Multielement NMR studies of the liquid-liquid phase separation and the metal-to-nonmetal transition in fluid lithium- and sodium-ammonia solutions.
(1)H, (7)Li, (14)N, and (23)Na high resolution nuclear magnetic resonance (NMR) measurements are reported for fluid solutions of lithium and sodium in anhydrous liquid ammonia across the metal-to-nonmetal transition (MNM transition), paying particular attention to the phenomenon of liquid-liquid phase separation which occurs in the composition/temperature region close to the MNM transition. Our results are discussed in terms of the electronic structure of fluid metal-ammonia solutions at low temperatures (ca. 240 K). We find that the electronic phase transition to the metallic state in these solutions, especially at temperatures close to the liquid-liquid critical consolute temperature, occurs from a nonmetallic, electrolytic solution containing a predominance of electron spin-paired, (diamagnetic) charged bosonic states. The possible implications of these observations to the nature of the liquid-liquid phase separation are discussed, both from the views of N. F. Mott, regarding the MNM transition in sodium-ammonia solutions, and those of R. A. Ogg, regarding the possibility of high-temperature superconductivity in these solutions. Similarities between the electronic structure of metal-ammonia solutions and the high-temperature cuprate superconductors are also briefly emphasized.
Department of Chemistry, Centre for Advanced Electron Spin Resonance (CAESR), Inorganic Chemistry Laboratory, Department of Chemistry, University of Oxford , Oxford OX1 3QR, U.K.
Matthew T J H
MT
Lodge
P
P
Cullen
Nicholas H
NH
Rees
Neil
N
Spencer
Kiminori
K
Maeda
Jeffrey R
JR
Harmer
Martin O
MO
Jones
Peter P
PP
Edwards