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First-principles cumulant approach to the vibronic structure of spin defects

Jinsoo Park1,2,3,*, Yu Jin1,4, Arpan Kundu1, Jorge O. Sofo5,†, and Giulia Galli1,6,7,‡

  • *Contact author: js.park@postech.ac.kr
  • †Contact author: sofo@psu.edu
  • ‡Contact author: gagalli@uchicago.edu
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Phys. Rev. B 114, L291402 – Published 5 November, 2026

DOI: https://doi.org/10.1103/7xrx-2fd2

Abstract

Color centers in wide-band-gap semiconductors are leading platforms for solid-state quantum technologies, yet a quantitative description of their vibronic structure has remained elusive due to the complexity of multiphonon processes in localized defect states. Here we present a first-principles Green's function framework based on the retarded cumulant ansatz (RCA) to describe electron-phonon interactions in spin defects; our approach goes beyond the adiabatic and lowest-order perturbation theory approximations underlying widely used approaches. Applied to the negatively charged nitrogen-vacancy (NV−) center in diamond within the harmonic approximation, our method reveals that multiphonon satellites persist over a 400 meV energy window even at zero temperature, driven by quantum zero-point fluctuations. We demonstrate that accurate spectral functions require mode-, momentum-, spin-, and orbital-resolved electron-phonon matrix elements sampled across the full Brillouin zone, to account for hybridized and propagating phonon channels. We find that the vibronic structure of the NV− center exhibits strong spin and orbital anisotropy, with different orbitals coupling to qualitatively distinct parts of the phonon spectrum, and spin-selective coupling affecting both sideband positions and intensities.

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Phys. Rev. B 114, L291402– Published 5 November, 2026
  • Received 10 June 2026
  • Revised 17 September 2026
  • Accepted 24 September 2026
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