An Explicit Electron-Vibron Model for Olfactory Inelastic Electron Transfer Spectroscopy

Abstract

The vibrational theory of olfaction was posited to explain subtle effects in the sense of smell inexplicable by models in which molecular structure alone determines an odorant's smell. Amazingly, behavioral and neurophysiological evidence suggests that humans and some insects can be trained to distinguish isotopologue molecules which are related by the substitution of isotopes for certain atoms, such as a hydrogen-to-deuterium substitution. How is it possible to smell a neutron? The physics of olfaction may explain this isotopomer effect. Inelastic electron transfer spectroscopy (IETS) has been proposed as a candidate mechanism for such subtle olfactory effects: the vibrational spectrum of an appropriately-quantized odorant molecule may enhance a transfer rate in a discriminating electron transfer (ET) process. In contrast to other semi-classical or quantum-master-equation-based models of olfactory IETS, the model presented here explicitly treats the dynamics of a dominant odorant vibrational mode, which provides an indirect dissipative path from the electron to the thermal environment. A direct dissipative path to the environment also is included. Within this model, a calculation of ET rate is developed, along with a calculation of power dissipation to the thermal environment. Under very weak direct dissipative coupling, spectroscopic behaviors of the indirect path are revealed, and the resulting ET rate exhibits resonant peaks at certain odorant frequencies. Resonant peaks in ET rate also correlate to peaks in power dissipation. Spectroscopic behaviors are masked by strong direct dissipative coupling. Results support a rate-based discrimination between a preferred ligand and an isotopomer if indirect dissipative coupling dominates.