Isochoric thermal conductivity of solid nitrogen

The isochoric thermal conductivity of solid nitrogen has been investigated on four samples of different densities in the temperature interval from 20 K to the onset of melting. In α-N₂ the isochoric thermal conductivity exhibits a dependence weaker than Λ1/T; in β-N₂ it increases slightly with...

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Опубліковано в: :Физика низких температур
Дата:2005
Автори: Konstantinov, V.A., Manzhelii, V.G., Revyakin, V.P., Sagan, V.V.
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Опубліковано: Фізико-технічний інститут низьких температур ім. Б.І. Вєркіна НАН України 2005
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Цитувати:Isochoric thermal conductivity of solid nitrogen / V.A. Konstantinov, V.G. Manzhelii, V.P. Revyakin, V.V. Sagan // Физика низких температур. — 2005. — Т. 31, № 5. — С. 553-557. — Бібліогр.: 12 назв. — англ.

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Digital Library of Periodicals of National Academy of Sciences of Ukraine
id nasplib_isofts_kiev_ua-123456789-121462
record_format dspace
spelling Konstantinov, V.A.
Manzhelii, V.G.
Revyakin, V.P.
Sagan, V.V.
2017-06-14T11:49:38Z
2017-06-14T11:49:38Z
2005
Isochoric thermal conductivity of solid nitrogen / V.A. Konstantinov, V.G. Manzhelii, V.P. Revyakin, V.V. Sagan // Физика низких температур. — 2005. — Т. 31, № 5. — С. 553-557. — Бібліогр.: 12 назв. — англ.
0132-6414
PACS: 66.70.+f, 63.20.Ls
https://nasplib.isofts.kiev.ua/handle/123456789/121462
The isochoric thermal conductivity of solid nitrogen has been investigated on four samples of different densities in the temperature interval from 20 K to the onset of melting. In α-N₂ the isochoric thermal conductivity exhibits a dependence weaker than Λ1/T; in β-N₂ it increases slightly with temperature. The experimental results are discussed within a model in which the heat is transported by low-frequency phonons or by «diffusive» modes above the mobility edge. The growth of the thermal conductivity in β-N₂ is attributed to the decreasing «rotational» component of the total thermal resistance, which occurs as the rotational correlations between the neighboring molecules become weaker.
This study was supported by the Ukrainian Ministry of Education and Science, Project (7/286-2001 «Novel quantum and unharmonic effects in mixtures of cryocrystals».
en
Фізико-технічний інститут низьких температур ім. Б.І. Вєркіна НАН України
Физика низких температур
Физические свойства криокристаллов
Isochoric thermal conductivity of solid nitrogen
Article
published earlier
institution Digital Library of Periodicals of National Academy of Sciences of Ukraine
collection DSpace DC
title Isochoric thermal conductivity of solid nitrogen
spellingShingle Isochoric thermal conductivity of solid nitrogen
Konstantinov, V.A.
Manzhelii, V.G.
Revyakin, V.P.
Sagan, V.V.
Физические свойства криокристаллов
title_short Isochoric thermal conductivity of solid nitrogen
title_full Isochoric thermal conductivity of solid nitrogen
title_fullStr Isochoric thermal conductivity of solid nitrogen
title_full_unstemmed Isochoric thermal conductivity of solid nitrogen
title_sort isochoric thermal conductivity of solid nitrogen
author Konstantinov, V.A.
Manzhelii, V.G.
Revyakin, V.P.
Sagan, V.V.
author_facet Konstantinov, V.A.
Manzhelii, V.G.
Revyakin, V.P.
