TY - JOUR
T1 - Assessment of interstitial potentials for rapid prediction of absolute band energies in crystals
AU - Harnett-Caulfield, Liam
AU - Walsh, Aron
N1 - Publisher Copyright:
© 2021 Author(s).
PY - 2021/7/14
Y1 - 2021/7/14
N2 - Electronic band alignment is a demanding process for first-principles simulations, but an important factor in materials selection for applications including electrocatalysis and photoelectrochemistry. Here, we revisit a bulk alignment procedure, originally developed by Frensley and Kroemer, using modern computational tools. The electrostatic potential in the interstitial region, obtained from density functional theory, with four exchange correlation functionals, is used to predict the valence band offsets of 27 zinc blende semiconductors. The results are found to be in qualitative agreement with Frensley and Kroemer’s original data. In addition to absolute electron energies, the possibility of extracting effective ionic charges is investigated and compared to Bader partial charges. With further developments, such a procedure may support rapid screening of the bulk ionization potential and electron affinity of crystals, as we illustrate with an extension to rock salt and perovskite structure types.
AB - Electronic band alignment is a demanding process for first-principles simulations, but an important factor in materials selection for applications including electrocatalysis and photoelectrochemistry. Here, we revisit a bulk alignment procedure, originally developed by Frensley and Kroemer, using modern computational tools. The electrostatic potential in the interstitial region, obtained from density functional theory, with four exchange correlation functionals, is used to predict the valence band offsets of 27 zinc blende semiconductors. The results are found to be in qualitative agreement with Frensley and Kroemer’s original data. In addition to absolute electron energies, the possibility of extracting effective ionic charges is investigated and compared to Bader partial charges. With further developments, such a procedure may support rapid screening of the bulk ionization potential and electron affinity of crystals, as we illustrate with an extension to rock salt and perovskite structure types.
UR - http://www.scopus.com/inward/record.url?scp=85109916559&partnerID=8YFLogxK
U2 - 10.1063/5.0044866
DO - 10.1063/5.0044866
M3 - Article
C2 - 34266274
AN - SCOPUS:85109916559
SN - 0021-9606
VL - 155
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 2
M1 - 024113
ER -