JOURNAL OF CHEMICAL PHYSICS

VOLUME 112, NUMBER 19

15 MAY 2000

High-pressure phases of solid nitrogen by Raman and infrared spectroscopy

Roberto Binia)
` Dipartimento di Chimica dellUniversita di Firenze, Via G. Capponi 9, I-50121 Firenze, Italy LENS, European Laboratory for Non-linear Spectroscopy, Largo E. Fermi 2, I-50125 Firenze, Italy

Lorenzo Ulivib)
Istituto di Elettronica Quantistica, Consiglio Nazionale delle Ricerche, and INFM Via Panciatichi 56/30, I-50127 Firenzo, Italy

Jorg Kreutzc)
Fachbereich Physik, Universitat Kaiserslautern, E. Schrodinger Str., 67663 Kaiserslautern, Germany

Hans J. Jodld)
Fachbereich Physik, Universitat Kaiserslautern, E. Schrodinger Str., 67663 Kaiserslautern, Germany LENS, European Laboratory for Non-linear Spectroscopy, Largo E. Fermi 2, I-50125 Firenze, Italy

Received 5 November 1999; accepted 24 February 2000 Raman and infrared spectra of solid nitrogen have been collected between 25 K and room temperature up to 41 GPa. A careful analysis of the spectral band transformations occurring across the high pressure transitions among the , loc , , and phases allowed to dene the phase diagram in the whole P-T region investigated. In particular, the transition between the and phases has been observed in the range 30230 K and the corresponding phase-boundary drawn. A signicant metastability region spanning about 10 GPa in pressure hinders the transformation between the and phases when pressure is varied at low temperature. Group theory arguments suggest a centrosymmetric structure for the phase and the number of Raman and infrared 1 and 2 components can be reproduced both with cubic and tetragonal structures. An appreciable coupling among neighboring molecules is observed, at room temperature, only in the phase where the relative orientations of the molecules are xed. 2000 American Institute of Physics. S0021-9606 00 01219-8
I. INTRODUCTION

Diamond anvil cells are extensively used to study the properties of simple molecular solids in the high-pressure regime.1 Among this class of crystals nitrogen is considered in many respects a model system.2,3 This is attested by the large number of experimental and theoretical investigations carried out on condensed nitrogen. Five solid phases , , , , have been identied at pressures up to 10 GPa and temperatures below 300 K see Fig. 1 . Recent infrared results4 have complemented previous Raman data5,6 allowing the characterization of a sixth structural modication ( loc) discovered in the P-T plane between the and the phases. The complete vibrational analysis, based on group theoretical arguments, allowed to propose a cubic structure for the phase. The loc phase which closely recalls that of the disklike molecules of the phase have xed orientation in the loc phase and the amplitude of the uctuations around the new positions progressively decrease lowering the temperature. Spectroscopic experiments on solid nitrogen have been performed at room temperature up to more than 100 GPa,712 x-ray data, available up to 50 GPa, agree on a phase transition at 16.5 GPa which was assigned to the phase
a

Electronic mail: bini@chim.uni.it Electronic mail: ulivi@ieq..cnr.it c Electronic mail: kreutz@physik.uni-kl.de d Electronic mail: jodl@physik.uni-kl.de
b

transition.8,10 Recent x-ray experiments using synchrotron radiation revealed another transition at 11 GPa between the cubic phase and a new phase which is probably coincident with the already described loc phase.13 More contrasting are the results derived from Raman experiments. At room temperature, two transitions were detected by Reichlin et al. at 20 and 66 GPa.9 Later, Schneider et al. xed the stability limit of the phase between 17 and 20 GPa, and another phase was supposed to exist above 20 GPa up to 4050 GPa.7 These results were recently contradicted by a line shape analysis of the internal Raman bands up to 30 GPa.14 At lower temperature 30015 K the pressure range investigated is much smaller ( P 30 GPa), 5,6,1521 furthermore below 100 K only Raman19 and infrared up to 7 GPa 4,21 experiments have been performed above the phase boundary 2 GPa . As to the phase, the results are consistent with a mul tisite rhombohedral R3 c structure having eight molecules per cell. Six molecules are located on sites with C 2 symmetry while the other two molecules are on sites with a S 6 symmetry. The stretching modes relative to the two sites are indicated, according to the terminology used for the phase, as 2 and 1 , respectively. On the basis of group theoretical arguments one Raman band of symmetry A 1g is expected for the 1 mode while three bands, two Raman, of symmetry A 1g and E g , and one infrared, of symmetry E u , are predicted in the 2 region. In the low-temperature Raman spectrum only two peaks one for each the 1 and the 2 were
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FIG. 2. Room temperature Raman spectra of solid nitrogen, in the loc and phases, showing the 2 and 1 bands. The splitting of the 2 band is observable above 17 GPa. FIG. 1. Phase diagram of nitrogen. The boundary between the and the phases is a result of this study and will be discussed in the last section. Stars represent data from Ref. 4; empty circles and full squares derive, respectively, from infrared and Raman results of the present study.

