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Discovery of Metallic Fluid Hydrogen at 140 GPa and Ten-fold Compressed Liquid Density
W.J. Nellis
This paper is the history of the discovery of metallic, fluid hydrogen at 3000 K achieved with a two-stage light-gas gun (2SG) at the Lawrence Livermore National Laboratory (LLNL). The temperature is low in that the electrons are highly degenerate and the experimental lifetime is long in that the fluid is in thermal equilibrium. The necessary technology and experimental data were developed over a period of twenty-five years without realizing the end result would be metallic fluid hydrogen. The requirements for success were physical intuition, creative thinking concerning experiments to be performed and how to interpret results, persistence, a willingness to take risks, and luck. Knowing where to look is not luck, but the cooperation of nature is required to make any discovery. The biggest impediment was the funding system, which discourages risk. [two-stage gun, dense hydrogen, semiconductor-metal transition, dynamic compression]

1. Introduction Interest in the metallization of hydrogen dates from 1935 when Wigner and Huntington[1] predicted that at sufficiently high density at temperature T = 0 K solid H2 would dissociate into solid H. Both electrons are localized on the H2 molecule and so the molecular solid is an insulator. At sufficiently high density the PdV compressive energy of the monatomic solid is less than that of molecular solid, which drives the dissociative transition from the molecular to the monatomic phase. Solid H has one electron per band and is a metal. Thus, this phase transition is accompanied by an insulator-metal transition (IMT). In 1935 Wigner and Huntington estimated the pressure corresponding to the density of this IMT to be about 25 GPa (0.25 Mbar). The quantum physics in their calculation had then only recently been developed and their calculation was a test of the new quantum theory. However, this IMT is yet to be observed experimentally up to pressures approaching 400 GPa near 0 K. Theoretical predictions of metallization below 400 GPa have been proven incorrect by experiments in diamond anvil cells (DACs). The facts that this IMT of element

Z = 1 has neither been observed experimentally nor correctly predicted theoretically pose as challenging a problem as ever encountered in condensed matter physics. Pressures above 300 GPa have been achieved in H2 in a DAC, but still higher pressure is required. Based on history, it will be some time before the IMT of H2 driven by pressure alone will be observed experimentally. However, the addition of thermal energy might drive this transition. The free energy has a term - TS, where S is entropy. Dissociation at sufficiently high T increases entropy and minimizes free energy. However, to produce a metal, T should be small relative to the Fermi 1). Thus far, it temperature TF of condensed H (T/TF has not been possible to heat H2 in a DAC because hydrogen rapidly diffuses out of its sample holder. Some other method is needed. 2. Dynamic adiabatic compression with a two-stage gun Compressions by a single shock wave, multiple shock waves, and along an isentrope are adiabatic because they occur in a time small compared to times re-

Department of Physics, Harvard University, Cambridge MA 02138, U.S.A. Electronic address: nellis@physics.harvard.edu

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quired for significant thermal transport and mass diffusion out of the sample. They are also slow compared to atomic collision times, so that dynamically compressed material is in thermal equilibrium. In fact, temperature is tunable between relatively high temperatures achieved by a single shock on the Hugoniot and relatively low temperatures on the isentrope. Tuning is done by choice of the relative amounts of shock and isentropic heating. This technique is most effective in the case of a compressible low-density material, such as liquid H2 , contained between two high-density incompressible anvils. Pressures up to ~100 GPa, densities up to 12-fold of liquid-H2 density, and temperatures up to several 1000 K were achieved by impact of a 20-g projectile accelerated to as much as 7 km/s with a 2SG at LLNL (Fig. 1). Single-shock Hugoniot equation-of-state data are obtained by measuring impact velocity, the velocity of the shock wave induced in the target sample, and conserving mass, momentum, and internal energy via the Hugoniot equations. The kinetic energy of 20 g traveling 7 km/s is 0.5 MJ, comparable to that of the 1012 protons and antiprotons accelerated close to the speed of light at the Fermilab. The 2SG uses the same energy of a projectile to study novel states of condensed matter, as Fermilab uses to study novel states of sub-nuclear matter. The samples were liquid H2 at 20 K, 25 mm in di-

ameter, and 0.5 mm thick, contained between two 2-mmthick anvils of c-cut single-crystal Al2 O3 . The dynamically compressed samples were 0.05 mm thick. Four

Fig. 2. Photograph of holder of liquid-H2 sample. Outer diameter of holder is 12.5 cm. Liquid-H2 coolant was transferred down to Cu connector with 900 bend at bottom of stainless-steel fill tube. On top of holder are vent line for H2 gas that evaporates from coolant and inlet to condense H2 or D2 gas into liquid sample at 20 K. Above holder (not shown) was 0.5-liter reservoir of liquid-H2 that kept 0.l liter of coolant in sample holder filled until gun was fired. Stainless steel coaxial cables 0.5 mm in diameter were used to measure voltage and allow electrical current to flow. Cryogenic assembly was wrapped with -100 layers of aluminized mylar for thermal insulation in evacuated target chamber (10-4 to 10-3 torr) of gas gun. This increased lifetime of coolant, giving more time in which to fire gun. No one is in gun-room when gun is fired.

