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Ammonia as a case study for the spontaneous ionization of a simple hydrogen-bonded compound

Ammonia as a case study for the spontaneous ionization of a simple hydrogen-bonded compound ARTICLE Received 19 Oct 2013 | Accepted 17 Feb 2014 | Published 24 Mar 2014 DOI: 10.1038/ncomms4460 Ammonia as a case study for the spontaneous ionization of a simple hydrogen-bonded compound 1,2 1,3 1 4 5 2 Taras Palasyuk , Ivan Troyan , Mikhail Eremets , Vadym Drozd , Sergey Medvedev , Patryk Zaleski–Ejgierd , 2 1 6,7 8,w 3,5 Ewelina Magos–Palasyuk , Hongbo Wang , Stanimir A. Bonev , Dmytro Dudenko & Pavel Naumov Modern ab initio calculations predict ionic and superionic states in highly compressed water and ammonia. The prediction apparently contradicts state-of-the-art experimentally estab- lished phase diagrams overwhelmingly dominated by molecular phases. Here we present experimental evidence that the threshold pressure of B120 GPa induces in molecular ammonia the process of autoionization to yet experimentally unknown ionic compound— ammonium amide. Our supplementary theoretical simulations provide valuable insight into the mechanism of autoionization showing no hydrogen bond symmetrization along the transformation path, a remarkably small energy barrier between competing phases and the impact of structural rearrangement contribution on the overall conversion rate. This discovery is bridging theory and experiment thus opening new possibilities for studying molecular interactions in hydrogen-bonded systems. Experimental knowledge on this novel ionic phase of ammonia also provides strong motivation for reconsideration of the theory of molecular ice layers formation and dynamics in giant gas planets. 1 2 3 Max Planck Institute for Chemistry, 55128 Mainz, Germany. Institute of Physical Chemistry PAS, Warsaw 01-224, Poland. A. V. Shubnikov Institute of 4 5 Crystallography, Russian Academy of Sciences, 119333 Moscow, Russia. Florida International University, Miami, Florida 33199, USA. Max Planck Institute 6 7 for Chemical Physics of Solids, 01187 Dresden, Germany. Lawrence Livermore National Laboratory, Livermore, California 94550, USA. Department of Physics, Dalhousie University, Halifax, Nova Scotia, Canada B3H3J5. Max Planck Institute for Polymer Research, 55128 Mainz, Germany. w Present address: University of Warwick, Coventry CV4 7AL, UK. Correspondence and requests for materials should be addressed to T.P. (email: [email protected]) or to M.E. (email: [email protected]) or to P.Z.-E. (email: [email protected]). NATURE COMMUNICATIONS | 5:3460 | DOI: 10.1038/ncomms4460 | www.nature.com/naturecommunications 1 & 2014 Macmillan Publishers Limited. All rights reserved. ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms4460 ypically, molecular compounds in condensed phase exhibit formation of a new phase. Although the measured angular range primarily strong covalent intramolecular and secondary (2y) was insufficient to derive an exact structure solution, Tweak (that is, van der Waals) intermolecular bonds. diffraction patterns above 135 GPa were consistent with the External compression to higher densities is expected to promote assumed coexistence of two phases: the one of P2 2 2 and the 1 1 1 phase transformations in which electrons within intramolecular other of Pma2 symmetry (Fig. 1a,d,e). Moreover, the pressure bonds delocalize to form extended covalent framework or evolution of hkl(400) and hkl(011) reflections (the ‘D’splitting) polymeric solids, at intermediate pressure ranges, and metallic was also consistent with theoretically calculated for Pma2 1–7 phases at higher pressures . In fact, transformation of a simple structure (Fig. 1b,c). In recent density-functional-theory (DFT) molecular compound to an ionic solid upon compression is a very study, the same Pma2 symmetry has been suggested for an ionic rare phenomenon. So far, the only experimentally confirmed phase, thermodynamically stable already above 90 GPa , example is the formation of nitrosonium (NO ) nitrate although it was not experimentally confirmed in the previous (NO3 ), which forms from molecular nitrogen oxides (N O study performed on a single crystal up to 123 GPa . (refs 8–10), mixture of NO and NO (ref. 11), N O (refs 12–15)) In view of these results, further experimental characterization 2 2 4 16,17 or N /O mixture . In this particular case, depending on the of spectroscopic properties of the observed new phase was 2 2 initial substrate, the autoionization process requires higher required. For that purpose, we implemented IR absorption and pressure, elevated temperature and/or specific irradiation of Raman scattering techniques. In addition, following the theore- visible, infrared (IR) or X-ray wavelength range. At such tical suggestion from the ref. 19, we repeated DFT study for conditions, disintegration of molecules is induced promoting ammonia under pressure. We considered the thermodynamic the formation of ionic compounds via a radical-mediated stability of the known molecular (P2 2 2 ) and the proposed ionic 1 1 1 mechanism. (Pma2) phases as a function of pressure. Having reproduced the Ammonia belongs to an important group of archetypal binary previously reported relation between the enthalpies of both compounds forming molecular hydrogen-bonded (HB) solids. phases, we further performed group theory analysis to calculate On the one hand, state-of-the-art experimentally established optical phonon and molecular vibration spectra (both IR and phase diagrams of HB solids (H O, NH ,H S, HHal (Hal¼ Cl, Raman active) and their evolution under pressure. 2 3 2 Br, I)) prove the exclusive domination of molecular forms. On the Most remarkable changes in the optical spectra (both IR and other hand, modern theoretical studies intriguingly predict new Raman) were observed in the 126–133 GPa pressure range forms of water and ammonia with partial or complete charge correlating with pressures at which major changes in the XRD separation. Ionic forms are predicted to be stable at room patterns also took place. Although optical spectra changed temperature and pressure as high as B1,500 GPa and B90 GPa substantially in the whole measured spectral range 18 19 for water and ammonia , respectively. It has been also (Supplementary Fig. 1A–C), we found it instructive to describe predicted that at certain high-pressure/high-temperature (HT/ here only the most pronounced changes. HP) conditions water and ammonia become a protonic conductor in which the hydrogen atoms undergo rapid hops IR absorption. Despite relatively low resolution of the measured between neighbouring molecules forming a superionic solid or spectra unavoidable for ammonia, the most pronounced new ionic fluid . Two recent attempts aiming at verification of the feature was the appearance of a broad and intensive absorption later prediction in ammonia provided contradicting conclusions band in the wavenumber range from B1,800 to B2,700 cm making definitive experimental confirmation of new superionic (Fig. 2a,b and Supplementary Fig. 2A,B and Supplementary 21,22 form elusive . Discussion). Another major indication of phase transition was Here we undertake extensive experimental and theoretical observed in the region43,000 cm —the range of high-fre- studies in the broadest pressure range ever considered before quency molecular vibrons, which initially were associated solely (from ambient to 300 GPa) including X-ray diffraction (XRD), IR with ‘N–H’ stretching modes of NH molecules (with the max- absorption and Raman scattering measurements, in order to imum centred near 3,500 cm ). Under external pressure, that explore the possible existence of hypothetical thermodynamically group clearly shifted to the lower frequency region centred at stable, but hitherto experimentally not confirmed high-pressure B3,250 cm . Having compared the measured and calculated forms of ammonia. On the basis of obtained results, we report spectra, we associate the new broadband of enhanced absorption experimental proofs of the pressure-induced formation of (centred at B2,250 cm ) with the lower frequency group of ammonium amide (NH NH ) along with the theoretical 4 2 þ NH -derived vibrons. At the same time, the appearance of elucidation of the autoionization process in molecular ammonia additional absorption related to ‘N–H’ stretching modes related under pressure. to NH and NH ions (Fig. 2c) accounts for the red shift (shift 4 2 to lower frequencies) of measured signal43,000 cm that for- merly has been associated exclusively with ‘N–H’ stretching of Results NH molecules. Structural study. We started our studies from the pressure region We note that the measured spectrum of the known molecular for which phase composition and properties of ammonia are phase, P2 2 2 , as well as its pressure evolution, remained in good 1 1 1 relatively well established. At pressure of 70 GPa, our X-ray dif- agreement with the previously reported experimental and fraction studies