\mathcal{PT}-Symmetry in Hartree-Fock Theory

DOI10.1021/ACS.JCTC.9B00289MaRDI QIDQ6315936zbMATH OpenWikidataFDO

Authors Hugh G. A. Burton, Alex J. W. Thom, Pierre-François Loos

Publication date 20 March 2019

Full work available at URL https://doi.org/10.1021/ACS.JCTC.9B00289

Abstract: $mathcalPT$-symmetry --- invariance with respect to combined space reflection $mathcalP$ and time reversal $mathcalT$ --- provides a weaker condition than (Dirac) Hermiticity for ensuring a real energy spectrum of a general non-Hermitian Hamiltonian. $mathcalPT$-symmetric Hamiltonians therefore form an intermediate class between Hermitian and non-Hermitian Hamiltonians. In this work, we derive the conditions for $mathcalPT$-symmetry in the context of electronic structure theory, and specifically, within the Hartree-Fock (HF) approximation. We show that the HF orbitals are symmetric with respect to the $mathcalPT$ operator extit{if and only if} the effective Fock Hamiltonian is $mathcalPT$-symmetric, and extit{vice versa}. By extension, if an optimal self-consistent solution is invariant under $mathcalPT$, then its eigenvalues and corresponding HF energy must be real. Moreover, we demonstrate how one can construct explicitly $mathcalPT$-symmetric Slater determinants by forming $mathcalPT$ doublets (i.e. pairing each occupied orbital with its $mathcalPT$-transformed analogue), allowing $mathcalPT$-symmetry to be conserved throughout the self-consistent process. Finally, considering the ce{H2} molecule as an illustrative example, we observe $mathcalPT$-symmetry in the HF energy landscape and find that the symmetry-broken unrestricted HF wave functions (i.e. diradical configurations) are $mathcalPT$-symmetric, while the symmetry-broken restricted HF wave functions (i.e. ionic configurations) break $mathcalPT$-symmetry.

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