Quantum Vibronic Effects on the Excitation Energies of the Nitrogen-Vacancy Center in Diamond

Abstract

We investigate the impact of quantum vibronic coupling on the electronic properties of solid-state spin defects using stochastic methods and first principles molecular dynamics with a quantum thermostat. Focusing on the negatively charged nitrogen-vacancy center in diamond as an exemplary case, we found a significant dynamic Jahn-Teller splitting of the doubly degenerate single-particle levels within the diamond's band gap, even at 0 K, with a magnitude exceeding 180 meV. This pronounced splitting leads to substantial renormalizations of these levels and subsequently, of the vertical excitation energies of the doubly degenerate singlet and triplet excited states. Our findings underscore the pressing need to incorporate quantum vibronic effects in first-principles calculations, particularly when comparing computed vertical excitation energies with experimental data. Our study also reveals the efficiency of stochastic thermal line sampling for studying phonon renormalizations of solid-state spin defects.

41 pages and 14 figures in total. To be published in J. Phys. Chem. Lett

References in corpus (11)

• Quantum ESPRESSO toward the exascale
• Self-consistent hybrid functional for condensed systems
• First-principles theory of the luminescence lineshape for the triplet transition in diamond NV centre
• Nuclear quantum effects in solids using a colored-noise thermostat
• Colored-noise thermostats à la carte
• Phonon-Induced Population Dynamics and Intersystem Crossing in Nitrogen-Vacancy Centers
• New infrared emission of the NV centre in diamond: Zeeman and uniaxial stress studies
• State-selective intersystem crossing in nitrogen-vacancy centers
• \emph{Ab initio} calculation of spin-orbit coupling for NV center in diamond exhibiting dynamic Jahn-Teller effect
• Anharmonicity Measure for Materials
• Photoluminescence spectra of point defects in semiconductors: validation of first principles calculations