Moreover, our calculations show that the polarizability of these structures can vary by a factor of up to six, depending on the specific values of the HOMO-LUMO gap. To demonstrate this flexibility in α, Fig. also shows the four molecules corresponding to the four quartiles having a HOMO-LUMO gap of 4 ± 0.1 eV, selected to correspond to the maximum density of data. For this specific HOMO-LUMO gap, polarizability changes between 149.9 a.u. and 451.1 a.u. Tak- ing the tenfold enhancement between the polarizability of the free molecule and the absorbed α ′ into account and using approximate values of µ = 4 D and d = 1.5 nm with a full surface coverage, this would mean that changes in work function could range from 0.9 eV to 1.5 eV. These variations are larger than usually achievable by modifications of a semiconductor structure or controlling the surface coverage . Therefore, our analysis shows that work function can be, for practical purposes, freely tailored, even with a very specific design requirement on HOMO-LUMO gap. This flexibility is also relevant in the task of designing wavelength-selective detectors, which would imply hard constraint on HOMO-LUMO gap. If ∆E HL and α could not be controlled independently, then optical design restrictions would directly influence the electrochemical behavior. The decoupling of ∆E HL and α means that the wavelength of detection and the work function can be controlled independently. Fine-tuning the work functions to achieve matching on the metalorganic interface at the electrode is crucial for efficiency. Thus, with the existent "freedom of design" in (∆E HL , α)-space, we have demonstrated that an efficient detection can be theoretically achieved for any detection wavelength. Alternatively, since the work function can be tailored to match any detection wavelength, it is also possible to design detectors for different detection ranges having equivalent electrochemical proper-ties such as sensitivity, dark current, adhesion behavior as well as any other properties determined by the work function.