Phonon excitations in the quasi-one-dimensional Haldane phase of SrNi₂V₂O₈

Vibrational Raman spectra of a single crystal of the coupled Haldane chain compound SrNi₂V₂O₈ with uniaxial anisotropy were investigated in the 10–1000 cm⁻¹ frequency range at temperatures 7–300 K. No structural phase transition was observed. The number of phonon lines observed in the experiment and...

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Автори: Kurnosov, V., Gnezdilov, V., Lemmens, P., Pashkevich, Y., Bera, A.K., Islam, A.T.M.N., Lake, B.
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Опубліковано: Фізико-технічний інститут низьких температур ім. Б.І. Вєркіна НАН України 2017
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Цитувати:Phonon excitations in the quasi-one-dimensional Haldane phase of SrNi₂V₂O₈ / V. Kurnosov, V. Gnezdilov, P. Lemmens, Y. Pashkevich, A.K. Bera, A.T.M.N. Islam, B. Lake // Физика низких температур. — 2017. — Т. 43, № 12. — С. 1761-1772. — Бібліогр.: 36 назв. — англ.

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Digital Library of Periodicals of National Academy of Sciences of Ukraine
id nasplib_isofts_kiev_ua-123456789-175361
record_format dspace
spelling Kurnosov, V.
Gnezdilov, V.
Lemmens, P.
Pashkevich, Y.
Bera, A.K.
Islam, A.T.M.N.
Lake, B.
2021-01-31T20:37:52Z
2021-01-31T20:37:52Z
2017
Phonon excitations in the quasi-one-dimensional Haldane phase of SrNi₂V₂O₈ / V. Kurnosov, V. Gnezdilov, P. Lemmens, Y. Pashkevich, A.K. Bera, A.T.M.N. Islam, B. Lake // Физика низких температур. — 2017. — Т. 43, № 12. — С. 1761-1772. — Бібліогр.: 36 назв. — англ.
0132-6414
PACS: 78.30.–j, 63.20.–e
https://nasplib.isofts.kiev.ua/handle/123456789/175361
Vibrational Raman spectra of a single crystal of the coupled Haldane chain compound SrNi₂V₂O₈ with uniaxial anisotropy were investigated in the 10–1000 cm⁻¹ frequency range at temperatures 7–300 K. No structural phase transition was observed. The number of phonon lines observed in the experiment and their intensity were analyzed on the basis of the local symmetry considerations of different structural complexes. This approach was successful in explaining the discrepancy between the numbers of expected and experimentally observed phonon lines. Closeness of a real arrangement of some structural units to higher symmetry than the Wyckoff position results in strong interferential quenching of a number of Raman lines in the spectra.
en
Фізико-технічний інститут низьких температур ім. Б.І. Вєркіна НАН України
Физика низких температур
Низкотемпературная оптическая спектроскопия
Phonon excitations in the quasi-one-dimensional Haldane phase of SrNi₂V₂O₈
Article
published earlier
institution Digital Library of Periodicals of National Academy of Sciences of Ukraine
collection DSpace DC
title Phonon excitations in the quasi-one-dimensional Haldane phase of SrNi₂V₂O₈
spellingShingle Phonon excitations in the quasi-one-dimensional Haldane phase of SrNi₂V₂O₈
Kurnosov, V.
Gnezdilov, V.
Lemmens, P.
Pashkevich, Y.
Bera, A.K.
Islam, A.T.M.N.
Lake, B.
Низкотемпературная оптическая спектроскопия
title_short Phonon excitations in the quasi-one-dimensional Haldane phase of SrNi₂V₂O₈
title_full Phonon excitations in the quasi-one-dimensional Haldane phase of SrNi₂V₂O₈
title_fullStr Phonon excitations in the quasi-one-dimensional Haldane phase of SrNi₂V₂O₈
title_full_unstemmed Phonon excitations in the quasi-one-dimensional Haldane phase of SrNi₂V₂O₈
title_sort phonon excitations in the quasi-one-dimensional haldane phase of srni₂v₂o₈
author Kurnosov, V.
Gnezdilov, V.
Lemmens, P.
Pashkevich, Y.
Bera, A.K.
Islam, A.T.M.N.
Lake, B.
author_facet Kurnosov, V.
Gnezdilov, V.
Lemmens, P.
Pashkevich, Y.
Bera, A.K.
Islam, A.T.M.N.
Lake, B.
topic Низкотемпературная оптическая спектроскопия
topic_facet Низкотемпературная оптическая спектроскопия
publishDate 2017
language English
container_title Физика низких температур
publisher Фізико-технічний інститут низьких температур ім. Б.І. Вєркіна НАН України
format Article
description Vibrational Raman spectra of a single crystal of the coupled Haldane chain compound SrNi₂V₂O₈ with uniaxial anisotropy were investigated in the 10–1000 cm⁻¹ frequency range at temperatures 7–300 K. No structural phase transition was observed. The number of phonon lines observed in the experiment and their intensity were analyzed on the basis of the local symmetry considerations of different structural complexes. This approach was successful in explaining the discrepancy between the numbers of expected and experimentally observed phonon lines. Closeness of a real arrangement of some structural units to higher symmetry than the Wyckoff position results in strong interferential quenching of a number of Raman lines in the spectra.
