Fig. 5: Calculated reaction profile and transmission coefficient. | Nature Communications

Fig. 5: Calculated reaction profile and transmission coefficient.

From: Voltage-driven control of single-molecule keto-enol equilibrium in a two-terminal junction system

Fig. 5

a Reaction profile (in kcal mol−1) associated with the tautomerization reaction on the uncharged PES (black), and on the PES of the radical, cationic species obtained after charge injection (red), calculated at B3LYP/def2-TZVP level of theory. An electric field corresponding to the field exerted by the approximate threshold voltage in the junction has been included in different directions (shown in orange and blue arrows). The PES in the different directions of the electric field is linked by orange (−0.05 V Å−1) and blue (+0.05 V Å−1) dashed lines. b Schematic representation of the Marcus parabolas, describing the energy as a function of the environmental dielectric coordinate x, for the uncharged MB species (parabola in blue centered around xMB) and the charged MB (MB+) species (parabola in red centered around xMB+). As the molecule-metal potential difference changes, the MB+-parabola shifts vertically. c Calculated transmission coefficients (dimensionless) of the low- and high-conductance states. The blue and red curves represent low- and high-conductance states.

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