performed on polycrystalline samples revealed theoretical data for both low- and high-frequency spectral diffraction patterns corresponding to the molecular form of regions (Fig. 2b,d and Supplementary Fig. 1A). Such high degree ammonia crystallizing in the P2 2 2 space group. In our XRD 1 1 1 of consistency between experimental and simulated spectra study, the stability region of the P2 2 2 form was confirmed in 1 1 1 validates theoretical models implemented in our study as well the pressure range up toB114 GPa, in agreement with previously as in ref. 19. reported experimental data . Upon further compression a gradual, but pronounced redistribution of measured intensities was observed that along with distinct splitting of one particular Raman scattering. Disappearance of strong NH -derived vibrons reflection indicated substantial structural changes (Fig. 1a). The with simultaneous appearance of two new strong signals in observed diffraction patterns at pressures above 128 GPa could Raman spectra: a broadband at B3,100 cm and well-defined not be assigned to solely P2 2 2 symmetry suggesting the peak at B3,695 cm indicating major changes of ‘N–H’ 1 1 1 2 NATURE COMMUNICATIONS | 5:3460 | DOI: 10.1038/ncomms4460 | www.nature.com/naturecommunications & 2014 Macmillan Publishers Limited. All rights reserved. NATURE COMMUNICATIONS | DOI: 10.1038/ncomms4460 ARTICLE stretching modes of ammonia. We also observed significant ab 0.5 Theory changes in the spectral range corresponding to ‘N–H’ bending Experiment Pma2 modes (B1,600–2,100 cm ). In particular, characteristic modes 0.4 of NH species (B1,600 cm ) disappeared while new signals (GPa) 3 0.3  1 appeared around B1,800–2,100 cm (Fig. 3a). The measured 0.2 Raman scattering spectra are consistent with the available experimental data in the spectral region of internal ‘N–H’ 0.1 stretching vibrations (43,000 cm ). To our best knowledge, no 0.0 experimental report on low-frequency modes (o3,000 cm ) 80 100 120 140 160 180 has been previously reported in the pressure range of this study. Pressure (GPa) We thus compared the measured frequencies with those Δ calculated for the ionic Pma2 phase (Fig. 3b,c and Supplementary Fig. 1C). On that basis, we associated the new broad signal (B3,100 cm ) with ‘N–H’ stretching while the new signals at lower frequency (B1,800 cm ) with bending vibrons of both ammonium (NH ) and amide (NH ) species. 4 2 In contrast to measured spectra, our calculated spectra yielded no Raman active mode aroundB3,695 cm for Pma2 phase. However, during pressure release run of the same sample, we P2 2 2 1 1 1 found that the measured signal was significantly less intensive in comparison with other signals belonging to Pma2 phase (Supplementary Figs 3,4 and Supplementary Discussion). At the moment, we have no unambiguous explanation for the origin of 13 14 10 11 12 13 14 15 the observed signal except the one having relation to specific 2θ (°) 2θ (°) experimental conditions like inhomogeneity of pressure. There are certain unavoidable limitations of theory in simulating experimental conditions. Theory deals with an ideal crystal structure while pressure gradients (deviatoric stresses), kinetics effects (slow diffusion) and accumulation of defects and so on, may drive distortion of crystal structure, especially during phase transformation, and hence activate some modes (by breaking certain selection rules). This may also apply to fundamental molecular modes. This explains why not all signals can be 1.0 Molecular absolutely well reproduced by theoretical calculations. 0.8 (P2 2 2 ) 1 1 1 Comparison of the measured X-ray diffraction and spectro- 0.6 Pma2 scopic data with theoretically calculated results yields a good 0.4 P2 2 2 1 1 1 agreement providing strong evidence for the pressure-induced 0.2 molecular to ionic phase transition in ammonia. We thus report 0.0 120 140 160 180 ammonia as a first experimentally confirmed example of Pressure (GPa) pressure-induced complete ionic disproportionation of a binary HB compound. Indeed, it stands out from other HB solids in which ionic disproportionation is predicted to exhibit a dynamical (for example, H O (ref. 26), H S (ref. 27)) or still an 2 2 8 9 10 11 12 13 14 15 16 17 incomplete character under extreme conditions (for example, 2θ (°) H O (ref. 18)). Figure 1 | Structural study of solid ammonia under pressure. (a) Representative room temperature X-ray diffraction patterns at various pressure acquired at HPCAT beamline (l¼ 0.4125 Å). Reflections belonging Discussion to P2 2 2 and Pma2 are marked blue and magenta, respectively. Arrows are We now focus on a possible mechanism of the disproportionation 1 1 1 an eye guide for evolution of reflections hkl(400) and hkl(011) belonging to process in ammonia. Structural comparison of the low-pressure Pma2 space group proposed in ref. 19. (b) Enlarged view of XRD patterns. molecular and the high-pressure ionic phases reveals crucial clues Splitting is defined as ‘D’ – difference between the position of hhl(011) and on the underlying mechanism of the observed phase transition. hkl(400) reflections. (c). Pressure evolution of splitting. Comparison of First, from the structural point of view (Supplementary Fig. 5), calculated and experimentally measured data (dot curve is an eye guide). the transition from the molecular to the ionic phases involves a (d) Fragment of the experimental 2D CCD diffraction image corresponding to shift of closed packed planes: it thus resembles the well-known the integrated pattern shown in e.(e) Room temperature XRD pattern reversible hcp-to-fcc phase transition observed in relatively acquired at GSECARS beamline (l¼ 0.3,344 Å). Reflections (hkl)¼ (400) simple (for example, noble gases ) and more complex systems 29,30 and (011) are clearly resolved. Black curve represents integrated experi- (yttrium and other lanthanide trihydrides ). Indeed, the mental XRD pattern, blue (royal) and magenta curves correspond to experimentally observed continuous character of the intensity calculated patterns for P2 2 2 and Pma2 structure, respectively. The same change of the hkl(020) (molecular) and the hkl(210) (ionic) 1 1 1 applies to tick marks. Inset (left): a representative microphotograph of a reflections (Fig. 1a) provides direct evidence on the engagement sample chamber filled with solidified transparent ammonia taken under of those close packed layers and it also corroborates a quasi hcp- combined transmitted and reflected illumination at pressure 172 GPa. Gasket to-fcc nature of the transition. material was tungsten. Length of the scale bar corresponds to 50mm. Inset Second, in the molecular phase (P2 2 2 ), one can distinguish 1 1 1 (right): pressure evolution of the abundance of P2 2 2 phase (estimation is two types of hydrogen bonding with respect to the angle in the 1 1 1 based on the analysis of experimental and calculated XRD patterns). ‘N–H N’ fragment: an ‘intra-plane’ bond with the angle value of NATURE COMMUNICATIONS | 5:3460 | DOI: 10.1038/ncomms4460 | www.nature.com/naturecommunications 3 & 2014 Macmillan Publishers Limited. All rights reserved. Intensity (a.u.) Intensity (a.u.) Δ (degree) Abundance Intensity (a.u.) 400 011 011 ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms4460 ab c P2 2 2 Pma2 1 1 1 Theory (GPa) 100% (GPa) 3,500 3,000 0 2,000 4,000 0 2,000 4,000 –1 Wavenumber (cm ) 2,500 Stretching Lattice Bending modes modes modes 88 (GPa) Experiment 2,000 100% Tr Rot u 3 2 u 4 Theory 0 1,000 2,000 3,000 4,000 0 40 80 120 160 0 1,000 2,000 3,000 4,000 –1 –1 Wavenumber (cm ) Pressure (GPa) Wavenumber (cm ) Figure 2 | IR absorption study of solid ammonia under pressure. (a) Representative room temperature IR absorption spectra at various pressures. Colours depict features attributed to molecular phase (blue (royal)) and ionic (magenta) phases, respectively. The spectral region of ‘N–H’ stretching band corresponding to molecular phase is highlighted blue. New band of strong absorption not related to the molecular phase is highlighted pink. Blue arrow is an eye guide for pressure evolution of the soft ‘N–H’ stretching mode due to hydrogen bonding. (b). Pressure evolution of the measured positions of signals in the wavenumber range from 1,800–4,000 cm . Symbols represent experimental data while lines represent calculated data from ref. 19. Line thickness corresponds to signal intensity. Solid dark blue symbols correspond to experimental data reported in ref. 24 while solid light blue outlined symbols represent data measured in this work. Blue and magenta highlighted fields correspond to measured strong absorption associated with the molecular and the ionic phase respectively. (c) Comparison of theoretically calculated IR absorption spectra and their evolution with pressure. (d) Comparison of IR absorption spectra measured at 67 GPa and calculated at 60 GPa. ab c 3,800 (GPa) 3,600 2,000 3,400 1,800 3,200 88 3,000 1,600 2,800 2,000 3,000 4,000 80 120 160 80 120 160 –1 Raman shift (cm ) Pressure (GPa) Pressure (GPa) Figure 3 | Raman