Fig. 1. Photograph of two-stage light-gas gun. Length of gun is 20 m.

Fig. 3. Schematic of experiment to measure electrical conductivity of dynamically compressed liquid H2 . For higher values of conductivity a shunt resistor (not shown) was placed in parallel with conductivity cell. In this way current is flowing in shunt resistor prior to induced conduction in hydrogen. This permits current to branch in minimum time (ns).

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electrodes 0.75 mm in diameter were used to measure electrical conductivity. These dimensions are sufficiently large to enable ns time resolution with the ~100 ns experimental lifetime. Since the sample holder does not experience static pressures, its materials were chosen for their known physical properties at ambient pressure. Since material strength is not needed to confine the sample, construction materials were weak and a 100-GPa shock wave destroys the sample holder in each experiment. Thus, each experimental data point required assembly of its own cryogenic sample holder. A sample holder is shown in Fig. 2. A schematic of a sample holder is illustrated in Fig. 3. Effects on thermodynamic states achieved in hydrogen by single, multiple, and isothermal (0 K) compression are illustrated in Fig. 4. The projectile launched by the 2SG is a metalimpactor plate hot-pressed into a plastic sabot. The gun is driven by up to 5 kg of gunpowder, which compresses 60 g of H2 gas, the light gas in the gun. The 60 g of H2, if mixed with oxygen, has an explosive energy equivalent of 2 kg of TNT. The liquid-H2 coolant in the sample holder has an explosive energy content of another 2 kg of TNT. Care was taken to ensure that H2 does not mix with O2, and that if they did mix there is insufficient energy present to spark a reaction. The velocity of the projectile on impact with the target determines the pressure achieved. Projectile velocity was measured in free flight by X-radiography using two pulses with 0.05 sec

widths. Spatial centers of the pulses were separated by 300 mm. To perform the experiments discussed below, starting in 1976 I collaborated with A.C. Mitchell, without whom these experiments would not have been performed. In 1991 S.T. Weir joined us to measure electrical conductivities of quasi-isentropically compressed fluid hydrogen, the experiments that discovered the semiconductor-metal transition at 140 GPa. Several technicians built and installed sample holders in the target chamber of the 2SG, assisted in the measurements, and maintained and fired the 2SG. The hydrogen conductivities were reported previously[2, 3] and dynamic compression and its various scientific aspects have been reviewed[4]. 3. The History In 1976 I joined the Dynamic Compression Group in H Division. As a graduate student I had measured electrical and thermal properties of rare-earth metals from 4 to 300 K using liquid He, H2, and N2 as coolants. In the early 1970s, there was very little federal support for basic research in the U.S. When the opportunity arose to do condensed-matter research at high pressures at LLNL, I took it. Given the complexity of gas-gun experiments, I teamed with A.C. Mitchell who had extensive experience making fast measurements and knowledge of the shock-compression literature. In those days dynamic compression meant shock compression, that is, compression by a single shock wave (Hugoniot). My first measurements were Hugoniot curves of fluids in Jupiter, Saturn, Uranus, and Neptune. These planets accreted from nebular gases of H2 , He, CH4 , NH3 , and H2 O. The slow accretion process is isentropic starting from extremely low densities. Shock compression of liquids causes temperature to rise quickly with shock pressure. At some high pressure and temperature the isentrope from low density gas crosses the Hugoniot of the liquid. These shock-compressed fluids are semiconductors near the Hugoniot and highly degenerate metallic fluids at higher densities along isentropes starting from points on the Hugoniot. When the initial funding from outside LLNL to study planetary liquids disappeared in 1978, I obtained funding within LLNL by

Fig. 4. Illustration of how calculated pressure and density achieved by dynamic compression of liquid H2 are tuned by varying time over which pressure is applied. Single shocks (Hugoniot) produce high thermal and total pressures and relatively low compressions (long-dashed curves). Multiple shocks produced by reverberation achieve substantially lower temperatures and thermal pressures and substantially higher compressions (solid curves), relatively close to 0-K isotherm (short-dashed curve)[3].

