Electronic spin separation induced by nuclear motion near conical intersections

Abstract

AbstractThough the concept of Berry force was proposed thirty years ago, little is known about the practical consequences of this force as far as chemical dynamics are concerned. Here, we report that when molecular dynamics pass near a conical intersection, a massive Berry force can appear as a result of even a small amount of spin-orbit coupling (<10−3 eV), and this Berry force can in turn dramatically change pathway selection. In particular, for a simple radical reaction with two outgoing reaction channels, an exact quantum scattering solution in two dimensions shows that the presence of a significant Berry force can sometimes lead to spin selectivity as large as 100%. Thus, this article opens the door for organic chemists to start designing spintronic devices that use nuclear motion and conical intersections (combined with standard spin-orbit coupling) in order to achieve spin selection. Vice versa, for physical chemists, this article also emphasizes that future semiclassical simulations of intersystem crossing (which have heretofore ignored Berry force) should be corrected to account for the spin polarization that inevitably arises when dynamics pass near conical intersections.