Superatom Spectroscopy and the Electronic State Correlation between Elements and Isoelectronic Molecular Counterparts

• Published in: Proceedings of the National Academy of Sciences - PNAS 2010-01, Vol.107 (3), p.975-980
• Main Authors: Peppernick, Samuel J., Gunaratne, K. D. Dasitha, Castleman, A. W., Berry, R. Stephen
• Format: Article
• Language: English
• Subjects: Angular momentum; Anions; Atoms; Atoms & subatomic particles; Electronics; Electrons; Experiments; Ground state; Molecular orbitals; Molecules; Neutrality; Orbitals; Photoelectrons; Photons; Physical Sciences; Spectrum analysis
• ISSN: 0027-8424; 1091-6490
• DOI: 10.1073/pnas.0911240107

Detailed in the present investigation are results pertaining to the photoelectron spectroscopy of negatively charged atomic ions and their isoelectronic molecular counterparts. Experiments utilizing the photoelectron imaging technique are performed on the negative ions of the group 10 noble metal block (i.e. Nr⁻ Pd⁻, and Pt⁻) of the periodic table at a photon energy of 2.33 eV (532 nm). The accessible electronic transitions, term energies, and orbital angular momentum components of the bound electronic states in the atom are then compared with photoelectron images collected for isoelectronic early transition metal heterogeneous diatomic molecules, M-X⁻ (M = Ti, Zr, W; X = O or C). A superposition principle connecting the spectroscopy between the atomic and molecular species is observed, wherein the electronic structure of the diatomic is observed to mimic that present in the isoelectronic atom. The molecular ions studied in this work, TiO⁻, ZrO⁻, and WC⁻ can then be interpreted as possessing superatomic electronic structures reminiscent of the isoelectronic elements appearing on the periodic table, thereby quantifying the superatom concept.