Formation of a linear LiOH compound on Cu(001): reaction of H2O with Li adatoms at low coverages

S. Mizuno, H. Tochihara, T. Kadowaki, H. Minagawa, K. Hayakawa, I. Toyoshima, C. Oshima

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Abstract

The reaction of H2O with Li adatoms at low coverages on Cu(001) has been studied at room temperature by using high-resolution electron energy loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS) and work-function measurement. The coverage (θ) of Li was 0.125 except for the experiment of the work function (θ = 0.25). The O 1s XPS spectra from the H2O exposed Li/Cu(001) surface showed a single peak at 531.5 eV. It was found by comparing the area of the O 1s peaks of H2O/Li/Cu(001) with that of (√2 × 2√2) R45°O Cu(001) that the stoichiometry of oxygen to Li is 1:1. HREELS spectra showed a strong peak at 600 cm-1 and small peaks at 3600, 1300 and 1100 cm-1. The work function increased with increasing H2O exposure. These observations and the results of previous studies lead to the conclusion that the reaction product as a result of interaction of H2O with Li adatoms on Cu(001) is a linear triatomic molecule of LiOH which sits on the surface upright with Li down. The reaction scheme is expressed as Li(a) + H2O(a) → LiOH(a) + H(a), where (a) denotes adspecies. The strong 600 cm-1 peak in HREELS spectra is assigned to the Li-OH stretching mode. The intense loss-peak indicates the LiOH molecule formed on Cu(001) has an ionic-bond character. In fact the effective dynamic charge of the Li-OH stretching vibration is estimated to be ∼ 0.5e, and this is larger than that of the Li stretching vibration in the Li/Cu(001) system, ∼ 0.3e. Force constants of the LiOH admolecule are estimated. A transition state for the reaction is proposed.

Original languageEnglish
Pages (from-to)103-113
Number of pages11
JournalSurface Science
Volume264
Issue number1-2
DOIs
Publication statusPublished - 1992 Mar 1

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Adatoms
Electron energy loss spectroscopy
adatoms
Stretching
X ray photoelectron spectroscopy
Molecules
energy dissipation
electron energy
Reaction products
Stoichiometry
high resolution
photoelectron spectroscopy
spectroscopy
Oxygen
triatomic molecules
vibration
reaction products
stoichiometry
x rays
Experiments

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Condensed Matter Physics
  • Surfaces and Interfaces

Cite this

Mizuno, S., Tochihara, H., Kadowaki, T., Minagawa, H., Hayakawa, K., Toyoshima, I., & Oshima, C. (1992). Formation of a linear LiOH compound on Cu(001): reaction of H2O with Li adatoms at low coverages. Surface Science, 264(1-2), 103-113. https://doi.org/10.1016/0039-6028(92)90169-7

Formation of a linear LiOH compound on Cu(001) : reaction of H2O with Li adatoms at low coverages. / Mizuno, S.; Tochihara, H.; Kadowaki, T.; Minagawa, H.; Hayakawa, K.; Toyoshima, I.; Oshima, C.

In: Surface Science, Vol. 264, No. 1-2, 01.03.1992, p. 103-113.

Research output: Contribution to journalArticle

Mizuno, S, Tochihara, H, Kadowaki, T, Minagawa, H, Hayakawa, K, Toyoshima, I & Oshima, C 1992, 'Formation of a linear LiOH compound on Cu(001): reaction of H2O with Li adatoms at low coverages', Surface Science, vol. 264, no. 1-2, pp. 103-113. https://doi.org/10.1016/0039-6028(92)90169-7
Mizuno S, Tochihara H, Kadowaki T, Minagawa H, Hayakawa K, Toyoshima I et al. Formation of a linear LiOH compound on Cu(001): reaction of H2O with Li adatoms at low coverages. Surface Science. 1992 Mar 1;264(1-2):103-113. https://doi.org/10.1016/0039-6028(92)90169-7
Mizuno, S. ; Tochihara, H. ; Kadowaki, T. ; Minagawa, H. ; Hayakawa, K. ; Toyoshima, I. ; Oshima, C. / Formation of a linear LiOH compound on Cu(001) : reaction of H2O with Li adatoms at low coverages. In: Surface Science. 1992 ; Vol. 264, No. 1-2. pp. 103-113.
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abstract = "The reaction of H2O with Li adatoms at low coverages on Cu(001) has been studied at room temperature by using high-resolution electron energy loss spectroscopy (HREELS), X-ray photoelectron spectroscopy (XPS) and work-function measurement. The coverage (θ) of Li was 0.125 except for the experiment of the work function (θ = 0.25). The O 1s XPS spectra from the H2O exposed Li/Cu(001) surface showed a single peak at 531.5 eV. It was found by comparing the area of the O 1s peaks of H2O/Li/Cu(001) with that of (√2 × 2√2) R45°O Cu(001) that the stoichiometry of oxygen to Li is 1:1. HREELS spectra showed a strong peak at 600 cm-1 and small peaks at 3600, 1300 and 1100 cm-1. The work function increased with increasing H2O exposure. These observations and the results of previous studies lead to the conclusion that the reaction product as a result of interaction of H2O with Li adatoms on Cu(001) is a linear triatomic molecule of LiOH which sits on the surface upright with Li down. The reaction scheme is expressed as Li(a) + H2O(a) → LiOH(a) + H(a), where (a) denotes adspecies. The strong 600 cm-1 peak in HREELS spectra is assigned to the Li-OH stretching mode. The intense loss-peak indicates the LiOH molecule formed on Cu(001) has an ionic-bond character. In fact the effective dynamic charge of the Li-OH stretching vibration is estimated to be ∼ 0.5e, and this is larger than that of the Li stretching vibration in the Li/Cu(001) system, ∼ 0.3e. Force constants of the LiOH admolecule are estimated. A transition state for the reaction is proposed.",
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