Sagan, V.V.
topic Физические свойства криокристаллов
topic_facet Физические свойства криокристаллов
publishDate 2005
language English
container_title Физика низких температур
publisher Фізико-технічний інститут низьких температур ім. Б.І. Вєркіна НАН України
format Article
description The isochoric thermal conductivity of solid nitrogen has been investigated on four samples of different densities in the temperature interval from 20 K to the onset of melting. In α-N₂ the isochoric thermal conductivity exhibits a dependence weaker than Λ1/T; in β-N₂ it increases slightly with temperature. The experimental results are discussed within a model in which the heat is transported by low-frequency phonons or by «diffusive» modes above the mobility edge. The growth of the thermal conductivity in β-N₂ is attributed to the decreasing «rotational» component of the total thermal resistance, which occurs as the rotational correlations between the neighboring molecules become weaker.
issn 0132-6414
url https://nasplib.isofts.kiev.ua/handle/123456789/121462
citation_txt Isochoric thermal conductivity of solid nitrogen / V.A. Konstantinov, V.G. Manzhelii, V.P. Revyakin, V.V. Sagan // Физика низких температур. — 2005. — Т. 31, № 5. — С. 553-557. — Бібліогр.: 12 назв. — англ.
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AT manzheliivg isochoricthermalconductivityofsolidnitrogen
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AT saganvv isochoricthermalconductivityofsolidnitrogen
first_indexed 2025-11-25T21:07:28Z
last_indexed 2025-11-25T21:07:28Z
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fulltext Fizika Nizkikh Temperatur, 2005, v. 31, No. 5, p. 553–557 Isochoric thermal conductivity of solid nitrogen V.A. Konstantinov, V.G. Manzhelii, V.P. Revyakin, and V.V. Sagan B. Verkin Institute for Low Temperature Physics and Engineering of the National Academy of Sciences of Ukraine, 47 Lenin Ave., Kharkov 61103, Ukraine E-mail: konstantinov@ilt.kharkov.ua Received July 8, 2004 The isochoric thermal conductivity of solid nitrogen has been investigated on four samples of different densities in the temperature interval from 20 K to the onset of melting. In �-N2 the isochoric thermal conductivity exhibits a dependence weaker than ��1/T; in �-N2 it increases slightly with temperature. The experimental results are discussed within a model in which the heat is transported by low-frequency phonons or by «diffusive» modes above the mobility edge. The growth of the thermal conductivity in �-N2 is attributed to the decreasing «rotational» component of the total thermal resistance, which occurs as the rotational correlations between the neighbor- ing molecules become weaker. PACS: 66.70.+f, 63.20.Ls Introduction The thermal conductivity of simple molecular crys- tals is determined by both translational and orien- tational motion of molecules in the lattice sites. This motion can be either oscillatory or rotational depend- ing on the relation between the noncentral force and the rotational kinetic energy. Except for rare cases (quantum crystals), the motion of molecules at rather low temperatures is inherently oscillatory: the mo- lecules execute orientational vibrations about equi- librium directions. As the temperature rises, the root-mean-square (rms) amplitudes of the librations increase and the molecules can jump over some accessi- ble orientations. This may lead to a phase transition be- cause the long-range orientation order dissappears. By choosing crystals with different parameters of molecu- lar interaction and varying the temperature, it is possi- ble to change the degree of the orientational order and investigate the effect of the molecule rotation upon the thermal conductivity. Owing to their rather simple and largely similar physical properties [1,2], the N2-type crystals (N2, CO, N2O è CO2) consisting of linear molecules come as suitable objects for such studies. In these crystals the noncentral part of the molecular interaction is de- termined mostly by the quadrupole force. At low tem- peratures and pressures, these crystals have a cubic lattice with four molecules per unit cell. The axes of