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Title: Atomic solid state energy scale: Universality and periodic trends in oxidation state

Abstract

The atomic solid state energy (SSE) scale originates from a plot of the electron affinity (EA) and ionization potential (IP) versus band gap (E{sub G}). SSE is estimated for a given atom by assessing an average EA (for a cation) or an average IP (for an anion) for binary inorganic compounds having that specific atom as a constituent. Physically, SSE is an experimentally-derived average frontier orbital energy referenced to the vacuum level. In its original formulation, 69 binary closed-shell inorganic semiconductors and insulators were employed as a database, providing SSE estimates for 40 elements. In this contribution, EA and IP versus E{sub G} are plotted for an additional 92 compounds, thus yielding SSE estimates for a total of 64 elements from the s-, p-, d-, and f-blocks of the periodic table. Additionally, SSE is refined to account for its dependence on oxidation state. Although most cations within the SSE database are found to occur in a single oxidation state, data are available for nine d-block transition metals and one p-block main group metal in more than one oxidation state. SSE is deeper in energy for a higher cation oxidation state. Two p-block main group non-metals within the SSE database aremore » found to exist in both positive and negative oxidation states so that they can function as a cation or anion. SSEs for most cations are positioned above −4.5 eV with respect to the vacuum level, and SSEs for all anions are positioned below. Hence, the energy −4.5 eV, equal to the hydrogen donor/acceptor ionization energy ε(+/−) or equivalently the standard hydrogen electrode energy, is considered to be an absolute energy reference for chemical bonding in the solid state. - Highlights: • Atomic solid-state energies are estimated for 64 elements from experimental data. • The relationship between atomic SSEs and oxidation state is assessed. • Cations are positioned above and absolute energy of −4.5 eV and anions below.« less

Authors:
 [1];  [2];  [1];  [3];  [1]
  1. School of EECS, Oregon State University, Corvallis, OR 97331-5501 (United States)
  2. Department of Chemistry, Oregon State University, 153 Gilbert Hall, Corvallis, OR 97331-4003 (United States)
  3. Department of Statistics, Oregon State University, Corvallis, OR 97331-4606 (United States)
Publication Date:
OSTI Identifier:
22573937
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 231; Other Information: Copyright (c) 2015 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AFFINITY; ANIONS; ATOMS; CATIONS; CHEMICAL BONDS; ELECTRODES; ELECTRONEGATIVITY; ELECTRONS; ENERGY LEVELS; EXPERIMENTAL DATA; HYDROGEN; INORGANIC COMPOUNDS; IONIZATION POTENTIAL; OXIDATION; PERIODIC SYSTEM; PERIODICITY; SOLIDS; TRANSITION ELEMENTS

Citation Formats

Pelatt, Brian D., Kokenyesi, Robert S., Ravichandran, Ram, Pereira, Clifford B., Wager, John F., and Keszler, Douglas A., E-mail: Douglas.Keszler@oregonstate.edu. Atomic solid state energy scale: Universality and periodic trends in oxidation state. United States: N. p., 2015. Web. doi:10.1016/J.JSSC.2015.07.037.
Pelatt, Brian D., Kokenyesi, Robert S., Ravichandran, Ram, Pereira, Clifford B., Wager, John F., & Keszler, Douglas A., E-mail: Douglas.Keszler@oregonstate.edu. Atomic solid state energy scale: Universality and periodic trends in oxidation state. United States. doi:10.1016/J.JSSC.2015.07.037.
Pelatt, Brian D., Kokenyesi, Robert S., Ravichandran, Ram, Pereira, Clifford B., Wager, John F., and Keszler, Douglas A., E-mail: Douglas.Keszler@oregonstate.edu. Sun . "Atomic solid state energy scale: Universality and periodic trends in oxidation state". United States. doi:10.1016/J.JSSC.2015.07.037.
@article{osti_22573937,
title = {Atomic solid state energy scale: Universality and periodic trends in oxidation state},
author = {Pelatt, Brian D. and Kokenyesi, Robert S. and Ravichandran, Ram and Pereira, Clifford B. and Wager, John F. and Keszler, Douglas A., E-mail: Douglas.Keszler@oregonstate.edu},
abstractNote = {The atomic solid state energy (SSE) scale originates from a plot of the electron affinity (EA) and ionization potential (IP) versus band gap (E{sub G}). SSE is estimated for a given atom by assessing an average EA (for a cation) or an average IP (for an anion) for binary inorganic compounds having that specific atom as a constituent. Physically, SSE is an experimentally-derived average frontier orbital energy referenced to the vacuum level. In its original formulation, 69 binary closed-shell inorganic semiconductors and insulators were employed as a database, providing SSE estimates for 40 elements. In this contribution, EA and IP versus E{sub G} are plotted for an additional 92 compounds, thus yielding SSE estimates for a total of 64 elements from the s-, p-, d-, and f-blocks of the periodic table. Additionally, SSE is refined to account for its dependence on oxidation state. Although most cations within the SSE database are found to occur in a single oxidation state, data are available for nine d-block transition metals and one p-block main group metal in more than one oxidation state. SSE is deeper in energy for a higher cation oxidation state. Two p-block main group non-metals within the SSE database are found to exist in both positive and negative oxidation states so that they can function as a cation or anion. SSEs for most cations are positioned above −4.5 eV with respect to the vacuum level, and SSEs for all anions are positioned below. Hence, the energy −4.5 eV, equal to the hydrogen donor/acceptor ionization energy ε(+/−) or equivalently the standard hydrogen electrode energy, is considered to be an absolute energy reference for chemical bonding in the solid state. - Highlights: • Atomic solid-state energies are estimated for 64 elements from experimental data. • The relationship between atomic SSEs and oxidation state is assessed. • Cations are positioned above and absolute energy of −4.5 eV and anions below.},
doi = {10.1016/J.JSSC.2015.07.037},
journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = ,
volume = 231,
place = {United States},
year = {2015},
month = {11}
}