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

Abstract

We investigated 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 into 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.

First-Principles Investigation of Phosphorus-Doped Graphitic Carbon Nitride as Anchoring Material for the Lithium-Sulfur Battery

“…Introducing P elements in place of C/N is beneficial for generating lone pair electrons, thereby increasing the carrier concentration and potentially reducing the mobility gap [ 47 ]. This shift could facilitate movement towards the conjugated ring, affecting the electronic properties through quantum vibrational effects [ 48 , 49 ], which influences the electrical conductivity. These outcomes are consistent with prior research [ 50 , 51 ].…”

First-Principles Calculations of P-B Co-Doped Cluster N-Type Diamond

“…The band structure of P-doped diamond exhibits characteristics akin to a typical n-type semiconductor, where the impurity level and Fermi level align in the vicinity of the conduction band. And in Kundu's study, the negatively charged nitrogen vacancy center in diamond has an impact on the band due to electron-phonon coupling [21]. Considering that the doping structure of P-V is similar to that of N-V, there may also be an electron-phonon coupling effect in P-V-doped diamond, causing quantum vibration and leading to deviation in the band structure.…”

“…In edition Yang et al, proposed the utilization of density matrix perturbation theory to evaluate electron-phonon interactions using hybrid functionals for assessing transport properties in light atom-based amorphous semiconductors [20]. In 2024, Kundu et al, explored the impact of quantum vibronic coupling on the electronic characteristics of solid-state spin defects, emphasizing the necessity of integrating quantum vibronic effects into first-principles computations [21]. This paper undertakes a study on diamond P doping and P-B co-doping without the constraints of first-principles density functional theory.…”

Electron–vibrational renormalization in fullerenes through ab initio and machine learning methods

“…While the former investigates 2D materials using the special displacement method, our work focuses on fullerenes and utilizes the frozen phonon approach (with corrections for the effects due to crossings and anticrossings 26 ). Recent research hints that the special displacement method might yield not fully accurate predictions for band gap renormalizations in some cases, like C 214 N and C 510 N 62 using moderately sized supercells.…”