the molecules are along the body diagonals of cube. In N2 and CO2 having equivalent diagonal directions the crystal symmetry is Pa3, for the noncentrosymmetrical molecules CO and N2O the crystal symmetry is P213. In CO2 and N2O the noncentral interaction is very strong and the long-range orientational order can per- sist up to their melting temperatures. In N2 and CO the barriers impeding the rotation of the molecules are an order of magnitude lower; as a result, orientational disordering phase transitions occur at 35.7 and 68.13 K, respectively. In the high-temperature phases, the N2 and CO molecules occupy the sites of the hcp lattice of the spatial group P63/mmc. For a correct comparison with theory, thermal con- ductivity must be measured at constant density, which excludes the thermal expansion effect. Such investiga- tions were made on CO2 and N2O in [3]. Significant deviations from the dependence ��1/T were ob- served at T � �D. It was shown that these departures occurred when the thermal conductivity was approach- ing its lower limit. The concept of the lower limit of thermal conductivity [4] is based on the following: the mean free paths of the oscillatory modes participating in heat transfer are essentially limited, and the site-to-site heat transport proceeds as a diffusive process. The goal of this study was to investigate the isochoric thermal conductivity of solid nitrogen in both orientationally ordered and orientationally disor- dered phases. Earlier, the thermal conductivity of ni- © V.A. Konstantinov, V.G. Manzhelii, V.P. Revyakin, and V.V. Sagan, 2005 trogen was investigated only under saturated vapour pressure [5–7]. Experimental technique Constant-volume investigations are possible for molecular solids having a comparatively low thermal pressure coefficient (dP/dT)V. Using a high-pressure cell, it is possible to grow a solid sample of sufficient density. In subsequent experiments it can be cooled with practically unchanged volume, while the pres- sure in the cell decreases slowly. In samples of mode- rate densities the pressure drops to zero at a certain characteristic temperature Ò0 and the isochoric condi- tion is then broken; on further cooling, the sample can separate from the walls of the cell. In the case of a fixed volume, melting occurs in a certain temperature interval and its onset shifts towards higher tempera- tures as density of samples increases. This is seen, for example, in the V–T phase diagram of solid N2 [2] in Fig. 1. The deviations from the constant volume caused by the thermal and elastic deformation of the measuring cell were usually no more than 0.3% and could be taken into account. The investigation was made using a steady-state technique in a coaxial-geometry setup. The measuring beryllium bronze cell was 160 mm long with the inner diameter 17.6 mm. The maximum permissible pressure in it was 800 MPa. The inner measuring cylinder was 10.2 mm in diameter. Temperature sensors (platinum resistance thermometers) were placed in special chan- nels of the inner and outer cylinders to keep them un- affected by high pressure. In the process of growing the temperature gradient over the measuring cell was 1–2 K/ñm. The pressure in the inflow capillary was varied within 50–200 ÌÐà to grow samples of differ- ent densities. When the growth was completed, the capillary was blocked by freezing it with liquid hydro- gen, and the samples were annealed at premelting temperatures for one to two hours to remove density gradients. After measurement the samples were evapo- rated into a thin-walled vessel and their masses were measured by weighing. The molar volumes of the sam- ples were estimated from the known volume of the measuring cell and the sample masses. The total (dom- inant) systematic error of measurement was no more than 4% for the thermal conductivity and 0.2% for the volume. The purity of N2 was no worse than 99.97%. Results and discussion The isochoric thermal conductivity of solid N2 was investigated on four samples of different densities in the temperature interval from 20 K to the onset of melting. The experimental thermal cunductivities are shown in