observed below 21 GPa. Above this pressure a splitting of the 2 Raman band was detected.19 This observation has been interpreted as due to a phase transition to a new rhombohedral structure , which was speculated to have a R3c symmetry. In the infrared spectrum one band is observed in the 2 region, up to 7 GPa.21 Recently the infrared analysis was extended up to 9 GPa conrming this observation.4 In this paper we report on an extended study of both infrared and Raman spectra of solid nitrogen up to 40 GPa between room temperature and 25 K. Several isobaric and isothermal cycles were performed in order to clarify the stability range of the loc and of the phases. According to these results we were able to establish the phase diagram below 295 K and 40 GPa.
II. EXPERIMENT

red measurements. The temperature of the sample is measured by a Si-diode placed in the copper ring where the diamond is mounted, the resulting uncertainty on the sample temperature is estimated in 2 K. In all the experiments the sample was prepared starting from the disordered phase 2 to 3 GPa , the - phase transition was slowly crossed at room temperature, the sample annealed at about 300 K for not less than 21 hours below 5 GPa. All the cooling cycles were performed at constant pressure at the rate of 2 to 3 K per hour.
III. RESULTS

The phase diagram of solid nitrogen was carefully probed between 25 K and room temperature along several isobars up to 40 GPa in Raman and 30 GPa in infrared experiments. Also isothermal scans were performed up to the same nal pressures values at 25, 100, and 300 K. For the sake of clarity we will present the Raman and the infrared results in two distinct subsections.
A. Raman

High-pressure infrared and Raman spectra of solid nitrogen were measured using a membrane diamond anvil cell MDAC . The crystals were produced by loading the cell either cryogenically, or with gaseous N2 (purity 99.99%) by means of an high-pressure gas loading equipment. A ruby chip was inserted in the sample and the pressure determined from the peak wavelength of the R 1 ruby uorescence band. The uncertainty in the pressure determination is less than 1%. The complete apparatus for infrared experiments, including the optical beam condenser and the cryogenic system, has been extensively described in a previous report.22 Both infrared and Raman setup were the same employed in a previous experiment on nitrogen.4 The instrumental resolution was better than 0.1 and 0.3 cm 1 in infrared and Raman experiments respectively, while the frequency accuracy was 0.1 cm 1 in Raman and much higher 0.005 cm 1 in infra-

Room temperature spectra in the loc and phases see Fig. 2 relative to the intramolecular vibration region show two symmetric peaks, assigned to the 1 and 2 modes, up to about 17 GPa. Above this pressure the 2 peak starts to be asymmetric on the high-frequency side, and a weaker band is clearly detectable at 21 GPa. The two bands are fully resolved only above 30 GPa. This splitting of the 2 mode was already observed in previous Raman experiments at about 20 GPa and ascribed to the formation of a new crystal structure different from the phase.7,9 This doublet instead represents the A 1g and E g components of the 2 mode in the phase. X-ray experiments at 300 K report indeed, above the phase and up to 50 GPa, only the phase transition at 16.3 GPa leading to the phase.8,10 As to the lattice region, the