scattering study in solid ammonia under pressure. (a) Representative Raman spectra of solid ammonia collected at different pressures (fragment of high-frequency spectral range). The signal related to the second order Raman signal of diamond anvil is grey shadowed. Colours depict features attributed to molecular phase (blue (royal)) and ionic (magenta) phases, respectively. The light blue highlighted peak corresponds to the Raman signal associated with the most labile hydrogen bonding. (b,c) Pressure evolution of Raman shifts. Grey shadowed regions correspond to the signal of diamond anvil (the first and the second order Raman in b and c, respectively). Lines and symbols correspond to calculated and experimentally measured data. Thickness of lines and size of symbols correspond to intensities of presented data. The rest of colours and symbols designation is similar to that in a. 4 NATURE COMMUNICATIONS | 5:3460 | DOI: 10.1038/ncomms4460 | www.nature.com/naturecommunications & 2014 Macmillan Publishers Limited. All rights reserved. Raman intensity (a.u.) Absorption (a.u.) –1 Raman shift (cm ) –1 Wavenumber (cm ) –1 Raman shift (cm ) Absorption (a.u.) Absorption (a.u.) NATURE COMMUNICATIONS | DOI: 10.1038/ncomms4460 ARTICLE B158 and an ‘inter-plane’ bond with the angle value close to Phase A B169 (Supplementary Fig. 5). According to experimental Phase B spectroscopic data, the most labile hydrogen bond, the one 0.1 exhibiting strong softening in both the IR and Raman spectra, is Phase C located between the closely packed layers. We therefore call this bond ‘inter-plane’. We found that a gradual, pressure-induced elongation of the covalent component (‘N–H’) leads to complete proton transfer from one neutral NH molecule of to the other, ΔH* resulting in formation of the NH /NH pairs at B127 GPa. 4 2 –0.1 The resulting Pma2 arrangement, features a remarkably low anisotropy of the hydrogen bonds (B165 and B163 for ‘inter-‘ Phase A Phase B Phase C and ‘intra’plane type, respectively), much lower than in the case –0.2 of molecular P2 2 2 , phase. 1 1 1 At this point, one can clearly distinguish two major stages governing the observed molecular to ionic phase transition: the –0.3 first is the process of ‘interplane’ proton transfer; the second is the stage of structural rearrangement (in particular, sliding of the closely packed layers). Based on the spectroscopic observations, –0.4 Ionic Post-ionic/molecular Molecular we believe that the proton transfer ‘starts’ first at pressures well (exp.; Pma2) (model; eff.Pc) (exp.; P2 2 2 ) 1 1 1 below the observed actual structural transformation. Nonetheless, a definite answer to the question on which of the stages drives the phase transition is a matter of discussion, and, at this moment, 50 100 150 200 250 falls beyond the scope of the present paper. Pressure (GPa) We note, however, that the experimentally observed reversibility of the transformation points to the fact that Figure 4 | Description of hypothetical intermediate phase. Calculated curves for enthalpy difference (DH) for the three considered phases of ‘interplane’ proton transfer can effectively occurs within layers of quasi closely packed nitrogen atoms in either P2 2 2 or ammonia. Enthalpy of the high-pressure, ionic Pma2 (Phase A) establishes 1 1 1 the reference (zero) line. Note the convergence of the absolute enthalpy of Pma2. Intuitively, a gradual ionization of the initial molecular P2 2 2 phase with subsequent structural transformation to the experimental molecular P2 2 2 (Phase C) with the enthalpy of the 1 1 1 1 1 1 hypothetical model molecular Pc (Phase B) with the decreasing pressure. Pma2 phase also looks plausible; however, at this moment, we are ruling this possibility out. If the assumed reaction path was As an example, the enthalpy difference (DH*) corresponding to the proton transfer contribution calculated at pressure of 25 GPa is shown. Insets realized via an intermediate phase, ionized via proton transfer with the P2 2 2 symmetry preveserved, one would have expected illustrate schematically the structural similarities of the three phases 1 1 1 considered. signs of disproportionation/ionization at pressure range well preceding the pressure of the structural phase transition observed in the XRD data (the appearance of NH - and NH -related energy required for the proton transfer. The remaining difference 4 2 gives highly specific IR absorption bands and Raman signals, in energy (between the model molecular phase (Pc) and which is difficult to omit). Instead, both the spectroscopic and the experimentally observed one (P2 2 2 ) is associated with the 1 1 1 structural changes were observed in a narrow pressure range process of structural rearrangement. of 5–10 GPa indicating a simultaneous character of the trans- We therefore consider the Pc phase as a good approximation to formation. Furthermore, according to our DFT calculations, the experimental molecular phase and use it to model NH /NH 3 3 such intermediate ionic phase (ionic P2 2 2 ) is dynamically to NH /NH transition mechanism and calculate the associated 1 1 1 4 2 unstable below 50 GPa and relaxes spontaneously to the known energy changes. phase (molecular P2 2 2 ). On the contrary, an intermediate Because of the intermediate character of the hypothetical Pc 1 1 1 molecular phase of Pma2 symmetry is meta-stable below 50 GPa phase (both energetically and structurally), a simple proton featuring a local minimum in total energy profile: moreover, our transfer from one NH molecule to a neighbouring one results in calculation indicates that such meta-stable phase is separated a smooth transition from molecular to ionic phase (Fig. 5a). To from the ionic Pma2 phase by an exceedingly small, yet distinct, investigate the abovementioned implications of pressure-induced þ þ energy barrier. H transfer, resulting in NH /NH to NH /NH transition, we 3 3 4 2 For better understanding the proposed phase transition, we have modelled the process between the NH molecules in introduce a hypothetical molecular phase with the effective molecular phase and in 1-, 2- and 3-dimensional solids symmetry Pc, which is derived directly from the Pma2 (Fig. 4). (Supplementary Figs 6–9 and Supplementary Discussion). The This model structure exhibits a number of advantageous features resulting energy profiles for 3-dimensional solid are given in allowing for qualitative and quantitative analysis of the molecular Fig. 5b. to ionic phase transition. It shares features of both the ionic phase Although height of the energy barrier remains relatively small (arrangement of the nitrogen atoms, the shape and volume of the for all pressures, its presence effectively precludes N–H N bond unit cell are effectively identical as in the ionic phase) and the symmetrization, in contrast to highly compressed water, for molecular one (easily distinguishable, isolated ammonia mole- which the symmetrization occurs at PB100 GPa (ref. 31). cules). We note, that the difference between the hypothetical Note also the increasing contribution of the structural molecular (Pc) and the experimental molecular (P2 2 2 ) arises rearrangement process. In contrast to lower pressures at which 1 1 1 only from different NH packing–quasi fcc versus quasi hcp, the major part of energy is consumed for hydrogen transfer, the respectively. Calculated enthalpy corroborates the intermediate crystal structure rearrangement seems to become determinative at character of the Pc phase (Fig. 4). Furthermore, at this point, one higher pressures. This assumption qualitatively account for the can easily distinguish two types of energy contribution. Since we experimentally observed coexistence of two phases. According to assume the similarity (with respect to crystal structure) of the our XRD and Raman spectroscopy studies, the molecular phase Pma2 and Pc phases, the enthalpy difference (DH*) reflects the persists up to at least 172 GPa (Fig.1e inset). Moreover, in an NATURE COMMUNICATIONS | 5:3460 | DOI: 10.1038/ncomms4460 | www.nature.com/naturecommunications 5 & 2014 Macmillan Publishers Limited. All rights reserved. ΔH (eV per molecule) ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms4460 a b 65 GPa 50 GPa 25 GPa 0.1 10 GPa Phase B 0 GPa Phase A NH /NH 3 3 –0.1 –0.2 + – –0.3 NH /NH 4 2 –0.4 Molecular Ionic (Pc) (Pma2) Ionic Molecular (Pma2) (eff. Pc) Phase A Phase B Figure 5 | Modelling the mechanism of the autoionization in solid ammonia. (a) Schematic illustration of the computational scheme used to determine the minimal energy path of H transferred during the molecular to ionic phase transition. Red spheres indicate the ‘bridging’ hydrogen atoms transferred from one NH molecule to the other resulting in formation of the NH /NH ionic pair. (b) Calculated energy profiles depicting the enthalpy changes, DH*, 3 4 2 associated with the proton transfer between experimentally observed ionic phase and the proposed molecular phase of ammonia. Here, the calculated enthalpy of the ionic phase is set to 0. At the