Doublet Separations #

Hg 4f = 4.1 eV

Hg 4d = 19.2 eV

Hg 4p = 104 eV

Hd 5d = 1.9 eV

Common Overlaps for Hg 4f #

Si 2p – Sb 4p – La 4p – Al KLL (Al ka X-rays) – Br LMM (Al ka X-rays) – Ga 3p – Pt 5s – Co 3s – Po 5p

Auger Energies #

Note – these are listed in KINETIC ENERGY

Hg MNN ≈ 2160 eV

Common Binding Energies – Cu 2p #

Theory and Background #

Core level energies #

• Hg 4f₇/₂ ≈ 99.8–100.5 eV (metallic Hg near 99.9 eV).

• Hg 4f₅/₂ ≈ +4.2 eV higher (~104–105 eV).

• Spin–orbit splitting ≈ 4.2 eV, larger than many transition metals.

• Oxidation shifts:

  • Hg(II) compounds (oxides, halides) appear ~1–2 eV higher BE than Hg⁰.

  • Shifts can be subtle and vary with ligand environment.

Final-state effects #

• Metallic Hg has weak conduction-electron screening → 4f peaks are relatively symmetric, without strong Doniach–Šunjić tails.

• Compounds show broader, more symmetric peaks, sometimes with poorly resolved multiplet/satellite structure.

Satellites & shake features #

• Hg(II) compounds (oxides, halides, organomercury) can exhibit weak shake-up satellites a few eV above the main 4f peaks.

• Intensity is small; careful background subtraction needed to see them.

• Satellites can serve as confirmation of oxidized Hg, though they are not as distinct as in some transition metals.

Experimental Advice #

• Minimize air exposure: Hg can oxidize in air or adsorb contaminants that alter XPS.

• Avoid heating: Do not heat Hg samples in vacuum; volatilization will contaminate pumps/analyzer.

• Thin films & supported catalysts: Safer than bulk Hg — immobilized Hg compounds are preferred for analysis.

• Storage: Keep in sealed containers; prepare samples fresh when possible

Data Analysis Guidance #

• Line shapes:

  • Metallic Hg: symmetric GL (minimal asymmetry).

  • Oxides/halides: symmetric GL; broaden slightly.

• Constraints:

  • Fix spin–orbit splitting at ~4.2 eV.

  • Fix area ratio at 4f₇/₂ : 4f₅/₂ = 4 : 3.

• Background: Shirley or Tougaard; Tougaard may better handle loss features if visible.

• Shake-ups: Add only if clearly resolved; typically weak (<10% intensity).

• Chemical state separation: Use binding energy + presence of satellites + supporting regions (e.g. O 1s, Cl 2p) to confirm assignments.

Reference Datasets #

Coming soon

References #