Tracking excited states in wave function optimization using density matrices and variational principles

We present a method for finding individual excited states' energy stationary points in complete active space self-consistent field theory that is compatible with standard optimization methods and highly effective at overcoming difficulties due to root flipping and near-degeneracies. Inspired by both the maximum overlap method and recent progress in excited state variational principles, our approach combines these ideas in order to track individual excited states throughout the orbital optimization process. In a series of tests involving root flipping, near-degeneracies, charge transfers, and double excitations, we show that this approach is more effective for state-specific optimization than either the naive selection of roots based on energy ordering or a more direct generalization of the maximum overlap method. Furthermore, we provide evidence that this state-specific approach improves the performance of complete active space perturbation theory. With a simple implementation, a low cost, and compatibility with large active space methods, the approach is designed to be useful in a wide range of excited state investigations.Comment: 13 pages, submitted to JCT

Ab initio calculations to support accurate modelling of the rovibronic spectroscopy calculations of vanadium monoxide (VO)

Accurate knowledge of the rovibronic near-infrared and visible spectra of vanadium monoxide (VO) is very important for studies of cool stellar and hot planetary atmospheres. Here, the required ab initio dipole moment and spin-orbit coupling curves for VO are produced. This data forms the basis of a new VO line list considering 13 different electronic states and containing over 277 million transitions. Open shell transition, metal diatomics are challenging species to model through ab initio quantum mechanics due to the large number of low-lying electronic states, significant spin-orbit coupling and strong static and dynamic electron correlation. Multi-reference configuration interaction methodologies using orbitals from a complete active space self-consistent-field (CASSCF) calculation are the standard technique for these systems. We use different state-specific or minimal-state CASSCF orbitals for each electronic state to maximise the calculation accuracy. The off-diagonal dipole moment controls the intensity of electronic transitions. We test finite-field off-diagonal dipole moments, but found that (1) the accuracy of the excitation energies were not sufficient to allow accurate dipole moments to be evaluated and (2) computer time requirements for perpendicular transitions were prohibitive. The best off-diagonal dipole moments are calculated using wavefunctions with different CASSCF orbitals.Comment: Molecular Physics, 201

Can Density Matrix Embedding Theory with the Complete Activate Space Self-Consistent Field Solver Describe Single and Double Bond Breaking in Molecular Systems?

Density matrix embedding theory (DMET) [Phys. Rev. Lett.2012, 109, 186404] has been demonstrated as an efficient wave-function-based embedding method to treat extended systems. Despite its success in many quantum lattice models, the extension of DMET to real chemical systems has been tested only on selected cases. Herein, we introduce the use of the complete active space self-consistent field (CASSCF) method as a correlated impurity solver for DMET, leading to a method called CAS-DMET. We test its performance in describing the dissociation of a H-H single bond in a H10 ring model system and an N=N double bond in azomethane (CH3-N=N-CH3) and pentyldiazene (CH3(CH2)4-N=NH). We find that the performance of CAS-DMET is comparable to CASSCF with different active space choices when single-embedding DMET corresponding to only one embedding problem for the system is used. When multiple embedding problems are used for the system, the CAS-DMET is in a good agreement with CASSCF for the geometries around the equilibrium, but not in equal agreement at bond dissociation.Comment: 28 pages, 9 figures, TOC graphi