Metal–insulator transition in a layer adsorbed on a metal electrode

Mishra, Amrit Kumar; Kishore, R.; Schmickler, Wolfgang

doi:10.1016/j.jelechem.2004.05.030

Cited by 1 publication

(2 citation statements)

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“…This motivates us to model electron transfer reaction through metallic adlayer, with adsorbate coverage varying between zero (lone adsorbate) and one. An important distinction between a metallic and non-metallic adlayer arises due to the electronic coupling between the adjacent adsorbed atoms in the former case, which leads to a two-dimensional bond formation in the adlayer at high coverages [18,17]. Thus in the monolayer regime, the conventional picture of the electron transfer through a single, localized bridge electronic state, does not hold true.…”

Section: Introductionmentioning

confidence: 99%

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Electron transfer reaction through an adsorbed layer

Cruz

Mishra

2011

Journal of Electroanalytical Chemistry

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a b s t r a c tElectron transfer from a redox to an electrode through an adsorbed intermediate is considered in this paper. The formalism is developed to cover all regimes of coverage factor, from lone adsorbate to monolayer regime. The randomness in the distribution of adsorbates is handled using coherent potential approximation. Current-overpotential profile for all coverage regime is provided. Explicit analysis of the low and high coverage regime is done by supplementing with the density of states (dos) profile for adsorbate in both weak and strongly coupled sectors. The prominence of bonding and anti-bonding states in the strongly coupled adsorbates at low coverage gives rise to saddle point behaviour in the currentoverpotential profile. The variation of current with overpotential at low coverage is consistent with the Marcus inverted region prediction and the traditional direct electron transfer behaviour at high coverage is recovered through the present analysis.

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Section: Introductionmentioning

confidence: 99%

“…But in the monolayer regime, one obtains extended electron states in the adlayer. These states now form a two-dimensional band [11,12]. The localized adsorbate states interact strongly with the solvent polarization modes.…”

Section: Introductionmentioning

confidence: 99%