Fig. 2 with solid lines for smoothed values and a dashed line for measurement under saturated va- por pressure [2, 5–7]. Under the same P, T conditions, the discrepancy between our and literature data was no more than 5%. The molar volumes Vm, tempera- tures T0 (onset of V = const condition) and Tm (onset of sample melting) are shown in Table 1. This infor- mation is also available in Fig. 1. Table 1. Molar volumes Vm, temperatures T0 (onset of V = const condition) and temperatures Tm (onset of melting). Sample No Vm, ñm3/mole T0, K Tm, K 1 27.36 24 102 2 27.68 33 96 3 27.98 36 92 4 28.76 48 80 In �-N2 the temperature dependence of the iso- choric thermal conductivity is weaker than ��1/T and in similar to that observed for CO2 and N2O [3]. The thermal conductivity is practically constant im- mediately before the ��� transition. Earlier, the ther- mal conductivity was observed to grow in orienta- tionally disordered phases of some molecular crystals [8]. The Bridgman coefficients g / V T� ( ln ln )� calculated from the experimental results are 6.0 � 0.8 for �-N2 at T = 35 K and 4.3 � 0.5 for �-N2 at T = 60 K. The orientational motion of the molecules in �-N2 manifests itself as large-angle librations (immediately before the ��� transition the rms libration ampli- tudes � 2�1/2 exceed 30�) attended with hopping over a limited set of equivalent orientations related by the group symmetry elements [1]. The frequency of reorientations approaches 10–11 s–1 near the ��� trànsition [9]. The analysis of heat capacity data sug- 554 Fizika Nizkikh Temperatur, 2005, v. 31, No. 5 V.A. Konstantinov, V.G. Manzhelii, V.P. Revyakin, and V.V. Sagan 0 20 40 60 80 100 120 27 28 29 30 31 � �+ Tm T0 L� + L N2 4 3 2 1 �� 3 m T, K V ,ñ m /ì o le Fig. 1. V–T phase diagram of solid N2 according to [1,2]: molar volumes (----); arrows show the onset of V = const condition and melting. gests that practically free precession of the molecules is observed in �-N2 after the phase transition, which is accompanied by axial vibration through an angle � with respect to the hexagonal axis of the cell [1]. In the �-phase of N2 the frequency of reorientations varies from 9.5�1011 s–1 immediately after ��� transition to 5.5�1012 s–1 before melting [9]. This exceed considerably the Debye frequency 1.5�1012 s–1. No distinct libration modes were detected in �-N2 in inelastic neutron scat- tering experiments, and even the observed translational acoustic phonons were broadened considerably due to the translation-orientation interaction, excluding the case of the smallest wave vectors [10]. Remembering that the orientational motion of the molecules in �-N2 is essentially librational in charac- ter, the thermal conductivity can be calculated within a model in which the heat is transferred by low-fre- quency phonons or «diffusive» modes above the mo- bility edge. Earlier, the model was used to calculate the thermal conductivity of CO2 and N2O [11]. Let us describe the thermal conductivity as: � � � ( ) ( ) ( ) T nk v T l x x dxB D x x /TD � � � �� � � �� �3 1 3 4 2 0 e e , (1) wherå �D = v(h/kB) (6�2n)1/3, n is the number of atoms (molecules) per unit volume, v is the polariza- tion-averaged sound velocity, l(x) is the phonon mean free path. At T � �D the mean free path is mainly de- termined by the umklapp processes l(x) = lu, wherå: l CTu � �2 , C = (12�3/�2) n–1/3 (�2 k B /mv2). (2) Here � is the phonon wavelenth, � is the Grüneisen constant, m is the atomic (molecular) mass, C is the numerical coefficient. In the first approximation, the translation-orientation interaction in molecular crys- tals leads to extra scattering which can be taken into account through simple renormalization of the coeffi- cient C [12]. Remembering that the smallest phonon mean free path is about half the wavelength: l(x) = = ��/2, wherå � � 1, the «diffusivity» edge �* can be found as: � �* � CT 2 , (3) which corresponds to the effective temperature �* = = 2hv/�kBCT. (It is assumed that �* � �D, other- wise �* = �D.) Below, the term «diffusive» is applied to the modes whose mean free paths reached the smallest values [11]. The integral of thermal conduc- tivity