Spin solitons in organic charge-transfer salts

Abstract

Organic charge-transfer (CT) salts that crystallize in face-to-face stacks of π-electron donors (D) and acceptors (A) are one-dimensional electronic systems with strong coupling to lattice and molecular vibrations. Peierls–Hubbard models of CT salts resemble π-electron theory of conjugated polymers, although transfer integrals t along mixed DA stacks are considerably smaller. Strong D and A yield Peierls systems with dimerized ground states of ion radicals, D + and A −. Topological spin solitons separate regions of opposite dimerization, similarly to solitons in trans-polyacetylene, but are thermally accessible in ionic CT salts due to small t. Salts with still smaller t have Peierls transitions at T P < 300 K to undimerized stacks. A Peierls–Hubbard model, H CT, describes both types of salts and estimates of t are consistent with T P < 300 K in some salts and spin solitons in others with higher T P. Electron paramagnetic resonance (epr) spectra of single crystals provide direct evidence for spin solitons and one-dimensional electronic states. Spin solitons and H CT resolve longstanding conflicts between vibrational and magnetic data that indicate dimerized stacks in several prototypical CT salts, while structural data point to undimerized stacks with large thermal ellipsoids. The low energy scale, availability of single crystals and diversity of CT salts offer opportunities for detailed modeling.