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pointing out that we were studying reaction products of detonated explosives: H2 , N2 , CO, O2 , CO2 , NH3 , H2 O, hydrocarbons, and mixtures. Planetary fluids and products of reacted explosives are essentially the same molecular fluids at comparable pressures and temperatures. Previously, many experiments on liquids had been performed using shock waves generated by planar systems driven by high explosives. Our gas-gun experiments would reach twice the pressures achieved previously. Since very little Hugoniot data on cryogenic liquids had been measured with a 2SG, I wanted to do study many liquids. For this reason I designed cryogenic sample holders to contain liquid-H2 coolant, with the flexibility to readily adapt them for other cryogenicliquid coolants or for the flow of cold N2 gas. In this way, we studied liquid H2/D2, He, N2, CO, O2, Ar, CH4, Xe, CO2, and NH3. We also studied H2O, hydrocarbons, and synthetic Uranus, a mixture of water, ammonia, and isopropanol representative of the interiors of Uranus and Neptune. However, because temperature increases rapidly with single-shock pressure, at sufficiently high pressures materials get so hot that they reach a limiting or maximum shock compression of only four-fold (4 times initial density), insufficient to reach a degenerate (metallic) state in hydrogen. We also developed techniques to measure electrical conductivity under single shock by inserting electrodes into the liquid and we determined gray-body temperature from the spectral dependence of thermal emission from the shock front. For many liquids we measured states reached by a second shock starting from the first-shock state. These are called double-shock states. For liquid hydrogen, a maximum compression of about six-fold can be achieved with two shocks, again not sufficient to reach a degenerate phase. The states reached with one or two shocks cause multi-atomic molecular liquids to dissociate and react chemically. These fluids are semiconducting. In those days relatively little Hugoniot equation-ofstate data was available for solids used in shock experiments at the pressures achieved by the 2SG. The Hugoniot is required in the data analysis for any solid that affects the state reached in the liquid sample. Such solids are called standards and are used as impactor plates, metal walls containing liquid samples, and anvils used to achieve doubly or multiply shocked states.

Because of the rapid propagation of errors in the analysis of shock data, it is not acceptable to extrapolate data obtained at lower pressures. For this reason we measured the Hugoniots of Al, Cu, Ta, Pt, and Al2O3 up to 200 GPa and higher. While our original intent had been to compress liquid H2 quasi-isentropically with a reverberating shock wave, we first wanted to gain experience with the complex experimental system by doing single-shock and double-shock experiments on molecular reaction products of detonated explosives. These are easier to do than H2 . We almost spent too much time doing this before moving on to multiply shocked states. We investigated singly and doubly shocked states until 1990, one reason for which was they involved little risk. However, the Cold War ended in 1989 and we were at a defense laboratory. In 1990 Art Mitchell and I measured electrical conductivities of liquid H2 on the Hugoniot between 10 and 20 GPa, the first time the electrical conductivity of condensed hydrogen had been measured at any pressure. At the same time, at our small two-stage gun Sam Weir was shock-compacting powders of high-temperature superconducting oxides with a shock reverberating in the powder between Cu anvils. We decided to combine elements of both experiments; i.e., to measure the electrical conductivity of liquid H2 as it was compressed by a shock reverberating between two Al2O3 anvils. Computer simulations showed that a compression of about 10-fold would be achieved with about ~10 shocks. Because the pressure achieved by multiple shock compression is equal to the first shock pressure in one of the anvils, independent of the equation of state of the liquid, we could determine pressure in the liquid by measurement of impactor velocity. By using electrically insulating Al2O3 anvils, we could achieve a pressure of 200 GPa in dense fluid hydrogen, ten times higher than achieved by a single shock, and measure its electrical conductivity with electrodes (Fig. 3). All we had to do was replace the 5 mm-thick liquid H2 layer in the single-shock experiments with a composite specimen consisting of a 2 mmthick Al2O3 crystal, followed by a 0.5 mm-thick layer of liquid H2, followed by a second Al2O3 crystal. Conventional wisdom said that one should search for metallic hydrogen near 0 K, as Wigner and

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Huntington had said in 1935. Since by the early 1990s metallic hydrogen near 0 K had yet to be observed experimentally, something else needed to be tried in addition to compressing H2 in a DAC. We could make dense hydrogen at 200 GPa at a temperature that was less than that achieved by a single shock at 20 GPa and we knew how to measure electrical conductivity in the process. Suddenly it became obvious that we should try to find metallic hydrogen; i.e., to take the risk. Since the required pressure at 0 K predicted at the time was 300 GPa, it was quite possible that we would not find it. But what would we find at these conditions that essentially had not before been studied? It was important that the experiments be done and we set out to do them. In the early 1990s we no longer had funding in our group to do hydrogen experiments. So in 1991 Sam Weir and I wrote a proposal and submitted it to the Laboratory Directed Research and Development Program (LDRD). Sam was a postdoctoral researcher nearing the end of his appointment. The main goal of LDRD was to provide postdoctoral researchers with projects that would lead to a career at LLNL. The proposal should also study an interesting scientific problem. Because individual reviewers have varying biases as to the definition of interesting, the scientific importance of a proposed study is not necessarily obvious to the deciders. From 1985 to 1990 I tried yearly and unsuccessfully to get an

LDRD grant on a variety of topics. Sam was the only young person at LLNL at that time who knew how to measure electrical conductivities of shock-compressed matter. So the main point of our proposal was to give Sam the opportunity to carry his expertise into a career position. The reviewers understood

Fig. 5. Electrical conductivities of Cs (open inverted triangles) and Rb (open squares)[7], oxygen (solid triangles)[5], nitrogen (solid circles)[6] and hydrogen (solid diamonds)[3] versus a*/D-1/3, where a* is effective Bohr radius of electrons in atom that form conduction band in fluid and D is number density of atoms. D1/3a* is ratio of effective atom size to distance between atoms[6].