is subdivided into two parts describing the con- tributions to the thermal conductivity from the low-frequency phonons and the «diffusive» modes: � = �ph + �dif, (4) � � � ph e e ( ) ( ) ( ) * T nk v T l x x dxB D x x /T � � � �� � � �� � ! �3 1 3 4 2 0 ! " # $ $ , (5) � � � � dif e e ( ) ( * T nk v T vh k xT x B D /T /T B x x D � � � �� � � �� �3 2 3 4 � 1 2) dx � ! ! ! " # $ $ $ . (6) The results were computer-fitted by the least-square technique to the smoothed thermal conductivity values Isochoric thermal conductivity of solid nitrogen Fizika Nizkikh Temperatur, 2005, v. 31, No. 5 555 20 40 60 80 100 0 1 2 3 4 N2 �min �dif �ph �V T, K � , m W /ñ m Ê� Fig. 3. Fitting to smoothed values of experimental ther- mal conductivity and contributions to thermal conductivity from low-frequency phonons �ph and «diffusive» modes �dif calculated according to (5),(6); the lower limit of lat- tice heat conduetivity �min obtained as an asymptote of the dependence �V(T) (---). 20 40 60 80 100 2 3 4 5 4 3 2 1 N 2 T , K � , m W /ñ m Ê� Fig. 2. Isochoric thermal conductivity of four solid N2 sam- ples of different densities (see Table 1): smoothed values (%), measurement under saturated vapor pressure according to [2, 5–7] (---), the arrows indicate the onset of melting. for sample in the � phaså using n = 2.21�1022 cm–3 and v = 1.17�103 m/s [2] and varying the parameters C and �. The best agreement with experiment was ob- tained with C = 3.0�10–9 cm/K and � = 1.8. Corres- pondingly, C = 0.9�10–9 cm/K and � = 2.7 for CO2 and C = 1.5�10–9 cm/K and � = 2.3 for N2O [11]. The fitting to smoothed experimental thermal conductivi- ties and the contributions from the low-frequency phonons �ph and the «diffusive» modes �dif (calcu- lated by Eqs. (5),(6)) are shown in Fig. 3. It is seen that the «diffusive» behavior of the oscil- latory modes appears above 20 K, and immediately be- fore the ��� transition nearly half of the heat is transported by the «diffusive» modes. The curves �ph and �dif calculated for the � phase of N2 were extrapo- lated to the region of the existence of the � phase. The change from one structure to another may cause a jump of the partial contributions to the thermal con- ductivity but it will not be too large because a major part of the heat is transported by the «diffusive» modes and they are only slightly sensitive to the struc- ture of the crystal. The lower limit of thermal conduc- tivity �&min (Fig. 3, broken line) was calculated as- suming that all the modes were «diffusive»: & � � � � � � � � � �� � � �� � �min ( ) 3 6 1 1 3 2 3 2 3 2 � � / / B D x x n k v T x d e e x D/T 0 � � . (7) Note that �&min is again independent of structure and determined only by the crystal density and hence the Debye temperature were invariant for the constant vol- ume. The lower limit of thermal conductivity �&min fit- ted as an asymptote of the dependence �V (T) is � = 1.8 times higher than the value calculated according to Cahill and Pohl [4]. The discrepancy can partly be ac- counted for by the imperfection of the model. Neverthe- less, there is a certain correlation between � and the number of the degrees of freedom (three translational and z rotational degrees) of molecules: � � (3+z)/3 [11]. Cahill and Pohl considered amorphous substances and strongly disordered crystals consisting of atoms having no rotational degrees of freedom. The discussion of the lower limit of thermal con- ductivity of molecular crystals brings up the inevita- ble question: should the site-to-site transport of the rotational energy of the molecules be taken into ac- count? The above correlation suggests the positive an- swer. In this context, the heat transfer in molecular crystals, solid nitrogen in particular, can be inter- preted as follows. At low temperatures, when the phonon and libron branches are well separated, the phonons forming the heat flow are scattered by both phonons and librons [12]. As a result, the thermal re- sistance increases in comparison with the situation, e. g., in inert gases [3]. As the temperature rises, the phonon-libron interaction enhances and the mixed translation-orientation modes start to