Analytical gradients and nonadiabatic couplings for the state-average density matrix renormalization group self-consistent field method

We present analytical gradients and nonadiabatic couplings for a state-average density matrix renormalization group self-consistent-field (SA-DMRG-SCF) wavefunction. Our formalism follows closely the state-average complete active space self-consistent-field (SA-CASSCF) \emph{ansatz}, which employs a Lagrangian, and the corresponding Lagrange multipliers are obtained from a solution of the coupled-perturbed CASSCF (CP-CASSCF) equations. We introduce a definition of the MPS Lagrange multipliers based on the mixed-canonical form of the MPS, such that the sweep procedure is avoided in the solution of the CP-CASSCF equations. We employ our implementation for the optimization of a conical intersection in 1,2-dioxetanone, where we are able to fully reproduce the SA-CASSCF result up to arbitrary accuracy.