Time-dependent Hartree–Fock–Bogoliubov method for molecular systems: An alternative excited-state methodology including static electron correlation.

[Display omitted] • We developed time-dependent Hartree-Fock-Bogoliubov (TDHFB) method, a simple excited-state method with static correlation. • We employed the canonical-basis (Cb-)TDHFB formulation to avoid the violation of the electron number preservation. • The real-time Cb-TDHFB method can describe a multi-configurational character in excited states of bond dissociation. The Hartree–Fock–Bogoliubov (HFB) method, an efficient way to treat static electron correlations, has been applied to molecular systems in the ground state. In this letter, we propose a time-dependent (TD) HFB method for treating the excited states of molecules with static correlations at a reasonable computational cost. To avoid electron number violations, we also consider the canonical basis variant of the TDHFB method proposed by Ebata et al. Results of calculations for the elongated hydrogen molecule reveal that the TDHFB method can partially incorporate two-electron excited determinants. [ABSTRACT FROM AUTHOR]