TY - JOUR

T1 - Ground and excited state charge transfer at aqueous nanodiamonds

AU - Kirschbaum, Thorren

AU - Wang, Xiangfei

AU - Bande, Annika

N1 - Funding Information: Thorren Kirschbaum acknowledges support from the HelmholtzEinstein International Berlin Research School in Data Science (HEI-BRiDS). Xiangfei Wang acknowledges funding from the China Scholar-ship Council. Computing resources were kindly provided by the FreieUniversität Berlin hpc cluster Curta.74Open Access funding enabledand organized by Projekt DEAL

PY - 2024/3/15

Y1 - 2024/3/15

N2 - Nanodiamonds (NDs) are unique carbonaceous materials with exceptionally high stability, hardness, and notable electronic properties. Their applications in photocatalysis, biomedicine, and energy materials are usually carried out in aqueous environments, where they interact with aqueous adsorbates. Especially, electron density may rearrange from the diamond material toward oxidative adsorbates such as oxygen, which is known as charge transfer doping. In this article, we quantify the charge transfer doping for NDs with inhomogeneous surface coverings (hydroxyl, fluorine, and amorphous carbon), as well as NDs doped with heteroatoms (B, Si, N) using hybrid density functional theory (DFT) calculations. The transfer doping magnitude is largely determined by the NDs' highest occupied molecular orbital energies, which can in turn be modified by the surface covering and doping. However, local modifications of the ND structures do not have any local effects on the magnitude of the charge transfer. We furthermore analyze the impact of aqueous adsorbates on the excited states of an aqueous ND in the context of photocatalysis via time-dependent DFT. Here, we find that the excited electrons are biased to move in the direction of the respective oxidative adsorbate. Surprisingly, we find that also unreactive species such as nitrous oxide may attract the excited electrons, which is probably due to the positive partial charge that is induced by the local N (Formula presented.) O solvation geometry.

AB - Nanodiamonds (NDs) are unique carbonaceous materials with exceptionally high stability, hardness, and notable electronic properties. Their applications in photocatalysis, biomedicine, and energy materials are usually carried out in aqueous environments, where they interact with aqueous adsorbates. Especially, electron density may rearrange from the diamond material toward oxidative adsorbates such as oxygen, which is known as charge transfer doping. In this article, we quantify the charge transfer doping for NDs with inhomogeneous surface coverings (hydroxyl, fluorine, and amorphous carbon), as well as NDs doped with heteroatoms (B, Si, N) using hybrid density functional theory (DFT) calculations. The transfer doping magnitude is largely determined by the NDs' highest occupied molecular orbital energies, which can in turn be modified by the surface covering and doping. However, local modifications of the ND structures do not have any local effects on the magnitude of the charge transfer. We furthermore analyze the impact of aqueous adsorbates on the excited states of an aqueous ND in the context of photocatalysis via time-dependent DFT. Here, we find that the excited electrons are biased to move in the direction of the respective oxidative adsorbate. Surprisingly, we find that also unreactive species such as nitrous oxide may attract the excited electrons, which is probably due to the positive partial charge that is induced by the local N (Formula presented.) O solvation geometry.

KW - DFT

KW - excited states

KW - molecular modeling

KW - nanodiamonds

KW - transfer doping

UR - http://www.scopus.com/inward/record.url?scp=85179947725&partnerID=8YFLogxK

U2 - 10.1002/jcc.27279

DO - 10.1002/jcc.27279

M3 - Article

AN - SCOPUS:85179947725

VL - 45

SP - 710

EP - 718

JO - Journal of computational chemistry

JF - Journal of computational chemistry

SN - 0192-8651

IS - 11

ER -