Electronic structure of sodium nitrate: Investigations of laser desorption mechanisms

Journal Article · Thu Apr 18 04:00:00 EDT 1996 · Journal of Physical Chemistry

DOI:https://doi.org/10.1021/jp953108n· OSTI ID:263162

McCarthy, M I; Peterson, K A; Hess, W P ^[1]

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1. Pacific Northwest National Lab., Richland, WA (United States)

This theoretical study uses ab initio quantum mechanical methods to investigate the electronic properties of ground and excited state sodium nitrate. We calculated electronic properties of the crystalline material for bulk, clean, and defected surfaces. The results of these calculations are used to explain the photoexcitation/desorption mechanism and support the conclusions of an earlier experimental investigation of the laser desorption of NO from single-crystal sodium nitrate. The calculations indicate that the electronic structure of the bulk and cleavage surface are virtually identical (i.e., no shift in the resonant absorption profile is expected). This finding is consistent with the experimental results on the wavelength dependence of NO desorption yields for crystalline NaNO{sub 3}. However, changes in the absorption manifold are found to accompany the removal of external nitrate oxygens (producing surface nitrite groups). The presence of these chemical defects causes states to appear in the band gap producing a red shift in the absorption band. These calculations also indicate that the transition energies of the nitrate ion are unaffected by the presence of the surrounding ions. 34 refs., 8 figs., 2 tabs.

• DOE Contract Number: AC06-76RL01830
• OSTI ID: 263162
• Journal Information: Journal of Physical Chemistry, Journal Name: Journal of Physical Chemistry Journal Issue: 16 Vol. 100; ISSN JPCHAX; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

40 CHEMISTRY
66 PHYSICS
99 GENERAL AND MISCELLANEOUS
CALCULATION METHODS
CRYSTALS
DESORPTION
ELECTRONIC STRUCTURE
ENERGY-LEVEL TRANSITIONS
EXCITED STATES
GROUND STATES
HARTREE-FOCK METHOD
LASER RADIATION
NITRIC OXIDE
PHOTOCHEMICAL REACTIONS
SODIUM NITRATES