transport the heat. The heat transfer increases and extra scattering evolves due to the strong anharmonicity of the librational vibrations. Finally, under a very strong scattering when the heat is transported directly from molecule to molecule (Einstein model), both the rota- tional and translational energies should equally be taken into account. In �-N2 the isochoric thermal conductivity in- creases slightly with temperature. The absolute value of thermal conductivity is only 10–12% higher than its lower limit �&min . This means that in �-N2 most of the heat is transported by the «diffusive» modes. The con- cept of the «lower limit» of thermal conductivity pos- tulates its «saturation» rather than its growth. The in- crease in the isochoric thermal conductivity with temperature was observed earlier in orientationally disordered phases of some molecular crystals [8]. This effect can be due to the «rotational» component of the total thermal resistance, which decreases as the rota- tional correlation’s between the neighboring mole- cules become weaker. The dependence of the thermal conductivity on the molar volume can also be interpreted within this model. The Bridgman coefficient g / V T� ( ln ln )� is the weighted mean with respect to the phonons and «diffusive» modes whose volume dependences are con- siderably different [11]: g g g� ' � � � � ph ph dif dif . (8) Equation (8) describes the general tendency of the Bridgman coefficient to decrease as more of heat is being transported by «diffusive» modes. The calculation using the procedure [11] and the mean Gruneisen coefficient � = 2.2 for nitrogen [1,2] gives g = 5.2 at T = 35 K and 3.4 at T = 60 K, which is in reasonable agreement with the experimental values. Conclusions The isochoric thermal conductivity of solid N2 has been investigated on four samples of different densi- ties in the temperature interval from 20 K to the onset of melting. In �-N2 the isochoric thermal conductivity varies following a dependence weaker than ��1/T; in �-N2 it increases slightly with temperature. It is shown that the experimental results can be explained within a model in which the heat is transported by low-frequency phonons and by «diffusive» modes above the boundary of mobility. In �-N2 most of the 556 Fizika Nizkikh Temperatur, 2005, v. 31, No. 5 V.A. Konstantinov, V.G. Manzhelii, V.P. Revyakin, and V.V. Sagan heat transported by the «diffusive» modes. The weak growth of the thermal conductivity in �-N2 can be at- tributed to the decrease in the «rotational» component of the total thermal resistance due to the relaxing rota- tional correlations between the neighboring molecules. This study was supported by the Ukrainian Minis- try of Education and Science, Project (7/286-2001 «Novel quantum and unharmonic effects in mixtures of cryocrystals». 1. Physics of Cryocrystals, V.G. Manzhelii and Yu.A. Freiman (eds.), AIP, New York (1996). 2. V.G. Manzhelii, A.I. Prokhvatilov, V.G. Gavrilko, and A.P. Isakina, Structure and Termodynamic Properties of Cryocrystals, Begell House, inc., New York, Walingford, U.K. (1999). 3. V.A. Konstantinov, V.G. Manzhelii, S.A. Smirnov, and A.M. Tolkachev, Fiz. Nizk. Temp. 14, 189 (1988) [Sov. J. Low Temp. Phys. 14, 104 (1988)]. 4. D.G. Cahill, S.K. Watson, and R.O. Pohl, Phys. Rev. B46, 6131 (1992). 5. H.M. Roder, Cryogenics 2, 302 (1962). 6. L.A. Koloskova, I.N. Krupskii, V.G. Manzhelii, and B.Ya. Gorodilov, Fiz. Tverd. Tela 15, 1913 (1973) [Sov. Phys. Solid State 15, 1278 (1973)]. 7. P. Stachoviak, V.V. Sumarokov, J. Mucha, and A. Jezowski, Phys. Rev. B50, 543 (1994). 8. O.I. Purskii, N.N. Zholonko, and V.A. Konstantinov, Fiz. Nizk. Temp. 29, 1021 (2003) [Low Temp. Phys. 29, 771 (2003)]. 9. T.A. Scott, Phys. Lett. C27, 89 (1976). 10. B.M. Powell, G. Doling, and H.F. Nieman, J. Chem. Phys. 79, 982 (1983). 11. V.A. Konstantinov, Fiz. Nizk. Temp. 29, 567 (2003) [Low Temp. Phys. 29, 442 (2003)]. 12. V.G. Manzhelii, V.B. Kokshenev, L.A. Koloskova, and I.N. Krupskii, Fiz. Nizk. Temp. 1, 1302 (1975) [Sov. J. Low Temp. Phys. 1, 624 (1975)]. Isochoric thermal conductivity of solid nitrogen Fizika Nizkikh Temperatur, 2005, v. 31, No. 5 557