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spectra collected in this work are in good agreement with those reported by Schneider et al.,7 and the broadness of all the bands does not allow to improve their analysis. Isobaric coolingwarming cycles were performed between 5 and 41 GPa every 2 to 3 GPa. In these measurements pressure was varied, between one cycle and the other, only at room temperature. A more careful sampling 1 GPa , was carried out in the pressure region 1725 GPa where the transition to the phase was observed at low temperature.19 In the cooling cycles between 5 and 10 GPa the loc and loc phase transitions are identied, respectively, by a cusp and by a discontinuity in the frequency evolution with temperature of the 1 mode, as already reported by Scheerboom and Schouten5,6 Above 10 and up to 17 GPa only the discontinuity in the frequency of the 1 mode is observed, clearly indicating that only the loc phase transition occurs. Between 17 and 23 GPa we did not observe any particular change in the internal spectrum on cooling apart from a progressive better resolution of the 2 doublet decreasing temperature. In the 23 GPa cycle a distortion of the main peak of the 2 doublet, consisting in a pronounced asymmetry in the low frequency side, is observed at about 30 K. In the higher-pressure cycles such distortion is observed at progressively higher temperatures, being followed by a rapid intensication of the new lowfrequency band, and by a decrease of the intensity of the main peak of the 2 doublet in the phase. The complete transformation can be followed in Fig. 3 a , where the isobaric cooling at 30 GPa is reported. For comparison we report in Fig. 3 b the isothermal evolution with pressure of the same modes at 30 K. The clear resemblance of the spectral sequences reported in the two gures indicates that an identical succession of crystal structures is probed in the two isobaric and isothermal experiments. Identical conclusions are also extracted by the spectra measured in the lattice phonons region. In Fig. 4 we report the spectra measured along the same isobar at 30 GPa. The broad bands observed at room temperature are progressively better resolved as the temperature is lowered. At 116 K eight bands can be identied, six as main peaks and two as shoulders. This spectrum is very similar, apart from the width of the bands, to those measured at 30 K up to 20 GPa. Below 90 K the spectrum shows some changes at about 200 and 320 cm 1. The doublet at about 200 cm 1 transforms into a triplet where the band at lower frequency seems to be the new one. More complex is the evolution of the spectral feature at 320 cm 1: At 73 K the doublet is transformed into a structure which can be decomposed in four different peaks. The new peaks are the lowest and the highest in frequency. On further cooling the weaker peak of the original doublet progressively weakens and completely disappears at low temperature. In total, ten different clear peaks are identied at 30 K. This spectral structure is stable above 30 GPa in perfect agreement with the information obtained from the internal vibron region. Isobaric cycles have been performed starting from room temperature states reached also releasing pressure and the resulting spectra are completely equivalent to those recorded in the compression cycles. It is worth to mention the absolute

FIG. 3. a Raman spectra collected cooling along the 30 GPa isobar, showing the transition at about 90 K. b Spectra collected each one at the lowest temperature 30 K of different isobars showing the same phase transition at about 23 GPa.

lack of hysteresis observed following this procedure, because a strong hysteresis is on the contrary observed releasing pressure at low temperature. With this procedure, in fact, the high-pressure spectral features, observed above 23 GPa persist down to 10 GPa in low-temperature decompression cycles indicating a strong metastability affecting the nitrogen crystal at low temperature. The metastability region is indicated by a gray-shaded area in Fig. 1.
B. Infrared

Room temperature compression experiments showed the appearance of a weak peak in the 2 region, at about 2355 cm 1, when the pressure was raised above 11 GPa. The intensity of this peak rapidly increases rising pressure up to 20 GPa, then it remains almost constant. The frequency evolution of the infrared 2 component with pressure is reported in

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FIG. 5. Pressure shift of the infrared frequency of the 2 mode measured at room temperature. The frequency jump allows to precisely determine the phase transition between loc and the phase. The parameters of the straight lines are given in Table I.

FIG. 4. Raman spectra of the lattice modes collected as a function of temperature at 30 GPa.

Fig. 5. This is tted with two straight lines, whose intercept and slope are reported in Table I, among the other parameters tting the pressure evolution of the band frequencies measured in this study. A clear discontinuity is observed at 17.3 GPa where the frequency of this peak suddenly decreases of 1.5 cm 1. The appearance of the peak at about 11 GPa and the discontinuity in the frequency perfectly t the loc and pressure values of the two phase transitions reported by x-ray diffraction experiments below 20 loc GPa.8,10,13 Isobaric cooling cycles at 11 to 12 GPa and 19 GPa were carried on starting with room temperature samples in the loc

and in the phases, respectively. In both runs a single band is always observed in the 2 region. The cycles at 11 to 12 GPa reveal a discontinuity in the frequency of the peak at about 200 K very similar to those reported at lower pressures in Ref. 4 and interpreted as due to the loc phase transition. Several different samples in the phase were isothermally compressed at 3040 K. In Fig. 6 some spectra measured in the 2 region during compression cycles at 30 K are reported. The single band of the phase splits into two peaks above 18 GPa and a signicant increase of the absorption is observed. No further changes are detected when the pressure is further raised to 30 GPa. Releasing pressure the intensity of the doublet progressively decreases but the two peaks persist down to about 10 GPa showing, therefore, the same metastability already observed in the Raman experiment. The frequency data relative to the low-temperature compression full symbols and decompression empty symbols cycles are reported in Fig. 7.

