Optical lineshapes for orbital singlet to doublet transitions in a dynamical Jahn-Teller system: The NiV − center in diamond

We apply density functional theory to investigate interactions between electronic and vibrational states in crystal defects with multimode dynamical Jahn-Teller (JT) systems. Our focus is on transitions between orbital singlet and degenerate orbital doublet characterized by $E\ensuremath{\bigotimes}(e\ensuremath{\bigoplus}e\ensuremath{\bigoplus}\ensuremath{\cdots})$ JT coupling, which frequently occurs in crystal defects that are investigated for applications in quantum information science. We utilize a recently developed methodology to model the photoluminescence (PL) spectrum of the negatively charged split nickel-vacancy center $({\mathrm{NiV}}^{\ensuremath{-}})$ in diamond, where JT-active modes significantly influence electron-phonon interactions. Our results validate the effectiveness of the methodology in accurately reproducing the observed 1.4 eV PL lineshape. The strong agreement between our theoretical predictions and experimental observations reinforces the identification of the 1.4 eV PL center with the ${\mathrm{NiV}}^{\ensuremath{-}}$ complex. This study highlights the critical role of JT-active modes in affecting optical lineshapes and demonstrates the power of advanced techniques for modeling optical properties in complex systems with multiple JT-active frequencies.