Nonmetal-to-metal transitions are among the most fascinating phenomena in material science, associated with strong correlations, large fluctuations, and related features relevant to applications in electronics, spintronics, and optics. Dissolving alkali metals in liquid ammonia results in the formation of solvated electrons, which are localised in dilute solutions but exhibit metallic behaviour at higher concentrations, forming a disordered liquid metal. The electrolyte-to-metal transition in these systems appears to be gradual, but its microscopic origins remain poorly understood. Here, we provide a detailed time-resolved picture of the electrolyte-to-metal transition in solutions of lithium in liquid ammonia, employing ab initio molecular dynamics and many-body perturbation theory, which are validated against photoelectron spectroscopy experiments. We find a rapid flipping between metallic and electrolyte states that persist only on a sub-picosecond timescale within a broad range of concentrations. These flips, occurring within femtoseconds, are characterised by abrupt opening and closing of the band gap, which is connected with only minute changes in the solution structure and the associated electron density.

Charles University Faculty of Mathematics and Physics Ke Karlovu 3 121 16 Prague 2 Czech Republic

Department of Chemistry University of Manchester Oxford Road Manchester M13 9PL UK

Department of Chemistry University of Oxford Chemistry Research Laboratory Mansfield Road Oxford OX1 3TA UK

Institute of Organic Chemistry and Biochemistry of the Czech Academy of Sciences Flemingovo nám 2 166 10 Prague 6 Czech Republic

J Heyrovský Institute of Physical Chemistry Czech Academy of Sciences Dolejškova 3 18223 Prague Czech Republic

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Thompson, J. C.

Zurek, E., Edwards, P. & Hoffmann, R. A molecular perspective on lithiumammonia solutions. PubMed DOI

Mott, N. F. Metal-insulator transitions in metal-ammonia solutions. DOI

Hayama, S., Skipper, N. T., Wasse, J. C. & Thompson, H. X-ray diffraction studies of solutions of lithium in ammonia: the structure of the metal-nonmetal transition. DOI

Buttersack, T. et al. Photoelectron spectra of alkali metal-ammonia microjets: from blue electrolyte to bronze metal. PubMed DOI

Birch, A. J. Reduction by dissolving metals. DOI

Landau, L. & Zeldovich, Y. B. On the relation between the liquid and the gaseous states of metals.

Hensel, F. & Franck, E. U. Metal-nonmetal transition in dense mercury vapor. DOI

Jortner, J. & Cohen, M. H. Metal-nonmetal transition in metal-ammonia solutions. DOI

Mott, N. F. The transition to the metallic state. DOI

Mott, N.

Herzfeld, K. F. On atomic properties which make an element a metal. DOI

Thompson, J. C. Metal-nonmetal transition in metal-ammonia solutions. DOI

Cohen, M. H. & Thompson, J. C. The electronic and ionic structures of metal-ammonia solutions. DOI

Schmidt, P. W. Small angle X ray scattering from solutions of alkali metals in liquid ammonia. DOI

Ichikawa, K. & Thompson, J. C. Chemical potentials and related thermodynamics of sodium ammonia solutions. DOI

Chieux, P. Small angle neutron scattering studies of concentration fluctuations in the non metal to metal transition range: solutions of 7li in nd3. DOI

Cohen, M. H. & Jortner, J. Metal-nonmetal transition in metal-ammonia solutions via the inhomogeneous transport regime. DOI

Damay, P. & Schettler, P. Fluctuations in metal-ammonia solutions. DOI

Deng, Z., Martyna, G. J. & Klein, M. L. Quantum simulation studies of metal-ammonia solutions. DOI

Perdew, J. P., Burke, K. & Ernzerhof, M. Generalized gradient approximation made simple. PubMed DOI

Adamo, C. & Barone, V. Toward reliable density functional methods without adjustable parameters: the PBE0 model. DOI

Zhang, Y. & Yang, W. Comment on “generalized gradient approximation made simple”. DOI

Goerigk, L. & Grimme, S. A thorough benchmark of density functional methods for general main group thermochemistry, kinetics, and noncovalent interactions. PubMed DOI

