Quantum theory predicts a ground state or zero-point energy with a non-zero dynamic part for every bound system of particles. This minimum energy is larger for lighter particles causing large lattice dynamics. Large zero point effects lead to exotic states such as liquid ground state of helium and predicted to prompt novel quantum states in compressed light metallic systems, such as pressure-induced melting at T~0K and two-component superconductivity and superfluidity. At sufficiently low temperatures, where thermal energy is less dominant, observations of lattice quantum dynamics are possible by studying isotope effects in light metals. Under ambient conditions lithium is the lightest metal and also a superconductor: an ideal system to probe for lattice quantum effects! In our lab we extensively study properties of lithium in unexplored regions of its phase diagram and looking for deviations from semi-classical models and new exciting physical phenomena under extreme conditions of pressure, temperature and magnetic field. Indeed we find physics of lithium always full of new surprises! The following video summarizes the result of one of our studies where we find an anomalous isotope effect in lithium. Below you can read more about some of our findings in this area.
S. Deemyad and R. Zhang (2018). "Probing quantum effects in lithium." Physica C
Abstract:In periodic table lithium is the first element immediately after helium and the lightest metal. While fascinating quantum nature of condensed helium is suppressed at high densities, lithium is expected to adapt more quantum solid behavior under compression. This is due to the presence of long range interactions in metallic systems for which an increase in the de-Boer parameter (λ/σ, where σ is the minimum interatomic distance and λ is the de-Broglie wavelength) is predicted at higher densities. Physics of dense lithium offers a rich playground to look for new emergent quantum phenomena in condensed matter and has been subject of many theoretical and experimental investigations. In this article recent progress in studying the quantum nature of dense lithium will be discussed.
Ackland, G.J., M. Dunuwille, M. Martinez-Canales, I. Loa, R. Zhang, S. Sinogeikin, W. Cai, and S. Deemyad (2017). " Quantum and isotope effects in lithium metal" Science.
Abstract:For the past 70 years, the lowest-energy crystal structure of lithium was believed to be a relatively complex one called the 9R structure. Ackland et al. show that this is incorrect. The actual lowest-energy structure for lithium is the much simpler closest-packed face-centered cubic form. In addition, 6Li and 7Li isotopes have crystal phase transitions at slightly different pressures and temperatures. This difference is chalked up to large quantum mechanical effects between the isotopes. Lithium is the only metal that shows this type of quantum effect and presents a challenge for theoreticians to explain.Science, this issue p. 1254The crystal structure of elements at zero pressure and temperature is the most fundamental information in condensed matter physics. For decades it has been believed that lithium, the simplest metallic element, has a complicated ground-state crystal structure. Using synchrotron x-ray diffraction in diamond anvil cells and multiscale simulations with density functional theory and molecular dynamics, we show that the previously accepted martensitic ground state is metastable. The actual ground state is face-centered cubic (fcc). We find that isotopes of lithium, under similar thermal paths, exhibit a considerable difference in martensitic transition temperature. Lithium exhibits nuclear quantum mechanical effects, serving as a metallic intermediate between helium, with its quantum effect–dominated structures, and the higher-mass elements. By disentangling the quantum kinetic complexities, we prove that fcc lithium is the ground state, and we synthesize it by decompression.
S. F. Elatresh, W. Cai, N. W. Ashcroft, R. Hoffmann, S. Deemyad and S. A. Bonev. (2017). "Evidence from Fermi surface analysis for the low-temperature structure of lithium"Nature Communications
Abstract:The low-temperature crystal structure of elemental lithium, the prototypical simple metal, is a several-decades-old problem. At 1 atm pressure and 298 K, Li forms a body-centered cubic lattice, which is common to all alkali metals. However, a low-temperature phase transition was experimentally detected to a structure initially identified as having the 9R stacking. This structure, proposed by Overhauser in 1984, has been questioned repeatedly but has not been confirmed. Here we present a theoretical analysis of the Fermi surface of lithium in several relevant structures. We demonstrate that experimental measurements of the Fermi surface based on the de Haas–van Alphen effect can be used as a diagnostic method to investigate the low-temperature phase diagram of lithium. This approach may overcome the limitations of X-ray and neutron diffraction techniques and makes possible, in principle, the determination of the lithium low-temperature structure (and that of other metals) at both ambient and high pressure. The theoretical results are compared with existing low-temperature ambient pressure experimental data, which are shown to be inconsistent with a 9R phase for the low-temperature structure of lithium.
