Calculation of two-dimensional potential energy surfaces of CO on a rutile(110) surface: ground and excited states

Phys. Chem. Chem. Phys.

2014

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Due to its high photocatalytic activity, TiO2 is of eminent interest for a manifold of applications ranging from surface catalysis up to solar energy conversion. However, the fundamental mechanisms of the underlying surface photochemistry are by no means understood. Focussing on this drawback, laser-induced photodesorption of CO on an ideal rutile TiO2(110) surface is studied using first principles in terms of a model system. This paper presents both quantum chemical as well as quantum dynamical results, taking into account the desorption coordinate Z, the polar angle θ, and the azimuth angle ϕ of the adsorbate. Detailed insight into the fundamental mechanisms of the photodesorption process in this model system is obtained, and a new desorption scenario is elucidated.

Section: Methodssupporting

confidence: 82%

Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Photoinduced desorption of CO from rutile TiO₂: elucidation of a new desorption mechanism using first principles

Spieker

Phys. Chem. Chem. Phys.

2014

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“…It has been demonstrated in previous studies [6][7][8][9] that this embedded cluster is large enough to deal with photoreactions on titanium dioxide. Details on the basis set and the embedding scheme can be found elsewhere.…”

Section: Methodsmentioning

confidence: 99%

Photodesorption of water from rutile(110): ab initio calculation of five-dimensional potential energy surfaces of ground and excited electronic states and wave packet studies

Mitschker

Phys. Chem. Chem. Phys.

2015

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In this paper, we report on our results concerning the interaction of water with titanium dioxide in its rutile modification. The (110) surface is modelled by an embedded Ti9O18Mg7(14+) cluster. We present up to five-dimensional potential energy surfaces for the water molecule on this surface and include the dissociation of one hydrogen atom. The electronic ground state as well as one electronically excited state is included. To deal with the multi-configurational character of the wave function, we use the complete active space self-consistent field (CASSCF) approach. The resulting potential energy surfaces are fitted by means of an artificial neural network. As a first example of quantum dynamical studies based on our potential surfaces, we present results on the photodesorption of water from rutile(110).

Analyzing the local basis set superposition error for CO adsorbed on rutile(110)

Dononelli

Int J of Quantum Chemistry

2020

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One of the main tasks of quantum chemistry is to predict total energies for a given system within an almost nonapproximate method for a complete basis set. Unfortunately, although computational power is growing, approximate methods such as MP2 or CCSD(T) still have to be used as higher-level methods such as full CI are computationally too demanding. Nevertheless, when using these approximations, at least an almost-complete basis set should be used in order to avoid errors from basis set superposition or incompleteness. The aim of this work is to introduce a new method to analyze the local basis set superposition error (LBSSE) using local counterpoise corrections in order to converge a basis set for a given compound. Using this approach, we are able to define a basis set composition for a CO molecule adsorbed on rutile(110), which can be regarded as complete. In the presented work, CO adsorbed on rutile(110) and CO 2 adsorbed on a model Ti 3 O 9 cluster will be used as case examples. Therefore, in addition to a new LBSSE analysis method, adsorption energies of CO on rutile(110) at the MP2 and CCSD levels of theory are presented.