low-pressure limit (P-0 GPa) the ionic phase (Pma2) is calculated to be dynamically unstable. Upon relaxation, it spontaneously transforms into phase exhibiting purely molecular character. However, upon compression, the ionic phase stabilizes and already at PB10 GPa, our model predicts formation of two minima, separated by an energy barrier. At lower pressures, the molecular minimum is strongly favored. According to the proposed model, transition from Phase A to Phase B occurs spontaneously at the low-pressure limit. With increasing pressure, the model molecular Phase B destabilizes. At B62 GPa, the two structures exhibit enthalpy degeneracy and at P470 GPa spontaneously transforms into the ionic one. Both structures remain separated by a small, yet persistent energy barrier of B10 meV (calculated per NH molecule). additional XRD runs, a significant amount of P2 2 2 phase was We hope that the reported experimental evidence on the new 1 1 1 still detected, even up to the highest pressure of B203 GPa form of ammonia and the observed peculiar behaviour of (Supplementary Fig. 10 and Supplementary Discussion). hydrogen bonds under pressure will stimulate further experi- Finally, we note that the P2 2 2 -Pma2 transition is mental as well as further theoretical research on new forms of 1 1 1 predicted to occur at a pressure close to 90 GPa (ref. 19 and simple HB systems in general and in particular, on the conductive this study Fig. 4) yet is experimentally observed at pressures properties of the ionic ammonia, which may turn to be critical for close to 130 GPa. This discrepancy may in part be due to athermal better understanding the observed properties of giant planets in nature of the calculations where all entropic contributions our solar system. are neglected. In conclusion, ammonia presents a qualitatively new picture of Methods HB solid under pressure. Our detailed study provides first Experimental methods. Number of successful (pressure achieved4150 GPa) experiments:Raman—5 (including two pressure release runs). Re gaskets were used experimental evidence of the pressure-induced complete proton in two measurements, W gaskets were used in other three experiments. Combined transfer resulting in the formation of the ionic phase (formation (IRþ Raman)—5 (all were carried out using W gaskets with Au-lining), XRD of NH /NH pairs) in compressed solid ammonia. The proton 4 2 (synchrotron) measurements—6 (gasket materials: Re without Au-lining (2 transfer is found to be a continuous and reversible process measurements), W without Au-lining (four measurements)). Size of sample varied starting already at ambient pressure and completing at B125 depending on the technique used. Generally for the XRD and Raman measure- ments samples were of B10–12 mm initial thickness andB35 mm in diameter. For GPa. In fact, such a wide range of hydrostatic pressure required IR measurements, samples were significantly thinner (initial thickness t1mm) in for proton transfer is unprecedented. The final stage of order to get better resolved spectrum, especially, in the region of strong absorption autoionization process is found to be accompanied by the quasi of N–H molecular vibrations. first order transformation resembling a quasi hexagonal to cubic The Raman spectrum of diamond anvil was used for pressure calibration. Moreover, during XRD measurements ‘diamond-Raman-edge’ scale was cross- structural phase transition. checked by pressure estimation from equation of state of gasket materials (W, Re or Our theoretical calculations provide a deep insight into the Au). Neither diamond anvils nor gaskets were subjected to any passivation. mechanism underlying the observed phenomenon indicating no For experiments, samples of liquefied ammonia were loaded into diamond anvil hydrogen-bond symmetrization on the whole reaction path and cells in the temperature range 195–240 K. Beveled diamonds with a culet diameter of 100 mm (and less) were used to reach pressures above 1 mbar. Gasket holes were remarkably small energy barrier between competitive phases. An prepared using IR laser drilling. Angle dispersive X-ray diffraction studies were increasing energy cost of the structural rearrangement compo- conducted at the Advanced Photon Source (HPCAT, GSECARS), Argonne nent to the total energy is suggested to account for the overall National Laboratory, USA and European Synchrotron Radiation Facility (ID 9, ID slowing down of the autoionization process confirmed by the 27). Raman scattering was excited using a 25 mW HeNe (632.8 nm) laser. Raman spectra were collected in backscattered geometry using a single imaging spectro- experimental observation of the molecular form up to 203 GPa. meter HR460 (focal length 460 mm) equipped with a 900 grooves per mm grating, This unique scenario has no analogy among other known simple giving a resolution of B1cm , notch filters (Keiser Optical Systems) and liquid HB system such as water (H O), hydrogen halides (HCl, HBr and nitrogen cooled CCD detection. IR absorption spectra were measured in so on) or H S for which compression leads to either hydrogen transmission mode using Fourier transform IR) spectrometer (Bruker Equinox 55) bonds symmetrization or decomposition. equipped with a glow-bar source, KBr beamsplitter and MCT detector (HgCdTe). To 6 NATURE COMMUNICATIONS | 5:3460 | DOI: 10.1038/ncomms4460 | www.nature.com/naturecommunications & 2014 Macmillan Publishers Limited. All rights reserved. ΔH (eV per molecule) NATURE COMMUNICATIONS | DOI: 10.1038/ncomms4460 ARTICLE avoid spectra contamination by strong absorption lines of H Oand CO molecules 2 2 18. Wang, Y. et al. High pressure partially ionic phase of water ice. Nat. Commun. from the air, sample chamber of the spectrometer was purged with dry nitrogen. 2, 563 (2011). 19. Pickard, C. J. & Needs, R. J. Highly compressed ammonia forms an ionic crystal. Nat. Mat. 7, 775–779 (2008). Details of theoretical calculations. 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Alloys Comp. 446-447, 593–597 (2007). functional perturbation theory). Raman and IR intensities were calculated using the 31. Benoit, M., Marx, D. & Parrinello, M. Tunnelling and zero-point motion in formalism presented in refs 32,33. high-pressure ice. Nature 392, 258–261 (1998). 32. Porezag, D. & Pederson, M. R. Infrared intensities and Raman-scattering References activities within density-functional theory. Phys. Rev. B 54, 7830 (1996). 1. Hemley, R. J. Effect of high pressure on molecules. Annu. Rev. Phys. Chem. 51, 33. Gonze, X. & Lee, C. Dynamical matrices, Born effective charges, dielectric 763–800 (2000). permittivity tensors, and interatomic force constants from density-functional 2. Iota, V., Yoo, C. S. & Cynn, H. Quartzlike carbon dioxide: an optically perturbation theory. Phys. Rev. B 55, 10355 (1997). nonlinear extended solid at high pressures and temperatures. Science 283, 1510–1513 (1999). 3. Lipp, M. J., Evans, W. J., Baer, B. J. & Yoo, C.-S. High-energy density extended Acknowledgements CO solid. Nat. Mat. 4, 211–215 (2005). We gratefully acknowledge the expert and technical support during structural studies at 4. Goncharov, A. F., Gregoryanz, E., Mao, H.-K., Liu, Z. & Hemley, R. J. Optical synchrotron facilities of Advanced Photon Source (HPCAT (Stanislav Sinogejkin), evidence for a nonmolecular phase of nitrogen above 150 GPa. Phys. Rev. Lett. GSECARS (Vitali Prakapenka)) and European Synchrotron Radiation Facility (ID 27 85, 1262–1265 (2000). (Mohamed Mezouar), ID 9 (Michael Hanfland)). Authors are grateful to Prof. Marek 5. Eremets, M. I., Hemley, R. J., Mao, H.-K. & Gregoryanz, E. Semiconducting Tkacz and Prof Surendra Saxena for fruitful comments. A significant experimental part non-molecular nitrogen up to 240 GPa and its low-pressure stability. Nature of the work was done in 2008–2009 within the ‘KOLUMB’ Program (19th edition, 2008) 411, 170–174 (2001). of the Foundation for Polish Science which support is gratefully acknowledged by T.P. 6. Akahama, Y., Kawamura, H., Hausermann, D., Hanfland, M. & Shimomura, O. The support within the SPP1236 Program (ER 539/5-1) and DFG R530/6-1 grant is New High-pressure structural transition of oxygen at 96 GPa associated with gratefully acknowledged by T.P., I.T., M.E., S.M., H.W. and P.N. Work at LLNL per- metallization in a molecular solid. Phys. Rev. Lett. 74, 4690–4693 (1995). formed by S.A.B. was under the auspices of the US DOE. The support within the grant of 7. Desgreniers, S., Vohra, Y. K. & Ruoff, A. L. Optical response of very high the Polish National Science Centre nr 2011/01/M/ST3/00855 is gratefully acknowledged density solid oxygen to 132 GPa. J. Phys. Chem. 94, 1117–1122 (1990). by T.P., P.Z.-E and E.M.-P. (program ‘‘HARMONIA’’). 8. Somayazulu, M. et al. Novel broken symmetry phase from N O at high pressures and high temperatures. Phys. Rev. Lett. 87, 135504 (2001). 