Schaeffer A. M, Cai. W., Olejnik E. † , Molaison J. J., Sinogeikin S., dos Santos A. M., Deemyad S. (2015). "New boundaries for martensitic transition of 7Li under pressure." Nature Communications
Abstract: Physical properties of lithium under extreme pressures continuously reveal unexpected features. These include a sequence of structural transitions to lower symmetry phases, metal-insulator-metal transition, superconductivity with one of the highest elemental transition temperature and a maximum followed by a minimum in its melting line. The instability of lithium’s bcc structure, is well established by the presence of a temperature-driven martensitic phase transition. The boundaries of this phase, however, have not been previously explored above 3 GPa. All higher pressure phase boundaries are either extrapolations or inferred based on indirect evidence. Here, we explore the pressure dependence of the martensitic transition of lithium up to 7 GPa using a combination of neutron and X-ray scattering. We find a rather unexpected deviation from the extrapolated boundaries of hR3 phase of lithium. Furthermore, there is evidence that, above ~3 GPa, once in fcc phase, lithium does not undergo a martensitic transition.
Schaeffer, A. M., Temple S. R., Bishop J.K. and Deemyad S.(2015). "High-pressure superconducting phase diagram of 6Li: Isotope effects in dense lithium." Proceedings of the National Academy of Sciences .
Abstract: We measured the superconducting transition temperature of 6Li between 16 and 26 GPa, and report the lightest system to exhibit superconductivity to date. The superconducting phase diagram of 6Li is compared with that of 7Li through simultaneous measurement in a diamond anvil cell (DAC). Below 21 GPa, Li exhibits a direct (the superconducting coefficient, α, Tc∝ M−α, is positive), but unusually large isotope effect, whereas between 21 and 26 GPa, lithium shows an inverse superconducting isotope effect. The unusual dependence of the superconducting phase diagram of lithium on its atomic mass opens up the question of whether the lattice quantum dynamic effects dominate the low-temperature properties of dense lithium.
Schaeffer, A. M.,Talmadge W. B., Temple S. R. and Deemyad S. (2012). "High Pressure Melting of Lithium." Physical Review Letters .
Abstract: The melting curve of lithium between ambient pressure and 64 GPa is measured by detection of an abrupt change in its electrical resistivity at melting and by visual observation. Here we have used a quasi-four-point resistance measurement in a diamond anvil cell and measured the resistance of lithium as it goes through melting. The resistivity near melting exhibits a well documented sharp increase which allowed us to pinpoint the melting transition from ambient pressure to 64 GPa. Our data show that lithium melts clearly above 300 K in all pressure regions and its melting behavior adheres to the classical model. Moreover, we observed an abrupt increase in the slope of the melting curve around 10 GPa. The onset of this increase fits well to the linear extrapolation of the lower temperature bcc-fcc phase boundary.
Like temperature, pressure is a thermodynamic variable. Under pressure energy landscape of materials changes and material can transform to new forms. Materials with new structural, electronic and magnetic properties often are discovered once a material is subjected to extreme pressures.
High pressure phase diagram (P-T) are of substantial interest for the insight they provide in designing new materials with enhanced properties, testing theoretical models and in many cases modeling the condensed states of matter present within the Earth and other planets.
In our lab we are interested in exploring phase diagram of materials abundant in the solar systems, simple forms of matter such as metals or those with technologically interesting properties. Examples of some of the phase diagrams that we are studying are:
Structures of lithium isotopes under pressure
Melting curve of lithium
Structures of benzene derivatives under pressure
P-T phase diagram of polycyclic aromatic hydrocarbons
Superconducting phase diagram of Fe-based superconductors
Many of the valuable materials including gems and oil are produced at the extreme conditions of pressure and temperature deep within the earth.
Many of these are then meta-stable compounds which can keep their compositions in ambient conditions. Advances in high pressure techniques allow synthesizing materials in such conditions in tabletop experiments.
High-pressure synthesis inside a diamond anvil cell is a powerful method that can be utilized to synthesize materials which may need high pressure for synthesis but afterward may be stable even in ambient conditions. This method yields small quantities which are sufficient for preliminary studies and help in the discovery of interesting compounds. In addition, even small quantities of a valuable material may be sufficient as a seed for growing large single crystals. In our lab we are exploring the possibilities for synthesis of materials with novel properties at high pressure.
Exploring the frontiers of science often require new tools and innovations. In our group we are interested in developments of new methods. Here are two examples of the methods that we have been advancing in our lab.
Measurements of low melting temperature of metals and indirect resistance micro-calorimetry (IRMC) in a diamond anvil cell
By applying Mott's empirical equation of electrical resistivity of liquid metals to the size of the jump, the latent heat of fusion can be estimated.
Previously there has been no method for determining the latent heat of fusion of metals at extreme pressures in the Mega bar range. Our method brings this unique capability to determine the latent heat of fusion in metals with melting temperatures that can be achieved in a resistively heated DAC. This method also provides a simple solution for determining the melting temperature of metals and the latent heat of fusion of all alkali metals under extreme pressures.
Simultaneous comparative transport measurements in a diamond anvil cell (DAC)
Due to different DAC designs or particular experimental designs or goals, uncertainties in the determination of the temperature of a given sample exist.
