TY - JOUR

T1 - Tuning and understanding optical behavior in antizeolite borates: The critical role of lattice dynamics

AU - Inerbaev, Talgat M

AU - Sagatov, Nursultan E

AU - Bekker, Tatyana B

PY - 2025

Y1 - 2025

N2 - We present a comprehensive first-principles study of the structural, electronic, and optical properties of [PO 4 ] 3– -substituted antizeolite borate materials based on the antizeolite borate crystal lattice. The substituted structures are found to be both mechanically and dynamically stable, as confirmed by compliance with Born stability criteria and ab initio molecular dynamics simulations up to 1200 K, with no bond rupture or atomic diffusion observed. The static DFT calculations show that [PO 4 ] 3– substitution slightly affects the optical absorption. However, finite-temperature effects revealed by molecular dynamics at 300 K dramatically alter the optical response: thermal lattice motion reduces symmetry, enhances oscillator strengths, and induces a red shift in absorption for [PO 4 ] 3– modified structures. In contrast, the oscillator strength in pristine antizeolite borate is strongly suppressed at finite temperature, explaining the accuracy of static calculations. Our results demonstrate that while [PO 4 ] 3– substitution has minimal impact on the static electronic structure, lattice vibrations at room temperature play a decisive role in shaping the optical properties, highlighting the importance of dynamic effects in the design and interpretation of spectroscopic behavior in complex borate materials.

AB - We present a comprehensive first-principles study of the structural, electronic, and optical properties of [PO 4 ] 3– -substituted antizeolite borate materials based on the antizeolite borate crystal lattice. The substituted structures are found to be both mechanically and dynamically stable, as confirmed by compliance with Born stability criteria and ab initio molecular dynamics simulations up to 1200 K, with no bond rupture or atomic diffusion observed. The static DFT calculations show that [PO 4 ] 3– substitution slightly affects the optical absorption. However, finite-temperature effects revealed by molecular dynamics at 300 K dramatically alter the optical response: thermal lattice motion reduces symmetry, enhances oscillator strengths, and induces a red shift in absorption for [PO 4 ] 3– modified structures. In contrast, the oscillator strength in pristine antizeolite borate is strongly suppressed at finite temperature, explaining the accuracy of static calculations. Our results demonstrate that while [PO 4 ] 3– substitution has minimal impact on the static electronic structure, lattice vibrations at room temperature play a decisive role in shaping the optical properties, highlighting the importance of dynamic effects in the design and interpretation of spectroscopic behavior in complex borate materials.

KW - antizeolite borates

KW - LBBF

KW - phosphate doping

KW - optical properties

KW - molecular dynamics

UR - https://www.scopus.com/pages/publications/105033430264

UR - https://www.mendeley.com/catalogue/b245943c-64a5-3be5-9c7e-4437ad35ec35/

U2 - 10.1088/1402-4896/ae2dd6

DO - 10.1088/1402-4896/ae2dd6

M3 - Article

VL - 100

JO - Physica Scripta

JF - Physica Scripta

SN - 0031-8949

IS - 12

M1 - 125957

ER -