TABLE I. Parameters of the parabolic t to the pressure evolution of the frequencies of the internal modes 1 and 2 and Raman lattice modes P 1 to P 8 , and P A P B in the phase . The values are the zeroth-, rst-, and second-order coefcient, respectively, when pressure is measured in GPa and frequency in cm 1. The t reproduces the experimental values in the pressure range where they have been measured.
loc

Mode
1 (R) 2a (R) 2b (R) 2 (IR)

phase 295 K 2.94 1.90 2.75 0.026 2332.70 2327.87 2328.04 2329.54 152.55 117.23 107.01 83.32 70.75 59.73 63.50 39.79

phase 30 K 4.08 2.68 2.75 2.20 16.78 11.20 11.88 9.24 7.74 7.08 4.04 3.10 0.045 0.025 0.027 0.006 0.268 0.132 0.171 0.127 0.110 0.086 0.080 0.059 2333.72 2330.41 2329.55 2333.22 195.52 137.72 120.74 154.46 80.39

phase 295 K 3.60 2.48 2.51 2.02 11.00 9.80 8.98 3.42 4.89 0.029 0.018 0.021 0.009 0.094 0.091 0.082 0.031 2343.85 2332.92 2330.12 2320.18 2308.18 2325.95 2330.21 217.82 181.46 85.13 114.95 83.30 52.77 71.22 104.90 48.74 2.53

phase 30 K 3.10 2.45 2.65 3.06 3.81 2.69 1.88 9.71 7.01 11.33 9.46 8.04 7.36 5.17 2.65 2.65 3.86 0.022 0.028 0.029 0.020 0.033 0.022 0.011 0.074 0.037 0.107 0.100 0.070 0.057 0.028 0.005 0.016

2336.63 2334.11 2327.18

P1 PA P2 P3 PB P4 P5 P6 PC P7 P8

36.56

3.03

0.031

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FIG. 6. Low-temperature infrared absorption spectra in the region of the mode as a function of pressure.

Finally, once the 2 doublet was obtained, we raised the temperature isobarically at 27 GPa. The decrease of the doublet intensity was distinguished, as also observed in the isothermal decompressions at 3040 K, by a much faster reduction of the higher-frequency peak. The doublet structure is observed up to 120 K, where it is replaced by a single weak band which lasts up to room temperature.
IV. DISCUSSION A. Phase diagram

The combination of infrared and Raman studies in simple molecular crystals gives a full vibrational information which has been demonstrated to be extremely powerful to provide structural information. This approach has been recently applied to CH4, N2, and O2 crystals.4,2325 There are several open questions, especially at low temperature, about the number, the structures and the boundaries of the highpressure crystal phases of solid nitrogen. Our attention will be rst devoted to the identication of the different phase transitions resulting from the present studies, then an interpretation of the structural properties of the high-pressure and low-temperature phases will be attempted. At room temperature the appearance of a 2 infrared component indicates a rst phase transition at about 11 GPa. This observation agrees nicely with the x-ray data of Hanand et al.,13 and with the value 10.5 GPa reported by Scheerboom et al.6 on the basis of Raman experiments. This