To overcome the inaccuracy in comparing the temperature dependence of transport properties of different materials at high pressure, we have used a new design of resistivity measurement in a twin sample chamber built on an insulated gasket in a DAC. In this design, the transport properties of two samples will be measured simultaneously. The uncertainties in the temperatures of the two samples will be exactly the same and therefore their relative phase diagram will be compared precisely.
On left schematic drawing of electrical measurement circuit inside a cryostat. The lock-in A and B are running in two different frequency to eliminate interference. Inset shows the actual double quasi-four probes built on the gasket.
Measurement circuits for sample for A and B respectively:
SR830 Lock-in amplifiers,
SR830 Function generators (2 and 3).
CryoCon temperature controller (6).
Diode thermometer (7).
On right the correlation between the pressures in the two chambers up to 11 GPa. Three rubies across each sample chamber are distributed for evaluating the pressure gradient (blue boxes). The blue line has a slope of 1. Red is a linear fit to PA vs. PB.
"Suppression of ferromagnetism governed by a critical lattice parameter in CeTiGe3 with hydrostatic pressure or V substitution" Jin, Hanshang, Weizhao Cai, Jared Coles, Jackson R. Badger, Peter Klavins,*Shanti Deemyad, and Valentin Taufour.Physical Review B. 106, no. 7 (2022): 075131
"Structure and pressure dependence of the Fermi surface of lithium" Bhowmick, Tushar, Sabri F.Elatresh, Audrey D. Grockowiak, William Coniglio, Mohammad Tomal Hossain, Elisabeth J. Nicol, Stanley W. Tozer, Stanimir A. Bonev, and Shanti Deemyad.Physical Review B. 106, no. 4 (2022): L041112
"Pressure-induced metallization in the absence of a structural transition in the layered ferromagnetic insulator Cr2Ge2Te6" Cai, Weizhao, Luo Yan, Su Kong Chong, Jingui Xu, Dongzhou Zhang, Vikram V. Deshpande, Liujiang Zhou, and Shanti Deemyad*.Physical Review B. 106, no. 8 (2022): 085116
"Coexistence of vitreous and crystalline phases of H2O at ambient temperature" Shargh, Ali K., Aude Picard, Rostislav Hrubiak, Dongzhou Zhang, Russell J. Hemley, Shanti Deemyad*, Niaz Abdolrahim*,& Saveez Saffarian*.Proceedings of the National Academy of Sciences. 12, 119, no. 27 (2022): e21172811192021
"Pressure-induced ferroelectric-like transition creates a polar metal in defect antiperovskites Hg3Te2X2 (X = Cl, Br)" Weizhao Cai, Jiangang He*, Hao Li, Rong Zhang, Dongzhou Zhang, Duck Young Chung, Tushar Bhowmick, Christopher Wolverton, Mercouri G. Kanatzidis* & Shanti Deemyad*. Nature Communications 12, 1509 (2021). (doi:10.1038/s41467-021-21836-7)2020
"Pressure-Induced Superconductivity in the Wide Band Gap Semiconductor Cu2Br2Se6 with A Robust Framework" Cai W, Lin W, Yan Y, Hilleke KP, Coles J, Bao J-K, Xu J, Zhang D, Chung DY, Kanatzidis MG*, Zurek E*, Deemyad S*. Chemistry of Materials (2020) (doi:10.1021/acs.chemmater.0c02151)
"Fermi surface studies of the low-temperature structure of sodium" S. F. Elatresh,Mohammad Tomal Hossain, Tushar Bhowmick, A. Grockowiak, Weizhao Cai, W. A. Coniglio, Stanley W. Tozer, N. W. Ashcroft, S. A. Bonev*, Shanti Deemyad*, and Roald Hoffmann*. Physical Review B. Rapic Communications.(2020);101(22):220103. (doi: 10.1103/PhysRevB.101.220103)2019
"Pressure-induced Superconductivity and Flattened Se6 Rings in the Wide Bandgap Semiconductor Cu2I2Se6" Cai, W., Lin, W., Li, L.H., Malliakas, C. D., Zhang, R., Groesbeck, M., Bao, J. K., Zhang, D., Sterer, E., Kanatzidis, M. G., and S. Deemyad*, Journal of the American Chemical Society, 141, 38, 15174–15182, (2019) (doi: 10.1021/jacs.9b06794)
"Perovskites with a Twist: Strong In1+ Off-centering in the Mixed-Valent CsInX3 (X= Cl, Br)" McCall KM, Friedrich D, Chica DG, Cai W, Stoumpos CC, Alexander GC, Deemyad S, Wessels BW, Kanatzidis MG. Chemistry of Materials. (2019).