9. Yoo, C. S. et al. Disproportionation and other transformations of N O at high pressures and temperatures to lower energy, denser phases. J. Phys. Chem. B Author contributions 107, 5922–5925 (2003). The manuscript was written through contributions of all authors. All authors have given 10. Song, Y., Somayazulu, M., Mao, H.-K., Hemley, R. J. & Herschbach, D. R. High- approval to the final version of the manuscript. M.E., T.P. and I.T. conceived the pressure structure and equation of state study of nitrosonium nitrate from research. M.E., T.P. and I.T. conceived the research performed the experiments. T.P. synchrotron x-ray diffraction. J. Chem. Phys. 118, 8350–8356 (2003). proposed the model of the autoionization mechanism and P.Z.-E. performed relevant 11. Agnew, S. F., Swanson, B. I., Jones, L. H. & Mills, R. L. Disproportionation of DFT calculations. T.P., V.D. and S.M. contributed substantially to the analysis of nitric oxide at high pressure. J. Phys. Chem. 89, 1678–1682 (1985). structural and spectroscopic data. T.P. wrote the paper. V.D. and S.A.B. did the calcu- 12. Agnew, S. F., Swanson, B. I., Jones, L. H., Mills, R. L. & Schiferl, D. Chemistry of lations of the phonon spectra. E.M.-P., H.W., D.D., and P.N. contributed equally and N O at high pressure: observation of are versible transformation between 2 4 helped a lot in analysing the data. T.P. wrote the paper. molecular and ionic crystalline forms. J. Phys. Chem. 87, 5065–5068 (1983). 13. Bolduan, F., Jodl, H. J. & Loewenschuss, A. Raman study of solid N O : 2 4 temperature induced autoionization. J. Chem. Phys. 80, 1739–1743 (1984). Additional information 14. Song, Y., Hemley, R. J., Mao, H.-K., Liu, Z. & Herschbach, D. R. New phases of Supplementary Information accompanies this paper at http://www.nature.com/ N O at high pressures and high temperatures. Chem. Phys. Lett. 382, 686–692 2 4 (2003). naturecommunications 15. Song, Y. et al. High-pressure stability, transformations, and vibrational Competing financial interests: The authors declare no competing financial interests. dynamics of nitrosonium nitrate from synchrotron infrared and Raman spectroscopy. J. Chem. Phys. 119, 2232–2240 (2003). Reprints and permission information is available online at http://npg.nature.com/ 16. Sihachakr, D. & Loubeyre, P. High-pressure transformation of N /O mixtures 2 2 reprintsandpermissions/ into ionic compounds. Phys. Rev. B 74, 064113 (2006). 17. Meng, Y. et al. Hard x-ray radiation induced dissociation of N and O How to cite this article: Palasyuk, T. et al. Ammonia as a case study for the spontaneous 2 2 molecules and the formation of ionic nitrogen oxide phases under pressure. ionization of a simple hydrogen-bonded compound. Nat. Commun. 5:3460 Phys. Rev. B 74, 214107 (2006). doi: 10.1038/ncomms4460 (2014). NATURE COMMUNICATIONS | 5:3460 | DOI: 10.1038/ncomms4460 | www.nature.com/naturecommunications 7 & 2014 Macmillan Publishers Limited. All rights reserved. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Nature Communications Springer Journals

Ammonia as a case study for the spontaneous ionization of a simple hydrogen-bonded compound

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ARTICLE Received 19 Oct 2013 | Accepted 17 Feb 2014 | Published 24 Mar 2014 DOI: 10.1038/ncomms4460 Ammonia as a case study for the spontaneous ionization of a simple hydrogen-bonded compound 1,2 1,3 1 4 5 2 Taras Palasyuk , Ivan Troyan , Mikhail Eremets , Vadym Drozd , Sergey Medvedev , Patryk Zaleski–Ejgierd , 2 1 6,7 8,w 3,5 Ewelina Magos–Palasyuk , Hongbo Wang , Stanimir A. Bonev , Dmytro Dudenko & Pavel Naumov Modern ab initio calculations predict ionic and superionic states in highly compressed water and ammonia. The prediction apparently contradicts state-of-the-art experimentally estab- lished phase diagrams overwhelmingly dominated by molecular phases. Here we present experimental evidence that the threshold pressure of B120 GPa induces in molecular ammonia the process of autoionization to yet experimentally unknown ionic compound— ammonium amide. Our supplementary theoretical simulations provide valuable insight into the mechanism of autoionization showing no hydrogen bond symmetrization along the transformation path, a remarkably small energy barrier between competing phases and the impact of structural rearrangement contribution on the overall conversion rate. This discovery is bridging theory and experiment thus opening new possibilities for studying molecular interactions in hydrogen-bonded systems. Experimental knowledge on this novel ionic phase of ammonia also provides strong motivation for reconsideration of the theory of molecular ice layers formation and dynamics in giant gas planets. 1 2 3 Max Planck Institute for Chemistry, 55128 Mainz, Germany. Institute of Physical Chemistry PAS, Warsaw 01-224, Poland. A. V. Shubnikov Institute of 4 5 Crystallography, Russian Academy of Sciences, 119333 Moscow, Russia. Florida International University, Miami, Florida 33199, USA. Max Planck Institute 6 7 for Chemical Physics of Solids, 01187 Dresden, Germany. Lawrence Livermore National Laboratory, Livermore, California 94550, USA. Department of Physics, Dalhousie University, Halifax, Nova Scotia, Canada B3H3J5. Max Planck Institute for Polymer Research, 55128 Mainz, Germany. w Present address: University of Warwick, Coventry CV4 7AL, UK. Correspondence and requests for materials should be addressed to T.P. (email: [email protected]) or to M.E. (email: [email protected]) or to P.Z.-E. (email: [email protected]). NATURE COMMUNICATIONS | 5:3460 | DOI: 10.1038/ncomms4460 | www.nature.com/naturecommunications 1 & 2014 Macmillan Publishers Limited. All rights reserved. ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms4460 ypically, molecular compounds in condensed phase exhibit formation of a new phase. Although the measured angular range primarily strong covalent intramolecular and secondary (2y) was insufficient to derive an exact structure solution, Tweak (that is, van der Waals) intermolecular bonds. diffraction patterns above 135 GPa were consistent with the External compression to higher densities is expected to promote assumed coexistence of two phases: the one of P2 2 2 and the 1 1 1 phase transformations in which electrons within intramolecular other of Pma2 symmetry (Fig. 1a,d,e). Moreover, the pressure bonds delocalize to form extended covalent framework or evolution of hkl(400) and hkl(011) reflections (the ‘D’splitting) polymeric solids, at intermediate pressure ranges, and metallic was also consistent with theoretically calculated for Pma2 1–7 phases at higher pressures . In fact, transformation of a simple structure (Fig. 1b,c). In recent density-functional-theory (DFT) molecular compound to an ionic solid upon compression is a very study, the same Pma2 symmetry has been suggested for an ionic rare phenomenon. So far, the only experimentally confirmed phase, thermodynamically stable already above 90 GPa , example is the formation of nitrosonium (NO ) nitrate although it was not experimentally confirmed in the previous (NO3 ), which forms from molecular nitrogen oxides (N O study performed on a single crystal up to 123 GPa . (refs 8–10), mixture of NO and NO (ref. 11), N O (refs 12–15)) In view of these results, further experimental characterization 2 2 4 16,17 or N /O mixture . In this particular case, depending on the of spectroscopic properties of the observed new phase was 2 2 initial substrate, the autoionization process requires higher required. For that purpose, we implemented IR absorption and pressure, elevated temperature and/or specific irradiation of Raman scattering techniques. In addition, following the theore- visible, infrared (IR) or X-ray wavelength range. At such tical suggestion from the ref. 19, we repeated DFT study for conditions, disintegration of molecules is induced promoting ammonia under pressure. We considered the thermodynamic the formation of ionic compounds via a radical-mediated stability of the known molecular (P2 2 2 ) and the proposed ionic 1 1 1 mechanism. (Pma2) phases as a function of pressure. Having reproduced the Ammonia belongs to an important group of archetypal binary previously reported relation between the enthalpies of both compounds forming molecular hydrogen-bonded (HB) solids. phases, we further performed group theory analysis to calculate On the one hand, state-of-the-art experimentally established optical phonon and molecular vibration spectra (both IR and phase diagrams of HB solids (H O, NH ,H S, HHal (Hal¼ Cl, Raman active) and their evolution under pressure. 