Ab-Initio Investigation of Finite Size Effects in Rutile Titania Nanoparticles with Semilocal and Nonlocal Density Functionals

Sahoo, Sushree Jagriti; Jing, Xin; Suryanarayana, Phanish; Medford, Andrew J.

doi:10.1021/acs.jpcc.1c08915

Title: Ab-Initio Investigation of Finite Size Effects in Rutile Titania Nanoparticles with Semilocal and Nonlocal Density Functionals

Journal Article · 25 January 2022 · Journal of Physical Chemistry. C

DOI: https://doi.org/10.1021/acs.jpcc.1c08915 · OSTI ID:1988234

Sahoo, Sushree Jagriti ^[1]; Jing, Xin ^[2]; Suryanarayana, Phanish ^[2];

^[2]

Georgia Institute of Technology, Atlanta, GA (United States); Georgia Institute of Technology
Georgia Institute of Technology, Atlanta, GA (United States)

In this work, we employ hybrid and generalized gradient approximation (GGA) level density functional theory (DFT) calculations to investigate the convergence of surface properties and electronic gap of rutile titania nanoparticles with particle size. The surface energies and electronic gaps are calculated for cuboidal particles with minimum dimension ranging from 3.7 Angstrom (24 atoms) to 10.3 Angstrom (384 atoms) using a highly-parallel real-space DFT code to enable hybrid level DFT calculations of larger nanoparticles than are typically practical. We deconvolute the geometric and electronic finite size effects in surface energy, and evaluate the influence of defects on electronic gap and density of states (DOS). The electronic finite size effects in surface energy vanish when the minimum length scale of the nanoparticles becomes greater than 10 Angstrom. We show that this length scale is consistent with a computationally efficient numerical analysis of the characteristic length scale of electronic interactions. The surface energy of nanoparticles having minimum dimension beyond this characteristic length can be approximated using slab calculations that account for the geometric defects. In contrast, the finite size effects on the electronic gap and DOS is highly dependent on the shape and size of these particles. Furthermore, the DOS for cuboidal particles and more realistic particles constructed using the Wulff algorithm reveal that defect states within the electronic gap play a key role in determining the eigen value distribution of nanoparticles and the electronic gap does not converge to the bulk limit for the particle sizes investigated.

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Research Organization:: Georgia Institute of Technology, Atlanta, GA (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019410

OSTI ID:: 1988234

Journal Information:: Journal of Physical Chemistry. C, Journal Name: Journal of Physical Chemistry. C Journal Issue: 4 Vol. 126; ISSN 1932-7447

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Title: Ab-Initio Investigation of Finite Size Effects in Rutile Titania Nanoparticles with Semilocal and Nonlocal Density Functionals

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