Molecular modeling of the adsorption and initial photocatalytic oxidation step for para-nitrophenol on nano-sized TiO2 surface

► Para-nitrophenol adsorbs molecularly to anatase TiO2 (100) surface. ► The substituted groups play significant role in adsorption process. ► The adsorption energy is varied due to the geometry of the adsorbed molecule. ► The bridged perpendicular adsorption conformer prevails. ► Reactivity of the ring positions toward
- OH oxidation is varied upon adsorption.