2 3 2 Br, I)) prove the exclusive domination of molecular forms. On the Most remarkable changes in the optical spectra (both IR and other hand, modern theoretical studies intriguingly predict new Raman) were observed in the 126–133 GPa pressure range forms of water and ammonia with partial or complete charge correlating with pressures at which major changes in the XRD separation. Ionic forms are predicted to be stable at room patterns also took place. Although optical spectra changed temperature and pressure as high as B1,500 GPa and B90 GPa substantially in the whole measured spectral range 18 19 for water and ammonia , respectively. It has been also (Supplementary Fig. 1A–C), we found it instructive to describe predicted that at certain high-pressure/high-temperature (HT/ here only the most pronounced changes. HP) conditions water and ammonia become a protonic conductor in which the hydrogen atoms undergo rapid hops IR absorption. Despite relatively low resolution of the measured between neighbouring molecules forming a superionic solid or spectra unavoidable for ammonia, the most pronounced new ionic fluid . Two recent attempts aiming at verification of the feature was the appearance of a broad and intensive absorption later prediction in ammonia provided contradicting conclusions band in the wavenumber range from B1,800 to B2,700 cm making definitive experimental confirmation of new superionic (Fig. 2a,b and Supplementary Fig. 2A,B and Supplementary 21,22 form elusive . Discussion). Another major indication of phase transition was Here we undertake extensive experimental and theoretical observed in the region43,000 cm —the range of high-fre- studies in the broadest pressure range ever considered before quency molecular vibrons, which initially were associated solely (from ambient to 300 GPa) including X-ray diffraction (XRD), IR with ‘N–H’ stretching modes of NH molecules (with the max- absorption and Raman scattering measurements, in order to imum centred near 3,500 cm ). Under external pressure, that explore the possible existence of hypothetical thermodynamically group clearly shifted to the lower frequency region centred at stable, but hitherto experimentally not confirmed high-pressure B3,250 cm . Having compared the measured and calculated forms of ammonia. On the basis of obtained results, we report spectra, we associate the new broadband of enhanced absorption experimental proofs of the pressure-induced formation of (centred at B2,250 cm ) with the lower frequency group of ammonium amide (NH NH ) along with the theoretical 4 2 þ NH -derived vibrons. At the same time, the appearance of elucidation of the autoionization process in molecular ammonia additional absorption related to ‘N–H’ stretching modes related under pressure. to NH and NH ions (Fig. 2c) accounts for the red shift (shift 4 2 to lower frequencies) of measured signal43,000 cm that for- merly has been associated exclusively with ‘N–H’ stretching of Results NH molecules. Structural study. We started our studies from the pressure region We note that the measured spectrum of the known molecular for which phase composition and properties of ammonia are phase, P2 2 2 , as well as its pressure evolution, remained in good 1 1 1 relatively well established. At pressure of 70 GPa, our X-ray dif- agreement with the previously reported experimental and fraction studies performed on polycrystalline samples revealed theoretical data for both low- and high-frequency spectral diffraction patterns corresponding to the molecular form of regions (Fig. 2b,d and Supplementary Fig. 1A). Such high degree ammonia crystallizing in the P2 2 2 space group. In our XRD 1 1 1 of consistency between experimental and simulated spectra study, the stability region of the P2 2 2 form was confirmed in 1 1 1 validates theoretical models implemented in our study as well the pressure range up toB114 GPa, in agreement with previously as in ref. 19. reported experimental data . Upon further compression a gradual, but pronounced redistribution of measured intensities was observed that along with distinct splitting of one particular Raman scattering. Disappearance of strong NH -derived vibrons reflection indicated substantial structural changes (Fig. 1a). The with simultaneous appearance of two new strong signals in observed diffraction patterns at pressures above 128 GPa could Raman spectra: a broadband at B3,100 cm and well-defined not be assigned to solely P2 2 2 symmetry suggesting the peak at B3,695 cm indicating major changes of ‘N–H’ 1 1 1 2 NATURE COMMUNICATIONS | 5:3460 | DOI: 10.1038/ncomms4460 | www.nature.com/naturecommunications & 2014 Macmillan Publishers Limited. All rights reserved. NATURE COMMUNICATIONS | DOI: 10.1038/ncomms4460 ARTICLE stretching modes of ammonia. We also observed significant ab 0.5 Theory changes in the spectral range corresponding to ‘N–H’ bending Experiment Pma2 modes (B1,600–2,100 cm ). In particular, characteristic modes 0.4 of NH species (B1,600 cm ) disappeared while new signals (GPa) 3 0.3  1 appeared around B1,800–2,100 cm (Fig. 3a). The measured 0.2 Raman scattering spectra are consistent with the available experimental data in the spectral region of internal ‘N–H’ 0.1 stretching vibrations (43,000 cm ). To our best knowledge, no 0.0 experimental report on low-frequency modes (o3,000 cm ) 80 100 120 140 160 180 has been previously reported in the pressure range of this study. Pressure (GPa) We thus compared the measured frequencies with those Δ calculated for the ionic Pma2 phase (Fig. 3b,c and Supplementary Fig. 1C). On that basis, we associated the new broad signal (B3,100 cm ) with ‘N–H’ stretching while the new signals at lower frequency (B1,800 cm ) with bending vibrons of both ammonium (NH ) and amide (NH ) species. 4 2 In contrast to measured spectra, our calculated spectra yielded no Raman active mode aroundB3,695 cm for Pma2 phase. However, during pressure release run of the same sample, we P2 2 2 1 1 1 found that the measured signal was significantly less intensive in comparison with other signals belonging to Pma2 phase (Supplementary Figs 3,4 and Supplementary Discussion). At the moment, we have no unambiguous explanation for the origin of 13 14 10 11 12 13 14 15 the observed signal except the one having relation to specific 2θ (°) 2θ (°) experimental conditions like inhomogeneity of pressure. There are certain unavoidable limitations of theory in simulating experimental conditions. Theory deals with an ideal crystal structure while pressure gradients (deviatoric stresses), kinetics effects (slow diffusion) and accumulation of defects and so on, may drive distortion of crystal structure, especially during phase transformation, and hence activate some modes (by breaking certain selection rules). This may also apply to fundamental molecular modes. This explains why not all signals can be 1.0 Molecular absolutely well reproduced by theoretical calculations. 0.8 (P2 2 2 ) 1 1 1 Comparison of the measured X-ray diffraction and spectro- 0.6 Pma2 scopic data with theoretically calculated results yields a good 0.4 P2 2 2 1 1 1 agreement providing strong evidence for the pressure-induced 0.2 molecular to ionic phase transition in ammonia. We thus report 0.0 120 140 160 180 ammonia as a first experimentally confirmed example of Pressure (GPa) pressure-induced complete ionic disproportionation of a binary HB compound. Indeed, it stands out from other HB solids in which ionic disproportionation is predicted to exhibit a dynamical (for example, H O (ref. 26), H S (ref. 27)) or still an 2 2 8 9 10 11 12 13 14 15 16 17 incomplete character under extreme conditions (for example, 2θ (°) H O (ref. 18)). Figure 1 | Structural study of solid ammonia under pressure. (a) Representative room temperature X-ray diffraction patterns at various pressure acquired at HPCAT beamline (l¼ 0.4125 Å). Reflections belonging Discussion to P2 2 2 and Pma2 are marked blue and magenta, respectively. Arrows are We now focus on a possible mechanism of the disproportionation 1 1 1 an eye guide for evolution of reflections hkl(400) and hkl(011) belonging to process in ammonia. Structural comparison of the low-pressure Pma2 space group proposed in ref. 19. (b) Enlarged view of XRD patterns. molecular and the high-pressure ionic phases reveals crucial clues Splitting is defined as ‘D’ – difference between the position of hhl(011) and on the underlying mechanism of the observed phase transition. hkl(400) reflections. (c). Pressure evolution of splitting. Comparison of First, from the structural point of view (Supplementary Fig. 5), calculated and experimentally measured data (dot curve is an eye guide). the transition from the molecular to the ionic phases involves a (d) Fragment of the experimental 2D CCD diffraction image corresponding to shift of closed packed planes: it thus resembles the well-known the integrated pattern shown in e.