Water on ceria{111} : Comparison between 23 experimental vibrational studies in the literature and new modeling

• Theoretical and experimental vibrational signatures of H2O and OH- (dissociated water) adsorbed on stoichiometric ceria{111} surfaces are compared. The experimental ones were collected from low-coverage experiments in the literature, and the theoretical anharmonic frequencies were generated using density functional theory calculations employing the optPBE-vdW functional for coverages from 0.5 to a few monolayers. It is found that (i) the experiments and our calculations overall agree well, lending credibility to both; (ii) the calculations manage to resolve the large class of H-bonded motifs into frequency classes that can guide experimental assignments; (iii) it is possible to find a geometrical H-bond definition that also captures the OH vibrational frequency downshifts well: R(H center dot center dot center dot O) <= 2.5 angstrom and the O-H center dot center dot center dot O angle theta >= 100 degrees; and (iv) the frequency vs electric field relations for water and hydroxides (i.e., dissociated water) follow different and well-separated curves.

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NATURVETENSKAP  -- Kemi -- Teoretisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Theoretical Chemistry (hsv//eng)

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