Critical point search and linear response theory for computing electronic excitation energies of molecular systems. I. General framework, application to Hartree–Fock and DFT

Abstract

Computing excited states of many-body quantum Hamiltonians is a fundamental challenge in computational physics and chemistry, with state-of-the-art methods broadly classified into variational (critical point search) and linear response approaches. The Kähler manifold formalism provides a uniform framework that naturally accommodates both strategies for a wide range of variational models, including Hartree–Fock, complete active space self-consistent field, full CI, and adiabatic time-dependent density functional theory. In particular, this formalism leads to a systematic and straightforward way to obtain the final equations of linear response theory for nonlinear models, which provides, in the case of mean-field models (Hartree–Fock and density functional theory), a simple alternative to Casida’s derivations. We detail the mathematical structure of Hamiltonian dynamics on Kähler manifolds, establish connections to standard quantum chemistry equations, and provide theoretical and numerical comparisons of excitation energy computation schemes at the Hartree–Fock level.