High harmonic generation (HHG) in the vanadium monoanion (${\mathrm{V}}^{-}$) and its hexacarbonyl complex, $[\mathrm{V}{\left(\mathrm{CO}\right)}_6{]}^{-}$, is investigated using time-dependent density functional theory within the optimized effective potential formalism. By analyzing the field-free electronic structure, field-induced changes in the many-electron potential, and the partitions of the high harmonic spectra, we demonstrate that these anions are valuable for understanding the role of orbital spatial distribution in HHG. Both systems feature degenerate (or near-degenerate) orbitals, with some extending along the field polarization direction. Our analysis reveals that this spatial extensiveness enhances HHG intensity by several orders of magnitude. Additionally, the redistribution of electron density in $[\mathrm{V}{\left(\mathrm{CO}\right)}_6{]}^{-}$ under intense laser fields generates a negative potential near the nuclei, increasing the apparent ionization potential and significantly extending the high harmonic cutoff.

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• Atomic & molecular processes in external fields
• Molecules
• High-order harmonic spectroscopy