N  1s x-ray absorption study of the bonding interaction of bi-isonicotinic acid adsorbed on rutile TiO2(110)

Abstract

Articles you may be interested inA single centre water splitting dye complex adsorbed on rutile TiO2(110): Photoemission, x-ray absorption, and optical spectroscopy J. Chem. Phys. 135, 114703 (2011); 10.1063/1.3637497 X-ray absorption and photoemission spectroscopy of zinc protoporphyrin adsorbed on rutile TiO 2 ( 110 ) prepared by in situ electrospray deposition J. Chem. Phys. 132, 084703 (2010); 10.1063/1.3336747 Photoemission, resonant photoemission, and x-ray absorption of a Ru(II) complex adsorbed on rutile Ti O 2 ( 110 ) prepared by in situ electrospray deposition

Molecular damage in bi-isonicotinic acid adsorbed on rutile TiO2(110)

“…4 NEXAFS spectra for an undamaged and a damaged monolayer of biisonicotinic acid. For the undamaged preparation, the NEXAFS spectrum compares very well (within experimental error) to previous studies [11,12]. The LUMO occurs at an energy of 398.6 eV, the LUMO + 1 at 400.3 eV and the LUMO + 2 at 402.4 eV photon energy.…”

“…A similar adsorption geometry has also been found on the anatase TiO 2 surface [15,21]. Bi-isonicotinic anchors to the surface through the deprotonated carboxylic groups, and as such all four oxygen atoms in the molecule are equivalent [9][10][11]. Attachment of the molecule via the deprotonated carboxylic group is a common feature of aromatic carboxylic acid molecules adsorbed on TiO 2 [15][16][17][22][23][24].…”

“…1. The optimized 2M-bidentate bonding geometry of bi-isonicotinic acid adsorbed on rutile TiO 2 (1 1 0) in agreement with previous studies [9][10][11][12]. The geometry was optimized using CASTEP code [13] at the DFT-GGA level with a plane wave basis set cut-off of 300 eV and the Perdew Burke Ernzerhof functional.…”

“…Upon adsorption to rutile TiO 2 (1 1 0), bi-isonicotinic acid is expected to adopt a 2M-bidentate bonding geometry [9][10][11]17], as Fig. 1.…”

“…Any loss of integrity in the unoccupied molecular orbitals during the experiment through beam damage could completely undermine the RPES observations. Our previous studies of the adsorption and charge transfer dynamics of bi-isonicotinic acid adsorbed on a variety of surfaces [6][7][8][10][11][12][15][16][17] successfully eliminated molecular damage through continuously scanning the incident beam across the surface to maintain the exposure below a well characterized limit. This technique is also used in the present study, in which we focus our attention on the nature of the damage to the adsorbed bi-isonicotinic acid molecule.…”