Molecular electronics, electrically active

After a brief discussion of fundamentals of charge transport mechanisms, this chapter summarizes and discusses the most significant results obtained by using different junctions and in particular LAJs. In order to facilitate a systematic discussion, we make a functional distinction between non-active and active junctions we will refer to active junctions as those aimed at changing the electrical response by means of an external stimulus acting in situ to modify the molecular electronic structure non-active junctions are those used to measure and compare the electrical properties inherent to the different electronic structure of incorporated molecules, without any modification induced by an external signal. 

Note that through-molecule electronic interferences do not necessarily require a loop-like spatial topology of the molecule to be active. Molecular electronic states of different symmetry relative to the contacting nano-pads can do the job [112], Through-molecule interferences can be controlled by changing the molecular conformation [113, 114], by applying a lateral electric field to the ABA... 

Molecular electronic dipole moments, pi, and dipole polarizabilities, a, are important in determining the energy, geometry, and intermolecular forces of molecules, and are often related to biological activity. Classically, the pKa electric dipole moment pic can be expressed as a sum of discrete charges multiplied by the position vector r from the origin to the ith charge. Quantum mechanically, the permanent electric dipole moment of a molecule in electronic state Wei is defined simply as an expectation value ... 

Once the SAM has been formed on the surface of a metal, it is possible to modify it by adding different atoms or molecules, or by adding additional layers. All of these activities are expected to change the electrical and physical characteristics of the SAM, with the intention of leading to useful molecular electronic devices or other materials. 

Transition metal polypyridine complexes are highly redox-active, both in their electronic ground- and excited states. Their electron transfer reactivity and properties can be fine-tuned by variations in the molecular structure and composition. They are excellent candidates for applications in redox-catalysis and photocatalysis, conversion of light energy into chemical or electrical energy, as sensors, active components of functional supramolecular assemblies, and molecular electronic and photonic devices. 

The type of molecular recognition reaction determines the form of the transducer used (Table 5.3). Enzymatic reactions often involve an electron transfer. This electrical activity can be measured with amperometric, potentiometric or conductometric sensors. If the bioreaction includes the generation of H+ or OH ions, then a pH sensitive dye in combination with an optical device can be used. For antibody-antigen binding, the mass change on the surface of the transducer can be detected with a piezoelectric device. Exothermic or endothermic reactions can be followed with a temperature sensor. 

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