Analytical Gradient Theory for Spin-Free State-Averaged Second-Order Driven Similarity Renormalization Group Perturbation Theory (SA-DSRG-MRPT2) and Its Applications for Conical Intersection Optimizations (2111.07253v2)

Abstract: The second-order multireference driven similarity renormalization group perturbation theory (DSRG-MRPT2) theory provides an efficient means of correcting the dynamical correlation with the multiconfiguration reference function. The state-averaged DSRG-MRPT2 (SA-DSRG-MRPT2) method is the simplest means of treating the excited states with DSRG-MRPT2. In this method, the Hamiltonian dressed with dynamical correlation is diagonalized in the CASCI state subspace (SA-DSRG-MRPT2c) or the configuration subspace (SA-DSRG-MRPT2). This work develops the analytical gradient theory for spin-free SA-DSRG-MRPT2(c) with the density-fitting (DF) approximation. We check the accuracy of the analytical gradients against the numerical gradients. We present applications for optimizing minimum energy conical intersections (MECI) of ethylene and retinal model chromophores (PSB3 and RPSB6). We investigate the dependence of the optimized geometries and energies on the flow parameter and reference relaxations. The smoothness of the SA-DSRG-MRPT2(c) potential energy surfaces near the reference (CASSCF) MECI is comparable to the XMCQDPT2 one. These results render the SA-DSRG-MRPT2(c) theory a promising approach for studies of conical intersections.