Electronic and Vibrational Structure of Complexes of Tetracyanoquinodimethane with Cadmium Chalcogenide Quantum Dots
2014-08-07T00:00:00Z (GMT) by
This paper describes the use of visible, near-infrared, and mid-infrared steady-state optical spectroscopy to study the geometries in which tetracyanoquinodimethane (TCNQ) adsorbs to the surfaces of highly cadmium enriched and near-stoichiometric CdSe quantum dots (QDs) in the formation of QD-TCNQ charge transfer (CT) complexes. Several TCNQ molecules are spontaneously reduced by chalcogenides on the surface of each CdSe QD. The degree of CT depends on the geometry with which the TCNQ adsorbs and the degree of distortion of TCNQ’s geometry upon adsorption. Comparison of the electronic and vibrational spectra of CdSe QD-TCNQ complexes with those of CT complexes of TCNQ with molecular reductants (including molecular chalcogenides) and computer simulations of the geometries and vibrational spectra of the TCNQ-chalcogenide CT complexes show that (i) the Cd-enriched CdSe QDs reduce a factor of 7.4 more TCNQ molecules per QD than nearly stoichiometric CdSe QDs because surface selenides are more accessible in the Cd-enriched QDs than in the near-stoichiometric QDs and (ii) TCNQ interacts with surface selenides through several adsorption modes that result in different amounts of charge transfer and different degrees of geometric distortion of TCNQ. This study provides a framework for determining the range of adsorption geometries of small molecules on QD surfaces, and for optimizing QD surfaces to adsorb molecules in configurations with maximal electronic coupling between the QD and the adsorbate.