VOLUME 79, NUMBER 16 PHYSICAL REVIEW LETTERS 20OCTOBER 1997 Superfluidity in H2 Films M. C. Gordillo and D. M. Ceperley National Center for Supercomputing Applications and Department of Physics, University of Illinois at Urbana-Champaign, 405 N. Mathews Avenue, Urbana, Illinois 61801 (Received 29 April 1997) Path integral Monte Carlo calculations were used to study a 2D system of H2 molecules. The ground state on a flat substrate is a triangular lattice, a localized solid. We find that the introduction of some weakly attractive impurities (specifically alkali metal atoms) in the right concentration s,0.01 Å22d stabilizes a liquid hydrogen phase of concentration 0.04 Å22 which undergoes a Kosterlitz-Thouless superfluid transition below approximately 1.2 K. [S0031-9007(97)04345-7] PACS numbers: 67.70.+n, 67.90.+z Since hydrogen molecules are relatively light, quantum Silvera and Goldman [11], a reliable potential for simula- effects are important at low temperatures. In fact, because tions at low temperatures and pressures, and successfully 4 a para-H2 molecule is a boson and very similar to a He used for studies of H2 clusters [1] and surfaces. For ex- atom, it has been proposed that condensed molecular hy- ample, it was found [12,13] that the melting temperature drogen at low temperature could become superfluid as he- for a single monolayer of H2 molecules resting on several lium does. Unfortunately, the H2-H2 interaction is more layers of solid H2 was about 6 K, in good agreement with than 3 times as attractive as the He-He interaction, so that experimental measurements [9]. pure bulk hydrogen is solid at temperatures below 13.8 K. The H2-alkali atom interactions were modeled by a 12:6 This temperature is too high to observe superfluidity in the Lennard-Jones potential. To our knowledge, there are not liquid phase. values for s or e in the literature, so we deduced them One can reduce the tendency for hydrogen to be local- as follows. s was determined so that the minimum of the ized by decreasing the average number of neighbors of a potential would correspond to the average of the molecular H2 molecule. Monte Carlo simulations of H2 clusters with radius of H2 (determined from the density of the molecular 13 and 18 particles [1] show that there is indeed a tendency solid) and the radius of an alkali atom. e was determined for the system to be superfluid below 1 K. Much work has by the potential well felt by a H2 molecule on a alkali been devoted to studying experimentally and theoretically metal surface [14]. We used sH22K ­ 3.75 Å, eH22K ­ the behavior of H2 films in a variety of substrates, such as 9.54 K and sH22Cs ­ 4.06 Å, eH22Cs ­ 5.67 K. Our Vycor glass [2–6], MgO [7], or graphite [8,9], employing structural results depend little on the exact value of these different techniques. Unfortunately, the triple point tem- parameters. We believe that a hard-sphere interaction perature for the top layer of solid H2 is 5.74 K [9], still not would yield similar results since the attraction is weak. low enough to produce a superfluid. Our simulations were carried out in the canonical en- Here we report path integral Monte Carlo (PIMC) semble, i.e., in each run we input the temperature, the total calculations in a 2D system of p-H2 molecules to predict number of particles, and the area of the simulation cell. the conditions under which it could be superfluid. We We used an imaginary time step t ­ byM ­ 0.025 K, found that at low temperature, the stable state for a 2D H2 where b ­ 1ykBT and M is the number of time slices, surface is a solid, but we can stabilize a liquid phase by good enough for accurate quantitative predictions. The introducing certain impurities (alkali metal atoms) in the maximum number of H2 molecules used in our simulations right concentration. As a result the hydrogen undergoes a was 30. This is enough to distinguish between a 2D liquid Kosterlitz-Thouless (K-T) superfluid transition at ,1K. and a solid but not for properties near the critical tempera- PIMC is an exact simulation method, able to calcu- ture. For systems of pure hydrogen, we kept the number late thermodynamic properties of nonrelativistic bosonic of molecules constant and modified the cell size to vary the systems directly from the assumed interaction potential. density. However, when impurities were included, we kept Essentially it is a numerical method for performing ex- the cell size constant and varied the number of H2 particles. pectations of the many-body thermal density matrix using In the latter case, two different cells were used, depending Monte Carlo sampling. The method has been extensively on the assumed arrangement of the alkali atoms. First, used to calculate properties of superfluid and solid