TY - JOUR

T1 - Perturbation of the UV transitions of formaldehyde by TiO2 photocatalysts and Aun nanoclusters

AU - Høyer, Nicolai Machholdt

AU - Johnson, Matthew S.

AU - Mikkelsen, Kurt V.

PY - 2022

Y1 - 2022

N2 - In the gas phase, formaldehyde has an electric-dipole forbidden transition that becomes allowed by vibronic coupling. In this paper we explore whether perturbation by surfaces could also enhance light absorption by CH2O. We investigate the electronic transitions of formaldehyde in the gas phase and interacting with rutile (110) TiO2, Aun nanoclusters, and Aun on (110)-TiO2. These surfaces are chosen as being representative of metals and metal-oxide minerals, and also because of specific interest in photocatalysts and noble metal nanocluster catalysts. The oscillator strength of the forbidden n → π* transition of formaldehyde in vacuum is investigated by modelling vibrational coupling to the electronic transition with equation-of-motion coupled cluster theory. The excitation energies and oscillator strengths of formaldehyde are calculated for different orientations and distances to the surfaces using the coupled cluster singles and doubles linear response method within the Quantum Mechanical and Molecular Mechanical (QM/MM) model using the aug-cc-pVTZ basis set and compared with the values calculated in vacuo. The electronic transitions of formaldehyde vary very little when placed near a pure TiO2–surface with only minor variations depending on the orientation of formaldehyde. Introducing a gold nanoparticle (by itself or supported by TiO2) induces dramatic changes in the absorption properties. This is due to vibronic interactions and the effect of the broken symmetry on the n → π* transition. We see a large redshift in the transition of 90 nm and oscillator strengths larger than 1.0 × 10−4 for CH2O interacting with Aun.

AB - In the gas phase, formaldehyde has an electric-dipole forbidden transition that becomes allowed by vibronic coupling. In this paper we explore whether perturbation by surfaces could also enhance light absorption by CH2O. We investigate the electronic transitions of formaldehyde in the gas phase and interacting with rutile (110) TiO2, Aun nanoclusters, and Aun on (110)-TiO2. These surfaces are chosen as being representative of metals and metal-oxide minerals, and also because of specific interest in photocatalysts and noble metal nanocluster catalysts. The oscillator strength of the forbidden n → π* transition of formaldehyde in vacuum is investigated by modelling vibrational coupling to the electronic transition with equation-of-motion coupled cluster theory. The excitation energies and oscillator strengths of formaldehyde are calculated for different orientations and distances to the surfaces using the coupled cluster singles and doubles linear response method within the Quantum Mechanical and Molecular Mechanical (QM/MM) model using the aug-cc-pVTZ basis set and compared with the values calculated in vacuo. The electronic transitions of formaldehyde vary very little when placed near a pure TiO2–surface with only minor variations depending on the orientation of formaldehyde. Introducing a gold nanoparticle (by itself or supported by TiO2) induces dramatic changes in the absorption properties. This is due to vibronic interactions and the effect of the broken symmetry on the n → π* transition. We see a large redshift in the transition of 90 nm and oscillator strengths larger than 1.0 × 10−4 for CH2O interacting with Aun.

U2 - 10.1039/D1CP05820G

DO - 10.1039/D1CP05820G

M3 - Journal article

VL - 24

SP - 11395

EP - 11411

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 18

ER -