"Parallel background subtraction in diamond anvil cells for high pressure X-ray data analysis." Weizhao Cai, Mohammad Tomal Hossain, Jared Coles, Jordan Lybarger, Joseph Blanton, Eran Sterer and Shanti Deemyad*, High Pressure Research, (2019) 1-122018
"Effects of Non-Hydrostatic Stress on Structural and Optoelectronic Properties of Methylammonium Lead Bromide Perovskite." Zhang, R., Cai, W., Bi, T., Zarifi, N., Terpstra, T., Zhang, C., Vardeny, Z.V., Zurek*, E., Deemyad, S.*, Journal of Physical Chemistry Letters,( 2017), DOI: 10.1021/acs.jpclett.7b01367.
"Evidence from Fermi surface analysis for the low-temperature structure of lithium." Elatresh, S.F., W. Cai, N.W. Ashcroft, R. Hoffmann*, S. Deemyad*, and S.A. Bonev*, Proceedings of the National Academy of Sciences, 114(21): p. 5389-5394. (2017).
"Deuterium Isotope Effects in Polymerization of Benzene under Pressure." W. Cai, M. Dunuwille, J. He, J. K. Hinton(Bishop), M.C. MacLean, J.M Molaison, A.M. dos Santos, S. Sinogeikin and S. Deemyad*, Journal of Physical Chemistry Letters,2017, DOI: 10.1021/acs.jpclett.7b00536 (2017).
"High-pressure superconducting phase diagram of 6Li: Isotope effects in dense lithium." Schaeffer, A. M., Temple, S. R., Bishop, J. K. & Deemyad*, S. Proceedings of the National Academy of Sciences 112, 60-64, doi:10.1073/pnas.1412638112 (2015)2013
"Pathways to metallic hydrogen" Silvera I. F. and Deemyad S 7TH CONFERENCE ON CRYOCRYSTALS AND QUANTUM CRYSTALS, Wroclaw, Poland, (edited by M. Kazimierski)
"Strategy and enhanced temperature determination in a laser heated diamond anvil cell" Deemyad S, Papathanassiou, A. N. & Silvera, I. F. IF JOURNAL OF APPLIED PHYSICS 105, 093543 (2009)
"Temperature dependence of the emissivity of Pt in the IR" Deemyad S and Silvera IF REVIEW OF SCINTIFIC INSTRUMENTS 79, 086105 (2008)
"Melting line of hydrogen at high pressures" Deemyad S and Silvera IF PHYSICAL REVIEW LETTERS 100, 155701 (2008)
"Studies on the weak itinerant ferromagnet SrRuO3 under high pressure to 34 GPa" Hamlin JJ, Deemyad S, Schilling JS, Jacobsen MK, Kumar RS, Cornelius AL, Cao G and Neumeier JJ PHYSICAL REVIEW B 76, 014432 (2007)
"Pulsed laser heating and temperature determination in a diamond anvil cell" Deemyad S, Sterer E., Barthel C., Rekhi S., Tempere J. and Silvera IF REVIEW OF SCIENTIFIC INSTRUMENTS 76, 125104 (2005)
"Enhanced superconducting properties of bicrystalline YBa2Cu3Ox and alkali metals under pressure" Tomita T, Deemyad S, Hamlin JJ, Schilling JS, Tissen VG, Veal BW, Chen L and Claus H JOURNAL OF PHYSICS-CONDENSED MATTER 17, S921 (2005)
"High-pressure study of structural phase transitions and superconductivity in La1.48Nd0.4Sr0.12CuO4" Crawford MK, Harlow RL, Deemyad S, Tissen V, Schilling JS, McMarron E, Tozer SW, Cox DE, Ichikawa N, Uchida S, and Huang Q PHYSICAL REVIEW B 71, 104513 (2005)
"The superconducting phase diagram of Li metal to 67 GPa" [Cover Story of PRL] Deemyad S and Schilling JS PHYSCAL REVIEW LETTERS 91, 167001 (2003)
"Dependence of the superconducting transition temperature of single- and polycrystalline MgB2 on hydrostatic pressure" Deemyad S, Tomita T, Hamlin JJ, Beckett BR, Schilling JS, Hinks DG, Jorgensen JD, Lee S, and Tajima S (Invited paper for a special edition of Physica C on MgB2) PHYSICA C 385, 105 (2003)
"Dependence of the superconducting transition temperature of MgB2 on pressure to 20 GPa" Deemyad S, Schilling JS, Jorgensen JD, and Hinks DGPHYSICA C 361, 227 (2001)
"Hydrostatic pressure dependence of the superconducting and structural properties of MgB2" Schilling JS, Jorgensen JD, Hinks DG, Deemyad S, Hamlin JJ, Looney CW, and Tomita T, STUDIES OF HIGH TEMPERATURE SUPERCONDUCTORS (edited by A.V. Narlikar, Nova Science Publishers, N.Y.), 38, 321 (2001)