Anion photoelectron spectroscopy of free [Au25(SC12H25)18]-

Keisuke Hirata; Keishiro Yamashita; Satoru Muramatsu; Shinjiro Takano; Keijiro Ohshimo; Toshiyuki Azuma; Ryuzo Nakanishi; Takashi Nagata; Seiji Yamazoe; Kiichirou Koyasu; Tatsuya Tsukuda

doi:10.1039/c7nr04641c

Anion photoelectron spectroscopy of free [Au₂₅(SC₁₂H₂₅)₁₈]^-

Keisuke Hirata, Keishiro Yamashita, Satoru Muramatsu, Shinjiro Takano, Keijiro Ohshimo, Toshiyuki Azuma, Ryuzo Nakanishi, Takashi Nagata, Seiji Yamazoe, Kiichirou Koyasu, Tatsuya Tsukuda

SCI - Chemistry

Research output: Contribution to journal › Article › peer-review

29 Citations (Scopus)

Abstract

Previous theoretical studies have shown that the thiolated gold cluster compound [Au₂₅(SR)₁₈]^- can be viewed as a prototypical superatom with a closed electronic structure. The quantized electronic structure of [Au₂₅(SR)₁₈]^- has been experimentally demonstrated by optical and electrochemical methods in the dispersed state. Nevertheless, no direct information is available on the energy levels and densities of occupied states. Here, we report the photoelectron spectrum of [Au₂₅(SC₁₂H₂₅)₁₈]^- isolated under vacuum for the first time. The spectrum exhibits two distinct peaks, corresponding to electron detachment from the superatomic 1P orbitals and Au 5d orbitals of the Au₁₃ core. The adiabatic electron affinity of [Au₂₅(SC₁₂H₂₅)₁₈]⁰ was experimentally determined to be 2.2 eV, which is significantly smaller than that of [Au₂₅(SCH₃)₁₈]⁰ predicted theoretically.

Original language	English
Pages (from-to)	13409-13412
Number of pages	4
Journal	Nanoscale
Volume	9
Issue number	36
DOIs	https://doi.org/10.1039/c7nr04641c
Publication status	Published - 2017 Sept 28

ASJC Scopus subject areas

Materials Science(all)

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@article{45c3bd5180364208b610fc1fda019839,

title = "Anion photoelectron spectroscopy of free [Au25(SC12H25)18]-",

abstract = "Previous theoretical studies have shown that the thiolated gold cluster compound [Au25(SR)18]- can be viewed as a prototypical superatom with a closed electronic structure. The quantized electronic structure of [Au25(SR)18]- has been experimentally demonstrated by optical and electrochemical methods in the dispersed state. Nevertheless, no direct information is available on the energy levels and densities of occupied states. Here, we report the photoelectron spectrum of [Au25(SC12H25)18]- isolated under vacuum for the first time. The spectrum exhibits two distinct peaks, corresponding to electron detachment from the superatomic 1P orbitals and Au 5d orbitals of the Au13 core. The adiabatic electron affinity of [Au25(SC12H25)18]0 was experimentally determined to be 2.2 eV, which is significantly smaller than that of [Au25(SCH3)18]0 predicted theoretically.",

author = "Keisuke Hirata and Keishiro Yamashita and Satoru Muramatsu and Shinjiro Takano and Keijiro Ohshimo and Toshiyuki Azuma and Ryuzo Nakanishi and Takashi Nagata and Seiji Yamazoe and Kiichirou Koyasu and Tatsuya Tsukuda",

note = "Funding Information: This research was financially supported by the Elements Strategy Initiative for Catalysts and Batteries (ESICB), a Grant-in-Aid for Scientific Research (No. 26248003 and 17H01182), and the Nanotechnology Platform Program from the Ministry of Education, Culture, Sports, Science, and Technology (MEXT) of Japan. Publisher Copyright: {\textcopyright} 2017 The Royal Society of Chemistry.",

year = "2017",

month = sep,

day = "28",

doi = "10.1039/c7nr04641c",

language = "English",

volume = "9",

pages = "13409--13412",

journal = "Nanoscale",

issn = "2040-3364",

publisher = "Royal Society of Chemistry",

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T1 - Anion photoelectron spectroscopy of free [Au25(SC12H25)18]-

AU - Hirata, Keisuke

AU - Yamashita, Keishiro

AU - Muramatsu, Satoru

AU - Takano, Shinjiro

AU - Ohshimo, Keijiro

AU - Azuma, Toshiyuki

AU - Nakanishi, Ryuzo

AU - Nagata, Takashi

AU - Yamazoe, Seiji

AU - Koyasu, Kiichirou

AU - Tsukuda, Tatsuya

N1 - Funding Information: This research was financially supported by the Elements Strategy Initiative for Catalysts and Batteries (ESICB), a Grant-in-Aid for Scientific Research (No. 26248003 and 17H01182), and the Nanotechnology Platform Program from the Ministry of Education, Culture, Sports, Science, and Technology (MEXT) of Japan. Publisher Copyright: © 2017 The Royal Society of Chemistry.

PY - 2017/9/28

Y1 - 2017/9/28

N2 - Previous theoretical studies have shown that the thiolated gold cluster compound [Au25(SR)18]- can be viewed as a prototypical superatom with a closed electronic structure. The quantized electronic structure of [Au25(SR)18]- has been experimentally demonstrated by optical and electrochemical methods in the dispersed state. Nevertheless, no direct information is available on the energy levels and densities of occupied states. Here, we report the photoelectron spectrum of [Au25(SC12H25)18]- isolated under vacuum for the first time. The spectrum exhibits two distinct peaks, corresponding to electron detachment from the superatomic 1P orbitals and Au 5d orbitals of the Au13 core. The adiabatic electron affinity of [Au25(SC12H25)18]0 was experimentally determined to be 2.2 eV, which is significantly smaller than that of [Au25(SCH3)18]0 predicted theoretically.

AB - Previous theoretical studies have shown that the thiolated gold cluster compound [Au25(SR)18]- can be viewed as a prototypical superatom with a closed electronic structure. The quantized electronic structure of [Au25(SR)18]- has been experimentally demonstrated by optical and electrochemical methods in the dispersed state. Nevertheless, no direct information is available on the energy levels and densities of occupied states. Here, we report the photoelectron spectrum of [Au25(SC12H25)18]- isolated under vacuum for the first time. The spectrum exhibits two distinct peaks, corresponding to electron detachment from the superatomic 1P orbitals and Au 5d orbitals of the Au13 core. The adiabatic electron affinity of [Au25(SC12H25)18]0 was experimentally determined to be 2.2 eV, which is significantly smaller than that of [Au25(SCH3)18]0 predicted theoretically.

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Anion photoelectron spectroscopy of free [Au₂₅(SC₁₂H₂₅)₁₈]^-

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