Importance of reference Hamiltonians containing exact exchange for accurate one-shot $GW$ calculations of Cu${}_{2}$O

Importance of reference Hamiltonians containing exact exchange for accurate one-shot $G W$ calculations of Cu $_{2}$ O

Leah Y. Isseroff and Emily A. Carter

Phys. Rev. B 85, 235142 – Published 22 June 2012

Abstract

We show that a “one-shot” $G W$ approach (denoted $G_{0}$ $W_{0}$ ) can accurately calculate the photoemission/inverse-photoemission properties of Cu $_{2}$ O. As the results of any perturbative method are heavily dependent on the reference state, the appropriate reference Hamiltonian for $G_{0}$ $W_{0}$ is identified by evaluating the performance of density-functional-theory-based input wave functions and eigenvalues generated with selected exchange-correlation functionals. It is shown that a reference Hamiltonian employing the hybrid Heyd-Scuseria-Ernzerhof functional used in conjunction with $G_{0}$ $W_{0}$ produces an accurate photoemission/inverse-photoemission band gap and photoemission spectrum whose character is then further analyzed. The physical origin of why a hybrid functional is required for the zeroth-order wave function is discussed, giving insight into the unique electronic structure of Cu $_{2}$ O in comparison to other transition-metal oxides.

Received 17 January 2012

DOI:https://doi.org/10.1103/PhysRevB.85.235142

Authors & Affiliations

Leah Y. Isseroff¹ and Emily A. Carter^2,*

¹Department of Chemical and Biological Engineering, Princeton University, Princeton, New Jersey 08544-5263, USA
²Department of Mechanical and Aerospace Engineering, Program in Applied and Computational Mathematics, and Andlinger Center for Energy and the Environment, Princeton University, Princeton, New Jersey 08544-5263, USA

^*Author to whom all correspondence should be addressed: eac@princeton.edu

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Vol. 85, Iss. 23 — 15 June 2012

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