Benchmarking semiempirical and DFT methods for the interaction of thiophene and diethyl sulfide molecules with a Ti(OH)4(H2O) cluster

Abstract

Semiempirical methods pm6 and pm7 as well as density functional theory functionals exchange LSDA, exchange-correlation PW91 and PBE, hybrid B3LYP1 and PBE0 were compared for energy and geometry of thiophene, diethyl sulfide (DES) molecules and their binding to a frozen Ti(OH)(HO) complex having one coordinatively unsaturated Ti site representing small fragment of TiO anatase (001) surface. PBE0/6-31G(d) with DFT-D3 dispersion correction was the best method for description of thiophene and DES molecules geometries as comparison with experimental data demonstrated. Semiempirical methods pm6 and pm7 resulted in only three of four possible binding configurations of thiophene with the Ti(OH)(HO) complex while pm7 described correctly the enthalpy and all configurations of DES binding with the Ti(OH)(HO) complex. SBKJC pseudopotential and LSDA with and without dispersion correction produced flawed results for many configurations. PBE0 and PBE with and without dispersion correction and PW91 with 6-31G(d) basis set systematically produced dependable results for thiophene and DES binding to the Ti(OH)(HO) complex. PBE0-D3/6-31G(d), B3LYP1-D3/6-31G(d), and PBE-D3/6-31G(d) gave best match of binding energy for thiophene while PBE0/6-31G(d) gave best match of DES binding energy as comparison with CCSD(T) energy demonstrated. On the basis of the superior results obtained with PBE0/6-31G(d), it is the recommended method for modeling of adsorption over TiO surfaces. Such a conclusion is in agreement with recent literature.

Recent Advancements in the Understanding of the Surface Chemistry in TiO2 Photocatalysis

“…Adsorption of organic compounds can modify the band structure of TiO 2 and induce visible-light adsorption. For example, a recent study by Barbierikova et al [52] utilizing a small (TiO 2 ) 8 (H 2 O) cluster showed that adsorption of 4-chlorophenol on TiO 2 P25 resulted in the formation of surface charge transfer complexes.…”

Semiempirical computational study of oxygen vacancies in a decahedral anatase nanoparticle

“…According to the results obtained with PBE0 hybrid functional, the vacancies formation energy in Ti 84 O 167 anatase nanoparticle varies in the range of 1.48‐2.78 eV with facets vacancies of 1.92 and 2.78 eV . The functional PBE0 delivers the most accurate structural information among other functionals such as PW91, PBE, and B3LYP . However, it underestimates the band gap of anatase while GGA functionals PBE, PW91, and PBEx overestimate the band gap.…”

“…[25] The functional PBE0 delivers the most accurate structural information among other functionals such as PW91, PBE, and B3LYP. [38] However, it underestimates the band gap of anatase while GGA functionals PBE, PW91, and PBEx overestimate the band gap. Vacancies formation enthalpy delivered by PM6 are smaller than values produced with GGA functionals and larger than values from PBE0.…”

Computational models of (001) faceted anatase TiO2 nanoparticles

“…The last method was demonstrated to provide an outstanding accuracy for adsorption complexes over TiO 2 . 19 The interatomic distance of Ti─Ti in the (001) facet was calculated to be 3.28-3.35, 3.29-3.46 and 3.40-3.43 Å for these three methods, respectively. The distances between (001) planes measured as Ti─Ti distance were 11.08, 10.75 … 10.78 and 9.75 Å, respectively.…”