Stark Effect and Nonlinear Impedance of the Asymmetric Ag-CO-Ag Junction: An Optical Rectenna

Abstract

We present first-principles analysis of the Stark effect of CO adsorbed on an atomically sharp silver asperity, and current versus potential (I–V) characteristics of the Ag-CO-Ag junction. The analysis supports the suggestion that CO-bridged plasmonic junctions represent rectifying nanoantennas at optical frequencies and that the CO vibrational spectrum serves as a molecular voltmeter [M. Banik et al. ACS Nano 2012, 6, 10343]. The Stark effect is principally controlled by the field-induced charge redistribution between the antibonding 2π*-orbitals of CO and the s-electrons of Ag. The Stark tuning rate of the CO stretch, 1.5 × 10–6 cm–1/V cm–1, is ∼25% larger on atomically sharp asperities than on flat Ag, and remains constant over a large window of applied fields (±0.8 V/A). As such, both sign and strength of local electric field can be quantitatively determined by the vibrational shift of CO. The I–V curve of the Ag-CO-Ag junction is nonlinear, rendering it an effective rectifier with responsivity S = (∂...