transition is straightforwardly assigned to the - loc secondorder phase transition. We have studied this transformation in a previous report between 5 and 10 GPa below 270 K establishing the blockage dynamics of the disklike molecules of the phase in lower symmetry sites leading to the formation of the two site structure of the loc phase.4 Increasing further the pressure at room temperature, the discontinuity in the frequency evolution of the 2 infrared component, reported in Fig. 5, reveals another phase transition at 17.3 GPa ( loc ). Again the agreement with the x-ray data8,10,13 is excellent. The transition reported in previous Raman analysis phase 7 but not observed in the x-ray at about 20 GPa measurements is now easily resolved. In fact, the only evidence of that phase transition was the splitting of the 2 mode7,9 which we demonstrated to be present already at 17 GPa. No other phase transitions were detected at room temperature up to 41 GPa. In the isobaric cooling and warming cycles above 10 GPa two types of transition were observed. The rst, detected below 16 GPa and assigned to the loc transition, is characterized by the splitting of the 2 Raman band and by the discontinuity in the frequency dependence on temperature of the 2 infrared component. The second, observed above 22 GPa in all the isobaric cycles, is characterized, in Raman, by the disappearance of the most intense component of the 2 doublet of the phase, by the rapid intensication of the other component and by the appearance of a lower frequency peak see Fig. 3 a and, in infrared, by the formation of a doublet, which replaces the single 2 infrared component of the phase see Fig. 6 . The changes in the Raman spectrum closely recall the ones measured by Schiferl et al.19 at 15 K and interpreted as the transition between the and the phases. All our data concerning the loc , the loc , and the phase transitions, derived both from infrared and Raman experiments are reported in Fig. 1, where according to these results, we propose the new phase diagram of nitrogen up to 40 GPa and below room temperature. The full line indicating the loc phase boundary is drawn according to the linear relation extracted by the Raman data reported in Ref. 5. A linear t has been used also to reproduce our data concerning the phase boundary, which accordingly is described by the relation P GPa 0.115 T K 18.270. As to the loc transition, we used our infrared data from the present experiment circles and those reported in a previous report stars 4 to redraw the phase boundary. The best linear relation is given by: P GPa 0.0695 T K 1.838. In the low-temperature part of the phase diagram Fig. 1 a shaded area indicates the P-T region where we found metastability especially in the decompression cycles. The scarce reversibility of the phase transition was put in evidence by a reproducible behavior in recovering the spectral signatures characteristic of the phase releasing pressure. We explain this metastability as due to the close resemblance of the structures of the and phases.
B. The phase

loc

FIG. 7. Pressure evolution of the frequency of the 2 infrared mode measured at 30 K. Full and empty symbols refer, respectively, to pressure increase and release experiments.

In order to get a better insight into the structural properties of these high-pressure phases, we have tried to identify,

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according to group theoretical arguments, the crystal structures which account for the observed vibrational spectral pattern. In the loc phase, one single Raman peak for the 1 mode and one infrared and two Raman bands for the 2 mode have been detected. This observation, made in a previous report up to 10 GPa as a function of temperature,4 is conrmed by the present results collected up to 17 GPa and higher temperatures. Moreover, the sharpness of the bands, the practically Lorentzian line shape, especially for the infrared mode,4 and the excellent signal to noise ratio indicate a good crystal quality and do not allow to speculate about the presence of other weak or partially hidden peaks. According to these considerations the three-site tetragonal structure 16 ( P4 2 /ncm;D 4h ) proposed by Hanand et al. for the loc 13 phase, on the basis of room temperature x-ray diffraction experiment, poorly agrees with the observed spectroscopic vibrational pattern. In this structure four molecules, corresponding to the spherelike molecules of the phase 1 mode , have C 2h symmetry and should originate three Raman components while only one is observed experimentally. The disklike molecules of the phase sit now on two different sites: four have C 2 v and eight C 2 symmetry. From the four C 2 v molecules two Raman and one infrared peaks are expected while three Raman and one infrared peaks should be obtained by the C2 molecules. Consequently, according to the proposed tetragonal structure,13 a much higher number of peaks, in infrared as well as in Raman, should be observed in both 1 and 2 regions. Also taking into account other tetragonal structures having a two-site structure in a 3:1 ratio between 2 and 1 type molecules, we always get from symmetry considerations a larger number of peaks than that experimentally observed. In a previous report4 we assumed that also the loc phase was cubic since the second-order transition between the and the loc phases indicates a continuity of the structural properties.5,6 A local molecular rearrangement inducing a site symmetry reduction sufces to account for the vibrational changes during the transformation. On the basis of group theory arguments we found three crystal structures (Fm3,F132,Fm3m) that t perfectly both infrared and Raman experimental spectra of the loc phase.
C. The and phases

FIG. 8. Low-temperature pressure evolution of the Raman active lattice modes through the phase transition. The parameters of the quadratic ts are listed in Table I.

