A Multireference Picture of Electronic Excited States in Vanadyl and Copper Tetraphenyl Porphyrin Molecular Qubits.

ABSTRACT: The nature of electronic excited states has a deep impact on the dynamics of molecular spins but remains poorly understood and characterized. Here we carry out a thorough multiconfigurational investigation for two prototypical molecular qubits based on vanadyl and copper tetraphenyl porphyrins. State-average CASSCF and NEVPT2 calculations have been employed with four different active spaces of growing complexity to account for the d-d, second d-shell, ligand-to-metal charge transfer states, and π-π* excited states, revealing an in-depth picture of low-lying excited states in agreement with experimental observations. The largest active spaces attempted (13,14) for the vanadyl and (17,12) for the copper compounds reveal that the lowest-lying excited states originate from π-π* quartet excitat

SUBMITTER: Sarkar A 

PROVIDER: S-EPMC12337143 | biostudies-literature | 2025 Aug

REPOSITORIES: biostudies-literature