karlsruhe, Inst Nanotechnol, D-76021 Karlsruhe, Germany
[2] Univ Karlsruhe, Inst Phys Chem, D-76128 Karlsruhe, Germany
[3] Univ Sherbrooke, Fac Med, Sherbrooke, PQ J1K 2R1, Canada
关键词
D O I
10.1021/jp022141o
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Electron autodetachment from isolated metal phthalocyanine-tetrasulfonate tetraanions (MPc(SO3)(4)(4-)) (M=Ni, Cu) was studied at room temperature in an FT-ICR mass spectrometer under UHV conditions. For M = Cu, the electron loss rate was measured for the as-prepared isomer mixture. In the case of M = Ni, two chromatographically purified fractions containing different compositions of constitutional isomers were studied. The observed rate constants for these fractions differed by a factor of 37 +/- 5. Photoelectron spectroscopy indicates that both Cu and Ni compounds comprise isomer ensembles which are electronically metastable. Model calculations suggest that the differing electron loss rates observed for the Ni isomer fractions reflect tunneling through repulsive Coulomb barrier surfaces, which are themselves strongly isomer dependent in shape and height.
引用
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页码:794 / 803
页数:10
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