Pavlak, I., Matasović, L., Buchanan, E. A., Michl, J. & Rončević, I. Electronic structure of metalloporphenes, antiaromatic analogues of graphene. PubMed DOI PMC

Bischoff, T., Reshetnyak, I. & Pasquarello, A. Band gaps of liquid water and hexagonal ice through advanced electronic-structure calculations. DOI

Ambrosio, F., Miceli, G. & Pasquarello, A. Electronic levels of excess electrons in liquid water. PubMed DOI

Lan, J., Rybkin, V. V. & Pasquarello, A. Temperature dependent properties of the aqueous electron. PubMed DOI PMC

Baranyi, B. & Turi, L. Ab initio molecular dynamics simulations of solvated electrons in ammonia clusters. PubMed DOI PMC

Carter-Fenk, K., Johnson, B. A., Herbert, J. M., Schenter, G. K. & Mundy, C. J. Birth of the hydrated electron via charge-transfer-to-solvent excitation of aqueous iodide. PubMed DOI

Stratt, R. M. & Xu, B.-C. Band structure in a liquid. PubMed DOI

Wang, L.-W., Bellaiche, L., Wei, S.-H. & Zunger, A. “Majority representation” of alloy electronic states. DOI

Zheng, C., Yu, S. & Rubel, O. Structural dynamics in hybrid halide perovskites: bulk Rashba splitting, spin texture, and carrier localization. DOI

Rubel, O., Bokhanchuk, A., Ahmed, S. J. & Assmann, E. Unfolding the band structure of disordered solids: From bound states to high-mobility Kane fermions. DOI

Kim, K. S. & Yeom, H. W. Radial band structure of electrons in liquid metals. PubMed DOI

Kittel, C., McEuen, P. & Sons, J. W.

Burns, G.

Hirasawa, M., Nakamura, Y. & Shimoji, M. Electrical conductivity and thermoelectric power of concentrated lithium-ammonia solutions. DOI

Vöhringer, P. Ultrafast dynamics of electrons in ammonia. PubMed DOI

Madsen, G. K., Carrete, J. & Verstraete, M. J. Boltztrap2, a program for interpolating band structures and calculating semi-classical transport coefficients. DOI

Ricci, F. et al. An ab initio electronic transport database for inorganic materials. PubMed DOI PMC

Kang, J. et al. Dynamic three-dimensional structures of a metal–organic framework captured with femtosecond serial crystallography. PubMed DOI PMC

Chakraborty, D. & Chandra, A. Voids and necks in liquid ammonia and their roles in diffusion of ions of varying size. PubMed DOI

Berendsen, H., van der Spoel, D. & van Drunen, R. Gromacs: a message-passing parallel molecular dynamics implementation. DOI

Kresse, G. & Hafner, J. Ab initio molecular dynamics for liquid metals. PubMed DOI

Kresse, G. & Hafner, J. Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium. PubMed DOI

Kresse, G. & Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. PubMed DOI

Kresse, G. & Furthmüller, J. Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. PubMed DOI

Grimme, S., Antony, J., Ehrlich, S. & Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. PubMed DOI

Kostal, V., Mason, P. E., Martinez-Seara, H. & Jungwirth, P. Common cations are not polarizable: effects of dispersion correction on hydration structures from ab initio molecular dynamics. PubMed DOI PMC

Blöchl, P. E. Projector augmented-wave method. PubMed DOI

Kresse, G. & Joubert, D. From ultrasoft pseudopotentials to the projector augmented-wave method. DOI

Ricci, A. & Ciccotti, G. Algorithms for brownian dynamics. DOI

Monkhorst, H. J. & Pack, J. D. Special points for Brillouin-zone integrations. DOI

Pizzi, G. et al. Wannier90 as a community code: new features and applications. PubMed

Hedin, L. New method for calculating the one-particle Green’s function with application to the electron-gas problem. DOI

Hybertsen, M. S. & Louie, S. G. Electron correlation in semiconductors and insulators: band gaps and quasiparticle energies. PubMed DOI