Frozen natural orbitals for the state-averaged driven similarity renormalization group

Abstract

We present a reduced-cost implementation of the state-averaged driven similarity renormalization group (SA-DSRG) based on the frozen natural orbital (FNO) approach. The natural orbitals (NOs) are obtained by diagonalizing the one-body reduced density matrix from SA-DSRG second-order perturbation theory (SA-DSRG-PT2). Subsequently, the virtual NOs with occupation numbers (ONs) smaller than a user-defined threshold are excluded from the high-level electron correlation treatment beyond SA-DSRG-PT2. An additive second-order correction is applied to the SA-DSRG Hamiltonian to reintroduce the correlation effect from the discarded orbitals. The FNO SA-DSRG method is benchmarked on 35 small organic molecules in the QUEST database. When keeping 98-99% of the cumulative ONs, the mean absolute error in the vertical transition energies due to FNO is less than 0.01 eV. Using the same FNO threshold, we observe a speedup of 9 times the conventional SA-DSRG implementation for nickel carbonyl with a quadruple-$\zeta$ basis set. The FNO approach enables third-order SA-DSRG perturbation theory computations on chloroiron corrole [FeCl(C$_{19}$H$_{11}$N$_4$)] with more than 1000 basis functions.