Multimode Jahn-Teller effect in bulk systems: A case of the NV0 center in diamond

Abstract

The multimode Jahn-Teller ( JT) effect in a bulk system of a neutral nitrogen-vacancy ( N V 0 ) center in diamond is investigated via first-principles density-functional-theory calculations and the intrinsic distortion path (IDP) method. The adiabatic potential energy surface of the electronic ground state of the N V 0 center is calculated based on the local spin-density approximation. Our calculations confirm the presence of the dynamic Jahn-Teller effect in the ground 2 E state of the N V 0 center. Within the harmonic approximation, the IDP method provides the reactive path of JT distortion from unstable high-symmetry geometry to stable low-symmetry energy minimum geometry, and it describes the active normal modes participating in the distortion. We find that there is more than one vibrational mode contributing to the distortion, and their contributions change along the IDP. Several vibrational modes with large contributions to JT distortion, especially those modes close to 44 meV, are clearly observed as the phonon sideband in photoluminescence spectra in a series of experiments, indicating that the dynamic Jahn-Teller effect plays an important role in the optical transition of the N V 0 center. The multimode Jahn-Teller (JT) effect in a bulk system of a neutral nitrogen-vacancy (NV 0 ) center in diamond is investigated via first-principles density-functional-theory calculations and the intrinsic distortion path (IDP) method. The adiabatic potential energy surface of the electronic ground state of the NV 0 center is calculated based on the local spin-density approximation. Our calculations confirm the presence of the dynamic Jahn-Teller effect in the ground 2 E state of the NV 0 center. Within the harmonic approximation, the IDP method provides the reactive path of JT distortion from unstable high-symmetry geometry to stable low-symmetry energy minimum geometry, and it describes the active normal modes participating in the distortion. We find that there is more than one vibrational mode contributing to the distortion, and their contributions change along the IDP. Several vibrational modes with large contributions to JT distortion, especially those modes close to 44 meV, are clearly observed as the phonon sideband in photoluminescence spectra in a series of experiments, indicating that the dynamic Jahn-Teller effect plays an important role in the optical transition of the NV 0 center. Disciplines Condensed Matter Physics

Orbital and Spin Dynamics of Single Neutrally-Charged Nitrogen-Vacancy Centers in Diamond

“…For the Orbach process we find a characteristic energy scale of ∆ = 12(2) meV (∆ = 13(4) meV) extracted from a fit to the lower (upper) spin-orbit branch. ∆ is associated to the energy splitting to the first vibronic level of the NV 0 ground state, predicted to be a Jahn-Teller system [20,34]. The value found here agrees with the bulk absorption measurements of Davies [20] (13.6(7) meV), and with recent density-functional theory calculations (21.4 meV) [34], suggesting that the measured increase of R recovery is predominantly due to two-phonon Orbach processes.…”

“…∆ is associated to the energy splitting to the first vibronic level of the NV 0 ground state, predicted to be a Jahn-Teller system [20,34]. The value found here agrees with the bulk absorption measurements of Davies [20] (13.6(7) meV), and with recent density-functional theory calculations (21.4 meV) [34], suggesting that the measured increase of R recovery is predominantly due to two-phonon Orbach processes. While a detailed model is beyond the scope of this work, we expect that our findings will aid in the further understanding of the vibronic structure of NV 0 .…”

Relative Populations and IR Spectra of Cu38 Cluster at Finite Temperature Based on DFT and Statistical Thermodynamics Calculations

“…The perfect OH symmetry could be deformed due to the Jahn–Teller effect ( Kabir et al, 2004 ; Guvelioglu et al, 2006 ). This effect must be considered when calculating the total energy ( Zlatar et al, 2010 ; Zhang et al, 2018 ) because the computed optical properties could change due to relative population at finite temperatures ( Opik and Pryce, 1957 ). In one of our recent works, we clarified the origin of Gibbs free energy differences between two similar structures with different symmetry point group due to rotational entropy, specifically the RTln(σ) factor ( Buelna-García et al, 2021 ).…”

Photoluminescence spectra of point defects in semiconductors: validation of first principles calculations

“…Note that PL line shapes computed with small supercells show sharper peaks and a gap of 5-10 meV between the ZPL and the PSB. The peaks located at 30 (23) meV from the ZPL for NV − (hk-VV 0 ) also stem from finite size effects. In our calculations, the contribution of the e type phonons is computed using the HR theory, which was shown to represent an accurate approximation in the recent work by Razinkovas et al [28].…”

“…As for many properties of condensed systems, Density Functional Theory (DFT) has turned out to be a valuable tool to compute PL spectra, which are used to interpret experiments as well as to provide predictions of the fingerprints of specific defects in materials [7][8][9]. For example, first principles spectra based on DFT have been recently reported for nitrides, e.g., GaN [10,11], AlN [12], and hexagonal born nitride (h-BN) [13][14][15][16][17][18], diamond [19][20][21][22][23][24][25][26][27][28][29], silicon carbide (SiC) [30][31][32][33], and monolayers of transition metal dichalcogenides (TMDC) [34]. These studies have been performed with several useful computational approaches; however, a systematic assessment of the theoretical and numerical approximations adopted in PL calculations has not yet been conducted.…”