Near exact excited states of the carbon dimer in a quadruple-zeta basis using a general non-Abelian density matrix renormalization group algorithm

Abstract

We extend our previous work [J. Chem. Phys, \textbf{136}, 124121], which described a spin-adapted (SU(2) symmetry) density matrix renormalization group (DMRG) algorithm, to additionally utilize general non-Abelian point group symmetries. A key strength of the present formulation is that the requisite tensor operators are not hard-coded for each symmetry group, but are instead generated on the fly using the appropriate Clebsch-Gordan coefficients. This allows our single implementation to easily enable (or disable) any non-Abelian point group symmetry (including SU(2) spin symmetry). We use our implementation to compute the ground state potential energy curve of the C${}_2$ dimer in the cc-pVQZ basis set (with a frozen-core), corresponding to a Hilbert space dimension of 10${}^{12}$ many-body states. While our calculated energy lies within the 0.3 mE${}_h$ error bound of previous initiator full configuration interaction quantum Monte Carlo (i-FCIQMC) and correlation energy extrapolation by intrinsic scaling (CEEIS) calculations, our estimated residual error is only 0.01 mE${}_h$, much more accurate than these previous estimates. Further, due to the additional efficiency afforded by the algorithm, we compute the potential energy curves of twelve states: the three lowest levels for each of the irreducible representations ${}^1\hat{I}{\pounds }_g^{+}$, ${}^1\hat{I}{\pounds }_u^{+}$, ${}^1\hat{I}{\pounds }_g^{-}$ and ${}^1\hat{I}{\pounds }_u^{-}$, to an estimated accuracy within 0.1 mE${}_h$ of the exact result in this basis.