the spectrum as a whole is detected and a new component rises on the low-frequency side of the 2 band. The Raman spectrum changes drastically at the formation of the phase, where it is composed by two strong and two weak bands. In Fig. 9 the frequency evolution with pressure of the four Raman and two infrared bands of the phase at 30 K is reported. The infrared values, limited to 27 GPa and including also the data collected releasing pressure, have been tted according to a linear law and compared with the Raman data. Only in one case the infrared and Raman frequencies coincide, namely the high-frequency infrared band and the most intense high-frequency Raman peak. However, the difference in frequency among the other bands 25 cm 1 is much larger than the uncertainty on the peak position 0.1 cm 1 , ensuring that different Davydov components are observed. This conclusion contrasts with the R3c structure proposed, by pure qualitative arguments, in Ref. 19. In fact, being this structure is non-centrosymmetric, all the crystal components, one for the 1 and three for the 2 mode, should be infrared

There are several aspects which must be considered in the interpretation of the phase transition and, consequently, of the phase. The observed number of lattice Rato ten see Fig. 4 . man bands changes from eight Only the peak at about 330 cm 1, represented by the shoulder of the most intense band in the low-pressure phase, clearly disappears at the transition, while three new modes appear in the high-pressure phase. All other bands of the phase show only a slope change. The evolution of the Raman phonon frequencies with pressure is shown in Fig. 8, and the tting parameters are listed in Table I. In the 1 region there are no changes in the spectral pattern, either in infrared and in Raman see Figs. 2 and 3 , and the evolution with pressure of the Raman peak is continuous also across the transition. On the contrary, larger changes during the transition are observed in the 2 region. In infrared, a strong intensication of

FIG. 9. Low-temperature evolution with pressure of 1 and 2 Raman components. In the inset the frequencies of the infrared 2 bands full dots , measured up to 27 GPa, are extrapolated to higher pressure and compared with the corresponding Raman components empty squares .

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and Raman active. A centrosymmetric structure seems to be more consistent with our data, in which case the coincidence of one infrared and one Raman 2 components should be considered accidental. The simplest approach to the phase transition con sists in the conservation across the transition of the R3 c structure with a site symmetry lowering. In this case it is not possible, either preserving or ignoring the 3:1 ratio between the 2 and 1 type molecules, to reproduce the observed spectral pattern. In order to account for the smooth changes between the and phases the next step is, in our opinion, to consider the nonisomorphic R3 c sub- and supergroups.26 No one, among the maximal nonisomorphic subgroups, can originate a number of internal components comparable to the experimental results, either considering a two-site in ratio of 3:1 structure, or a combination of three different sites with the 2 molecules split on two different sites. Among the minimal nonisomorphic supergroups, the ve cubic phases, due to the high symmetry of the factor group (O h ), satisfy the spectroscopic observations also considering only two site structures in a 3:1 ratio. The exact number of infrared and Raman components, detected in the 2 region, are reproduced only in one case. This result is obtained for the Pm3n structure (O 3 ), the same of the phase, with 24 molecules h on sites C s and eight on sites D 3 . According to the correlation diagram among molecular, site and factor group symmetries, four Raman and two infrared components are expected in the 2 region, while two Raman bands should be active in the 1 region. On the other hand the number of the lattice bands predicted according to this structure is 10 in infrared and 20 in Raman, while only 10 Raman peaks have been clearly identied. Finally, we considered those structures which, according to different theoretical approaches, were found to be stable in the P-T ranges that we have assigned to the phase. Most of the theoretical effort was devoted to the low temperature and pressure range characteristic of the phase. The trigonal R3 c structure, suggested by Schiferl et al. in Ref. 19, was conrmed rst by LeSar,27 and then by Etters et al.28 This conclusion was later re-discussed by these authors29 and a lower symmetry structure, R3c, found rst by Nose and Klein,30 was favored. To complete the calculation scenario it is worth mentioning also another constant pressure and temperature MD molecular dynamics calculation performed by Nose and Klein31 where, using a different potential with respect to that of Ref. 30, a stable tetragonal structure was found below 100 K at 7 GPa. Specic calculations along the 300 K isotherm were performed in Ref. 29 and for pressures higher than 20 GPa the Pm3n structure of the phase is replaced by a tetragonal structure with 32 molecules per unit cell. This structure was indicated as a minor variant of the phase where the molecules are frozen in sites of lower symmetry. From this analysis it results that, independently of the calculation, tetragonal structures are quite often found to distinguish high-pressure phases of solid nitrogen. For this reason we extended our analysis, based on group theory arguments, taking into account a tetragonal structure for the phase. Two-site structures never provide a vibrational pattern