helium we used a “supercell” with dimensions 18.9 Å 3 19.7 Å, and hydrogen at low temperatures [10]. with periodic boundary conditions. This corresponds to In the simulations reported here, we assume that the a complete monolayer of 30 H2 molecules of bulk hy- H2 molecules can be represented as spherical particles in- drogen. In our simulations with this cell, we used from teracting with semiempirical potentials. For the H2-H2 1–4 K or Cs atoms on a rectangular lattice. Second, we interaction, we chose the semiempirical form given by used a supercell with 4 K atoms on a triangular lattice 3010 0031-9007y97y79(16)y3010(4)$10.00 © 1997 The American Physical Society VOLUME 79, NUMBER 16 PHYSICAL REVIEW LETTERS 20OCTOBER 1997 with dimensions 17.32 Å 3 20.0 Å with a K-K distance melting temperature in 2D (6 K) [13]. As a result, the of 10 Å. The maximum CPU time for one of these solid is essentially in the ground state. The lower curve calculations was 150 CPU hours in a Convex Exemplar shows the energy of the pure H2 film versus coverage, SPP-1200. while the other three curves display the coverage depen- One might expect the introduction of some impurities dence when potassium atoms are present. The minimum could reduce the freezing temperature of the film, and energy coverage (corresponding to the structure with the produce a stable liquid phase. However, it is necessary to lowest homogeneous coverage) varies with the number of 22 choose carefully the type and concentration of impurities impurities; for a pure H2 film it is 0.064 Å , while for to obtain the desired effect. For example, classical noble a system with four impurities on a rectangular lattice it is gases are not good candidates because their interac- 0.04 Å22. If the concentration of impurities is 2 per cell, 22 tion with an H2 molecule is stronger than between H2 the equilibrium coverage increases to 0.053 Å . Cal- molecules. We have verified that the H2 molecules coat culations with Cs impurities (not shown for reasons of the noble gas, reducing their mobility and increasing the space), give the same equilibrium coverage as potassium. coverage of minimum energy. A system with the impurities located on a triangular lat- On the contrary, an alkali metal atom achieves the pur- tice has a lower equilibrium coverage s0.038 Å22d as com- pose of lowering the density of the stable state. The at- pared to a rectangular lattice for the same concentration of traction between an alkali metal atom and an H2 molecule impurities. is one of the weakest known [14,15] so that H2 molecules In order to determine the phase of the different systems, will not stick to the impurity. To achieve a stable liquid we calculated their structure factors, Sskd, as shown in it is necessary to have a large enough concentration of im- Fig. 2. The pure H2 film at the minimum coverage has purities. The introduction of a single impurity per simula- a solid structure factor with one sharp peak at 1.7 Å21 tion cell hardly changed the equilibrium coverage. With corresponding to a triangular lattice. The same figure two impurities per unit cell, the density of the stable state shows also the Sskd of a pure H2 system at half of a is changed, but the shift is not enough to create a liquid. monolayer coverage, which is liquidlike [12,13]. How- 22 However, for a sK ­ 0.01 Å (4 K atoms per cell) the ever, a layer with this density will be unstable and sepa- number of impurities is enough to have a low temperature rate into a complete monolayer and a very low density liquid. gas. Analysis of the structure factors for different cov- 22 In Fig. 1 we show the total energy per H2 molecule, erages allows us to say that for s,0.059 Å , a pure EH2 , as a function of the hydrogen coverage at 1 K. That film of H2 molecules is a fluid. However, as one can see temperature is low enough to observe exchange, since the from Fig. 1, those liquids are unstable in comparison to thermal de Broglie wavelength is larger than the inter- a solid. molecular distance. On the other hand, 1 K is much lower than the kinetic energy in the solid phase (,20 K) and the FIG. 2. Structure factor, Sskd, for three different hydrogen films at 1 K. The upper panel is for a solid 2D film of 22 FIG. 1. Energy vs H2 coverage for four different impurity pure H2 at sH2 ­ 0.064 Å . The other two Sskd’s in the densities at 1 K: a 2D film of pure H2 (lower solid curve, lower panel are liquids: a pure 2D H2 film at 2 K with 22 plusses); 2 K atoms per simulation cell (dashed curve and 3’s); coverage 0.04 Å (full line 1 crosses), and a H2 film with 4 K atoms on a rectangular lattice (squares and dotted curve), 4 K atoms per simulation cell arranged in a triangular lattice 22 and 4 K atoms in a triangular lattice (diamonds).