Analytical First-Order Derivatives of Second-Order Extended Multiconfiguration Quasi-Degenerate Perturbation Theory (XMCQDPT2): Implementation and Application

Abstract

Analytical gradient theory for the second-order extended multiconfiguration quasi-degenerate perturbation theory (XMCQDPT2), which can be regarded as the multistate version of the multireference second-order Møller-Plesset perturbation theory (MRMP2), is formulated and implemented. The theory is similar to the previous analytical gradient theory for MCQDPT2, but we take into account the intruder state avoidance (ISA) technique and the "extension" of the MCQDPT2 theory by Granovsky. Although the (X)MCQDPT2 theory is not invariant with respect to rotations among the active orbitals, the resulting analytical gradients are accurate. We demonstrate the utility of the current algorithm in optimizing the minimum energy conical intersections (MECIs) of ethylene, butadiene, benzene, the retinal model chromophore PSB3, and the green fluorescent protein model chromophore pHBI. The XMCQDPT2 MECIs are very similar to the XMS-CASPT2 MECIs in terms of molecular conformation and the computed energies. We also discuss possible improvements of the current algorithm.