(e) Room temperature XRD pattern reversible hcp-to-fcc phase transition observed in relatively acquired at GSECARS beamline (l¼ 0.3,344 Å). Reflections (hkl)¼ (400) simple (for example, noble gases ) and more complex systems 29,30 and (011) are clearly resolved. Black curve represents integrated experi- (yttrium and other lanthanide trihydrides ). Indeed, the mental XRD pattern, blue (royal) and magenta curves correspond to experimentally observed continuous character of the intensity calculated patterns for P2 2 2 and Pma2 structure, respectively. The same change of the hkl(020) (molecular) and the hkl(210) (ionic) 1 1 1 applies to tick marks. Inset (left): a representative microphotograph of a reflections (Fig. 1a) provides direct evidence on the engagement sample chamber filled with solidified transparent ammonia taken under of those close packed layers and it also corroborates a quasi hcp- combined transmitted and reflected illumination at pressure 172 GPa. Gasket to-fcc nature of the transition. material was tungsten. Length of the scale bar corresponds to 50mm. Inset Second, in the molecular phase (P2 2 2 ), one can distinguish 1 1 1 (right): pressure evolution of the abundance of P2 2 2 phase (estimation is two types of hydrogen bonding with respect to the angle in the 1 1 1 based on the analysis of experimental and calculated XRD patterns). ‘N–H N’ fragment: an ‘intra-plane’ bond with the angle value of NATURE COMMUNICATIONS | 5:3460 | DOI: 10.1038/ncomms4460 | www.nature.com/naturecommunications 3 & 2014 Macmillan Publishers Limited. All rights reserved. Intensity (a.u.) Intensity (a.u.) Δ (degree) Abundance Intensity (a.u.) 400 011 011 ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms4460 ab c P2 2 2 Pma2 1 1 1 Theory (GPa) 100% (GPa) 3,500 3,000 0 2,000 4,000 0 2,000 4,000 –1 Wavenumber (cm ) 2,500 Stretching Lattice Bending modes modes modes 88 (GPa) Experiment 2,000 100% Tr Rot u 3 2 u 4 Theory 0 1,000 2,000 3,000 4,000 0 40 80 120 160 0 1,000 2,000 3,000 4,000 –1 –1 Wavenumber (cm ) Pressure (GPa) Wavenumber (cm ) Figure 2 | IR absorption study of solid ammonia under pressure. (a) Representative room temperature IR absorption spectra at various pressures. Colours depict features attributed to molecular phase (blue (royal)) and ionic (magenta) phases, respectively. The spectral region of ‘N–H’ stretching band corresponding to molecular phase is highlighted blue. New band of strong absorption not related to the molecular phase is highlighted pink. Blue arrow is an eye guide for pressure evolution of the soft ‘N–H’ stretching mode due to hydrogen bonding. (b). Pressure evolution of the measured positions of signals in the wavenumber range from 1,800–4,000 cm . Symbols represent experimental data while lines represent calculated data from ref. 19. Line thickness corresponds to signal intensity. Solid dark blue symbols correspond to experimental data reported in ref. 24 while solid light blue outlined symbols represent data measured in this work. Blue and magenta highlighted fields correspond to measured strong absorption associated with the molecular and the ionic phase respectively. (c) Comparison of theoretically calculated IR absorption spectra and their evolution with pressure. (d) Comparison of IR absorption spectra measured at 67 GPa and calculated at 60 GPa. ab c 3,800 (GPa) 3,600 2,000 3,400 1,800 3,200 88 3,000 1,600 2,800 2,000 3,000 4,000 80 120 160 80 120 160 –1 Raman shift (cm ) Pressure (GPa) Pressure (GPa) Figure 3 | Raman scattering study in solid ammonia under pressure. (a) Representative Raman spectra of solid ammonia collected at different pressures (fragment of high-frequency spectral range). The signal related to the second order Raman signal of diamond anvil is grey shadowed. Colours depict features attributed to molecular phase (blue (royal)) and ionic (magenta) phases, respectively. The light blue highlighted peak corresponds to the Raman signal associated with the most labile hydrogen bonding. (b,c) Pressure evolution of Raman shifts. Grey shadowed regions correspond to the signal of diamond anvil (the first and the second order Raman in b and c, respectively). Lines and symbols correspond to calculated and experimentally measured data. Thickness of lines and size of symbols correspond to intensities of presented data. The rest of colours and symbols designation is similar to that in a. 4 NATURE COMMUNICATIONS | 5:3460 | DOI: 10.1038/ncomms4460 | www.nature.com/naturecommunications & 2014 Macmillan Publishers Limited. All rights reserved. Raman intensity (a.u.) Absorption (a.u.) –1 Raman shift (cm ) –1 Wavenumber (cm ) –1 Raman shift (cm ) Absorption (a.u.) Absorption (a.u.) NATURE COMMUNICATIONS | DOI: 10.1038/ncomms4460 ARTICLE B158 and an ‘inter-plane’ bond with the angle value close to Phase A B169 (Supplementary Fig. 5). According to experimental Phase B spectroscopic data, the most labile hydrogen bond, the one 0.1 exhibiting strong softening in both the IR and Raman spectra, is Phase C located between the closely packed layers. We therefore call this bond ‘inter-plane’. We found that a gradual, pressure-induced elongation of the covalent component (‘N–H’) leads to complete proton transfer from one neutral NH molecule of to the other, ΔH* resulting in formation of the NH /NH pairs at B127 GPa. 4 2 –0.1 The resulting Pma2 arrangement, features a remarkably low anisotropy of the hydrogen bonds (B165 and B163 for ‘inter-‘ Phase A Phase B Phase C and ‘intra’plane type, respectively), much lower than in the case –0.2 of molecular P2 2 2 , phase. 1 1 1 At this point, one can clearly distinguish two major stages governing the observed molecular to ionic phase transition: the –0.3 first is the process of ‘interplane’ proton transfer; the second is the stage of structural rearrangement (in particular, sliding of the closely packed layers). Based on the spectroscopic observations, –0.4 Ionic Post-ionic/molecular Molecular we believe that the proton transfer ‘starts’ first at pressures well (exp.; Pma2) (model; eff.Pc) (exp.; P2 2 2 ) 1 1 1 below the observed actual structural transformation. Nonetheless, a definite answer to the question on which of the stages drives the phase transition is a matter of discussion, and, at this moment, 50 100 150 200 250 falls beyond the scope of the present paper. Pressure (GPa) We note, however, that the experimentally observed reversibility of the transformation points to the fact that Figure 4 | Description of hypothetical intermediate phase. Calculated curves for enthalpy difference (DH) for the three considered phases of ‘interplane’ proton transfer can effectively occurs within layers of quasi closely packed nitrogen atoms in either P2 2 2 or ammonia. Enthalpy of the high-pressure, ionic Pma2 (Phase A) establishes 1 1 1 the reference (zero) line. Note the convergence of the absolute enthalpy of Pma2. Intuitively, a gradual ionization of the initial molecular P2 2 2 phase with subsequent structural transformation to the experimental molecular P2 2 2 (Phase C) with the enthalpy of the 1 1 1 1 1 1 hypothetical model molecular Pc (Phase B) with the decreasing pressure. Pma2 phase also looks plausible; however, at this moment, we are ruling this possibility out. If the assumed reaction path was As an example, the enthalpy difference (DH*) corresponding to the proton transfer contribution calculated at pressure of 25 GPa is shown. Insets realized via an intermediate phase, ionized via proton transfer with the P2 2 2 symmetry preveserved, one would have expected illustrate schematically the structural similarities of the three phases 1 1 1 considered. signs of disproportionation/ionization at pressure range well preceding the pressure of the structural phase transition observed in the XRD data (the appearance of NH - and NH -related energy required for the proton transfer. The remaining difference 4 2 gives highly specific IR absorption bands and Raman signals, in energy (between the model molecular phase (Pc) and which is difficult to omit). Instead, both the spectroscopic and the experimentally observed one (P2 2 2 ) is associated with the 1 1 1 structural changes were observed in a narrow pressure range process of structural rearrangement. of 5–10 GPa indicating a simultaneous character of the trans- We therefore consider the Pc phase as a good approximation to formation. Furthermore, according to our DFT calculations, the experimental molecular phase and use it to model NH /NH 3 3 such intermediate ionic phase (ionic P2 2 2 ) is dynamically to NH /NH transition mechanism and calculate the associated 1 1 1 4 2 unstable below 50 GPa and relaxes spontaneously to the known energy changes. phase (molecular P2 2 2 ). On the contrary, an intermediate Because of the intermediate character of the hypothetical Pc 1 1 1 molecular phase of Pma2 symmetry is meta-stable below 50 GPa phase (both energetically and structurally), a simple proton featuring a local minimum in total energy profile: moreover, our transfer from one NH molecule to a neighbouring one results in calculation indicates that such meta-stable phase is separated a smooth transition from molecular to ionic phase (Fig. 5a). To from the ionic Pma2 phase by an exceedingly small, yet distinct, investigate the abovementioned implications of pressure-induced þ þ energy barrier. H transfer, resulting in NH /NH to NH /NH transition, we 3 3 4 2 For better understanding the proposed phase transition, we have modelled the process between the NH molecules in introduce a hypothetical molecular phase with the effective molecular phase and in 1-, 2- and 3-dimensional solids symmetry Pc, which is derived directly from the Pma2 (Fig. 4). (Supplementary Figs 6–9 and