Fig. 6. (a) Charge densities (4 r2 * ) of valence electrons of H, N, O, Rb, and Cs atoms versus radial distance r from nucleus of each atom. For comparison charge densities have been shifted radially so that maximum of each curve is at 1 bohr. (b) Curves in (a) plotted on expanded scale[6].

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the scientific importance and awarded us the grant. It took the first-year to do the first experiment, which was successful. Sams two-year postdoctoral position expired in 1992 at the end of the first year of our LDRD-funded proposal. I requested that LDRD renew us for the second year to give me, his group leader, the best chance of getting Sam promoted to a career position. LDRD awarded us the second year of funding. Unfortunately, I was not able to convince the H Division Leader to promote Sam. So Sam moved to another division at LLNL; Art Mitchell was already retired. Fortunately, Art continued to work on this project in retirement and Sam came over to our 2SG when we performed shock reverberation experiments on hydrogen. It took three years to complete ten experiments and a year to analyze the data. In 1996 we published the first results. This work was published with trepidation because we knew we had not thought of every possibility that could explain our data. Nevertheless, we were confident of our interpretation. Fortunately, no criticism emerged that we could not answer. We then received funding for postdoctoral researchers, Ricky Chau and Marina Bastea. Our model to explain hydrogen did not depend on the fact that the sample was hydrogen. We expected similar results for liquid oxygen and nitrogen, as were observed[5, 6]. Measured conductivities of fluid Cs and Rb at similar conditions undergo the same semiconductor-metal transition[7]. Similar experiments on fluid hydrogen compressed by a reverberating shock driven by high explosives yielded similar results[8]. It took until 2002 to demonstrate that fluid H, N, O, Rb, and Cs all undergo the same Mott transition to minimum metallic conductivity (Fig. 5)[4, 6]. The semiconductor-metal transition occurs by overlap of quantummechanical radial charge-density distributions on adjacent atoms in each fluid (Fig. 6). Their metallic conductivities are relatively low, about 2000/(ohm-cm), because conductivity is dominated by disorder. The degeneracy factor of metallic H is T/TF ~0.01, essentially that of solid Cs at room temperature. The density dependence of the approach to minimum metallic conductivity is determined by the radial extent of the charge-

density distribution. 4. Risk The technology needed to perform and interpret these experiments existed before I started this project. This project had significant funding for fifteen years when we started searching for metallic hydrogen. The obvious question then is Why did it take so long? At LLNL one could get substantial funding with enough salesmanship. However, if the goal is not reached in ~3 years, most such projects are terminated. On the other hand, if one kept a low profile by not requesting support for a visible project, then one could work for a longer period at a slower rate. I chose the low-profile route. The difficulty with this is that one tends to become more conservative with time and does not want to risk failure because it might result in loss of funding that one does have. We were successful because we were able to persist in working on molecular liquids for twenty years. We were fortunate because the reviewers of our proposal awarded it to us. We were lucky because nature cooperated in giving us what we were looking for.

References [1] E. Wigner, H.B. Huntington: J. Chem. Phys., 3, 764 (1935). [2] S.T. Weir, A.C. Mitchell, W.J. Nellis: Phys. Rev. Lett., 76, 1860 (1996). [3] W.J. Nellis, S.T. Weir, A.C. Mitchell: Phys. Rev. B, 59, 3434 (1999). [4] W.J. Nellis: Rep. Prog. Phys., 69, 1479 (2006). [5] M. Bastea, A.C. Mitchell, W.J. Nellis: Phys. Rev. Lett., 86, 3108 (2001). [6] R. Chau, A.C. Mitchell, R.W. Minich, W.J. Nellis: Phys. Rev. Lett., 90, 245501 (2003). [7] F. Hensel, P. Edwards: Physics World, 4, 43 (1996). [8] V.E. Fortov, V.Ya. Ternovoi, M.V. Zhernokletov, M.A. Mochalov, A.L. Mikhailov, A.S. Filimonov, A.A. Pyalling, V.B. Mintsev, V.K. Gryaznov, I.L. Iosilevskii: JETP, 97, 259 (2003). [Received April 20, 2007] 2007

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