FIG. 10. Vibrational coupling splitting among the A 1g , E g , and E u components of the 2 mode in the , loc , and phases. Plotted it is the difference of the weaker Raman band full symbols and of the infrared band empty symbols with respect to the stronger Raman band. In the delta phase no active infrared band exists, and the Raman band does not show any detectable splitting.

similar to the experimental spectra: while, on the contrary, several solutions are offered by considering three site structures. In particular six crystal structures, two having C 4h and four D 4h symmetry, allow to obtain the exact number of observed infrared and Raman components of the internal modes.
D. Vibrational coupling

The accuracy of our Raman and infrared frequencies determination allows us to draw important conclusions about the size and the effect of the vibrational coupling in the , loc , and nitrogen phases. This problem has been discussed extensively in the literature, and also recently it has been the subject of a spectroscopic study on isotopic substituted samples.32 On the basis of molecular dynamics computations it has been argued that this effect should be very small in solid N2, giving a splitting between the E g and A 1g components of the 2 mode of 0.2 cm 1 at maximum.28 Consequently, when a larger splitting was observed rst,7 it was rather attributed to the occurrence of a phase transition. With the present knowledge of the phase diagram we can now readdress the question, comparing not only the frequencies of the A 1g and E g Raman modes, but also that of the infrared component E u , measured in this study. At room temperature, where the range of existence of the , loc and phases is wider, such an analysis allows the determination of the inuence of the different molecular orientations on the vibrational coupling. Concerning the Raman data, the two A 1g and E g components are split only above the loc transition, and are essentially degenerate below it, in the and loc phase. The separation is 1.0 cm 1 at the transition, and grows almost linearly with pressure, up to 40 GPa. This difference is represented in Fig. 10 solid squares . The frequency of the E u infrared component is, in the phase, lower than the two Raman ones, and the difference between this and the lowest Raman component empty squares amounts to about 1.5 cm 1. We can, therefore, state that the coupling affects the modes much more than

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predicted theoretically.28 A quantitative analysis, as done recently for oxygen,25 is complicated because of the different relative orientations of neighboring molecules in the phase, and is beyond the scope of the present work. The presence of an infrared peak at lower pressure allows to extend this analysis to the loc phase, where the A 1g and E g Raman bands are almost degenerate at room temperature. In this pressure range we notice that the infrared and Raman frequency coincide, in the limit of the present accuracy. Since the density change at the loc transition is only 5%,20 the jump of the frequency difference should be ascribed to the complete freezing of the rotation of the molecules in the phase. These results demonstrate that the vibrational coupling between nitrogen molecules is strongly dependent on the molecular orientation, and greater than the average for the particular orientation occurring in the phase.
V. CONCLUSIONS

cuss the vibrational coupling among neighboring molecules. The coupling is negligible in the and loc phases while it starts to be appreciable in the phase, pointing out the importance of the freezing of the relative orientation.
ACKNOWLEDGMENT

This work has been supported by the European Union under Contract ERB FMGE CT 950017.
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1

The analysis as a function of temperature of the internal and external vibrational modes of solid nitrogen between 5 and 41 GPa provides a denitive evidence of the phase transition between the and the phases. Several isobaric cooling cycles allowed to monitor this continuous and reversible phase-transition and to draw the relative phase-boundary for temperatures lower than 300 K. The comparison between isobaric and isothermal cycles put in evidence a metastability range of the order of 10 GPa at low temperature. In fact, when the pressure is changed below 100 K, either in compression or decompression cycles, the coexistence of the two phases is always observed preventing any conclusion on the structural evolution. At room temperature our vibrational data are in perfect agreement with the structural x-ray studies, as concerns the numbers and the position of phase tranbesitions, and the existence of an intermediate phase tween the and phases can be ruled out. The analysis of the Raman and infrared activity in the fundamental vibration region, discussed on the basis of group theory arguments, do not agree with the tetragonal structure proposed for the loc phase on the basis of x-ray data and a cubic structure, closer to that of the phase, is favored. For the phase our data are consistent with a centrosymmetric structure but a precise denition of the factor group symmetry is not possible. If a two-site structure is retained in the phase, as in the and phases, we found that a cubic structure factor group O h symmetry is the only one compatible with our results. Three-site structures offer, on the contrary, several solutions either considering cubic and tetragonal unit cells. Finally, the precise knowledge of the frequencies of Raman and infrared components of the 2 mode increasing pressure across different crystal structures provided an excellent basis to dis-