Supplementary Discussion). The This model structure exhibits a number of advantageous features resulting energy profiles for 3-dimensional solid are given in allowing for qualitative and quantitative analysis of the molecular Fig. 5b. to ionic phase transition. It shares features of both the ionic phase Although height of the energy barrier remains relatively small (arrangement of the nitrogen atoms, the shape and volume of the for all pressures, its presence effectively precludes N–H N bond unit cell are effectively identical as in the ionic phase) and the symmetrization, in contrast to highly compressed water, for molecular one (easily distinguishable, isolated ammonia mole- which the symmetrization occurs at PB100 GPa (ref. 31). cules). We note, that the difference between the hypothetical Note also the increasing contribution of the structural molecular (Pc) and the experimental molecular (P2 2 2 ) arises rearrangement process. In contrast to lower pressures at which 1 1 1 only from different NH packing–quasi fcc versus quasi hcp, the major part of energy is consumed for hydrogen transfer, the respectively. Calculated enthalpy corroborates the intermediate crystal structure rearrangement seems to become determinative at character of the Pc phase (Fig. 4). Furthermore, at this point, one higher pressures. This assumption qualitatively account for the can easily distinguish two types of energy contribution. Since we experimentally observed coexistence of two phases. According to assume the similarity (with respect to crystal structure) of the our XRD and Raman spectroscopy studies, the molecular phase Pma2 and Pc phases, the enthalpy difference (DH*) reflects the persists up to at least 172 GPa (Fig.1e inset). Moreover, in an NATURE COMMUNICATIONS | 5:3460 | DOI: 10.1038/ncomms4460 | www.nature.com/naturecommunications 5 & 2014 Macmillan Publishers Limited. All rights reserved. ΔH (eV per molecule) ARTICLE NATURE COMMUNICATIONS | DOI: 10.1038/ncomms4460 a b 65 GPa 50 GPa 25 GPa 0.1 10 GPa Phase B 0 GPa Phase A NH /NH 3 3 –0.1 –0.2 + – –0.3 NH /NH 4 2 –0.4 Molecular Ionic (Pc) (Pma2) Ionic Molecular (Pma2) (eff. Pc) Phase A Phase B Figure 5 | Modelling the mechanism of the autoionization in solid ammonia. (a) Schematic illustration of the computational scheme used to determine the minimal energy path of H transferred during the molecular to ionic phase transition. Red spheres indicate the ‘bridging’ hydrogen atoms transferred from one NH molecule to the other resulting in formation of the NH /NH ionic pair. (b) Calculated energy profiles depicting the enthalpy changes, DH*, 3 4 2 associated with the proton transfer between experimentally observed ionic phase and the proposed molecular phase of ammonia. Here, the calculated enthalpy of the ionic phase is set to 0. At the low-pressure limit (P-0 GPa) the ionic phase (Pma2) is calculated to be dynamically unstable. Upon relaxation, it spontaneously transforms into phase exhibiting purely molecular character. However, upon compression, the ionic phase stabilizes and already at PB10 GPa, our model predicts formation of two minima, separated by an energy barrier. At lower pressures, the molecular minimum is strongly favored. According to the proposed model, transition from Phase A to Phase B occurs spontaneously at the low-pressure limit. With increasing pressure, the model molecular Phase B destabilizes. At B62 GPa, the two structures exhibit enthalpy degeneracy and at P470 GPa spontaneously transforms into the ionic one. Both structures remain separated by a small, yet persistent energy barrier of B10 meV (calculated per NH molecule). additional XRD runs, a significant amount of P2 2 2 phase was We hope that the reported experimental evidence on the new 1 1 1 still detected, even up to the highest pressure of B203 GPa form of ammonia and the observed peculiar behaviour of (Supplementary Fig. 10 and Supplementary Discussion). hydrogen bonds under pressure will stimulate further experi- Finally, we note that the P2 2 2 -Pma2 transition is mental as well as further theoretical research on new forms of 1 1 1 predicted to occur at a pressure close to 90 GPa (ref. 19 and simple HB systems in general and in particular, on the conductive this study Fig. 4) yet is experimentally observed at pressures properties of the ionic ammonia, which may turn to be critical for close to 130 GPa. This discrepancy may in part be due to athermal better understanding the observed properties of giant planets in nature of the calculations where all entropic contributions our solar system. are neglected. In conclusion, ammonia presents a qualitatively new picture of Methods HB solid under pressure. Our detailed study provides first Experimental methods. Number of successful (pressure achieved4150 GPa) experiments:Raman—5 (including two pressure release runs). Re gaskets were used experimental evidence of the pressure-induced complete proton in two measurements, W gaskets were used in other three experiments. Combined transfer resulting in the formation of the ionic phase (formation (IRþ Raman)—5 (all were carried out using W gaskets with Au-lining), XRD of NH /NH pairs) in compressed solid ammonia. The proton 4 2 (synchrotron) measurements—6 (gasket materials: Re without Au-lining (2 transfer is found to be a continuous and reversible process measurements), W without Au-lining (four measurements)). Size of sample varied starting already at ambient pressure and completing at B125 depending on the technique used. Generally for the XRD and Raman measure- ments samples were of B10–12 mm initial thickness andB35 mm in diameter. For GPa. In fact, such a wide range of hydrostatic pressure required IR measurements, samples were significantly thinner (initial thickness t1mm) in for proton transfer is unprecedented. The final stage of order to get better resolved spectrum, especially, in the region of strong absorption autoionization process is found to be accompanied by the quasi of N–H molecular vibrations. first order transformation resembling a quasi hexagonal to cubic The Raman spectrum of diamond anvil was used for pressure calibration. Moreover, during XRD measurements ‘diamond-Raman-edge’ scale was cross- structural phase transition. checked by pressure estimation from equation of state of gasket materials (W, Re or Our theoretical calculations provide a deep insight into the Au). Neither diamond anvils nor gaskets were subjected to any passivation. mechanism underlying the observed phenomenon indicating no For experiments, samples of liquefied ammonia were loaded into diamond anvil hydrogen-bond symmetrization on the whole reaction path and cells in the temperature range 195–240 K. Beveled diamonds with a culet diameter of 100 mm (and less) were used to reach pressures above 1 mbar. Gasket holes were remarkably small energy barrier between competitive phases. An prepared using IR laser drilling. Angle dispersive X-ray diffraction studies were increasing energy cost of the structural rearrangement compo- conducted at the Advanced Photon Source (HPCAT, GSECARS), Argonne nent to the total energy is suggested to account for the overall National Laboratory, USA and European Synchrotron Radiation Facility (ID 9, ID slowing down of the autoionization process confirmed by the 27). Raman scattering was excited using a 25 mW HeNe (632.8 nm) laser. Raman spectra were collected in backscattered geometry using a single imaging spectro- experimental observation of the molecular form up to 203 GPa. meter HR460 (focal length 460 mm) equipped with a 900 grooves per mm grating, This unique scenario has no analogy among other known simple giving a resolution of B1cm , notch filters (Keiser Optical Systems) and liquid HB system such as water (H O), hydrogen halides (HCl, HBr and nitrogen cooled CCD detection. 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Lett. 382, 686–692 2 4 (2003). naturecommunications 15. Song, Y. et al. High-pressure stability, transformations, and vibrational Competing financial interests: The authors declare no competing financial interests. dynamics of nitrosonium nitrate from synchrotron infrared and Raman spectroscopy. J. Chem. Phys. 119, 2232–2240 (2003). Reprints and permission information is available online at http://npg.nature.com/ 16. Sihachakr, D. & Loubeyre, P. High-pressure transformation of N /O mixtures 2 2 reprintsandpermissions/ into ionic compounds. Phys. Rev. B 74, 064113 (2006). 17. Meng, Y. et al. Hard x-ray radiation induced dissociation of N and O How to cite this article: Palasyuk, T. et al. Ammonia as a case study for the spontaneous 2 2 molecules and the formation of ionic nitrogen oxide phases under pressure. ionization of a simple hydrogen-bonded compound. Nat. Commun. 5:3460 Phys. Rev. B 74, 214107 (2006). doi: 10.1038/ncomms4460 (2014). NATURE COMMUNICATIONS | 5:3460 | DOI: 10.1038/ncomms4460 | www.nature.com/naturecommunications 7 & 2014 Macmillan Publishers Limited. All rights reserved.

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