Molecular electron spin qubits with optical manipulation schemes are some of the most promising candidates for modern quantum technologies. Key values that determine a compound’s viability for optical-spin initialization and readout include its singlet-triplet gap and zero-field splitting (ZFS) parameters. Generally, these values are very small in magnitude and are thus difficult to reproduce with theoretical methods. Here we study a previously identified optically addressable molecular qubit, (C6F5)3trenVCNtBu (tren = tris(2-aminoethyl)amine), using the complete active space self-consistent field (CASSCF) and post-CASSCF methods (CASPT2, MC-PDFT, and HMC-PDFT). Of those methods, we successfully reproduce the singlet-triplet gap and ZFS parameters with reasonable accuracy using 0.5 HMC-PDFT and CASPT2. Four additional V3+ complexes with differing ligands were also investigated. We found that the ligands have minimal effect on the spin properties of the molecule and propose them to be optically addressable qubit candidates. These potential qubits are further analyzed in terms of ab initio ligand field theory (AILFT) to understand the influence of the ligands on the singlet-triplet gap and ZFS parameters.
Supporting Information for "Multireference Study of Optically Addressable Vanadium-based Molecular Qubit Candidates"
MC-PDFT functional dependence of ∆E and ZFS parameters; active space dependence of ∆E and ZFS Parameters; active space orbitals; HMC-PDFT and CASPT2 relative energies; CASSCF, MC-PDFT, HMC-PDFT and CASPT2 absolute energies; optimized coordinates; sample OpenMolcas input file.