issn 0132-6414
url https://nasplib.isofts.kiev.ua/handle/123456789/175361
citation_txt Phonon excitations in the quasi-one-dimensional Haldane phase of SrNi₂V₂O₈ / V. Kurnosov, V. Gnezdilov, P. Lemmens, Y. Pashkevich, A.K. Bera, A.T.M.N. Islam, B. Lake // Физика низких температур. — 2017. — Т. 43, № 12. — С. 1761-1772. — Бібліогр.: 36 назв. — англ.
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fulltext Low Temperature Physics/Fizika Nizkikh Temperatur, 2017, v. 43, No. 12, pp. 1761–1772 Phonon excitations in the quasi-one-dimensional Haldane phase of SrNi2V2O8 V. Kurnosov1, V. Gnezdilov1, 2, P. Lemmens2, Yu. Pashkevich3, A.K. Bera4, A.T.M.N. Islam4, and B. Lake4 1B. Verkin Institute for Low Temperature Physics and Engineering, NASU, Kharkov 61103, Ukraine 2Institute for Condensed Matter Physics, TU Braunschweig, D-38106 Braunschweig, Germany 3A.A. Galkin Donetsk Institute for Physics and Engineering, NASU, Kyiv 03680, Ukraine 4Helmholtz-Zentrum Berlin, Hahn-Meitner-Platz 1, Berlin 14109, Germany E-mail: kurnosov@ilt.kharkov.ua Received April 4, 2017, published online October 25, 2017 Vibrational Raman spectra of a single crystal of the coupled Haldane chain compound SrNi2V2O8 with uniax- ial anisotropy were investigated in the 10–1000 cm−1 frequency range at temperatures 7–300 K. No structural phase transition was observed. The number of phonon lines observed in the experiment and their intensity were analyzed on the basis of the local symmetry considerations of different structural complexes. This approach was successful in explaining the discrepancy between the numbers of expected and experimentally observed phonon lines. Closeness of a real arrangement of some structural units to higher symmetry than the Wyckoff position re- sults in strong interferential quenching of a number of Raman lines in the spectra. PACS: 78.30.–j Infrared and Raman spectra; 63.20.–e Phonons in crystal lattices. Keywords: Raman intensity, local symmetry consideration, interferential quenching. 1. Introduction A remarkable feature of one-dimensional (1D) magnetic systems is the suppression of long-range magnetic order even at zero temperature by strong quantum spin fluctua- tions. Spin-1 Heisenberg antiferromagnetic (AFM) chains (Haldane chains) are of current interest due to their exotic magnetic properties [1,2]. The Haldane phase of integer spin chains has a unique many-body singlet ground state and gapped magnetic excitations [3,4] in contrast to the gapless continuum of multispinon excitations of its half-integer coun- terpart, the spin-1/2 Heisenberg uniform AFM chain. The magnetic excitation spectra of an isolated Haldane chain were investigated in great detail using theoretical methods [5–7], as well as experimental techniques [8,9]. Raman scattering was proven to be a versatile tool to in- vestigate compounds that represent low-dimensional quantum spin systems [10]. In addition to spin excitations, also excita- tions of the lattice system or even coupled modes can be in- vestigated. This may help to better understand the effect of the lattice degrees of freedom on the spin system. Despite the great interest in Haldane chains materials, there are very few studies of these systems using Raman spectroscopy. To our present knowledge, detailed investigations only exist for the one S = 1 spin chain compound Y2BaNiO5 [11]. In real systems the presence of interchain interactions and anisotropy leads to complex behaviors and a rich phase diagram as theoretically described in Ref. 12. In this regard compounds ANi2V2O8, where A = Sr or Pb, are of interest since they have substantial interchain interactions and sin- gle-ion uniaxial anisotropy [13,14]. According to earlier experiments on powder samples [13,15] the ground state of SrNi2V2O8 was suggested to be 3D ordered below ~7 K. Later, in numerous experiments [16–22] it has been con- vincingly shown that SrNi2V2O8 has a nonmagnetic spin- singlet ground state. Our present research activities aim to analyze phonon excitations of the quasi-1D Haldane compound SrNi2V2O8 in detail. These are based on the study of the crystal sym- metry and phonon excitations that in many cases help to uncover fundamental properties. 2. Experimental Details of the SrNi2V2O8 single crystals growth and char- acterization can be found in Refs. 19, 20. Our Raman scatter- © V. Kurnosov, V. Gnezdilov, P. Lemmens, Yu. Pashkevich, A.K. Bera, A.T.M.N. Islam, and B. Lake, 2017 V. Kurnosov, V. Gnezdilov, P. Lemmens, Yu. Pashkevich, A.K. Bera, A.T.M.N. Islam, and B. Lake ing experiments were performed in a quasi-backscattering geometry on ab and ac surfaces of SrNi2V2O8 single crystals. A solid-state laser with the excitation wavelengths λ = 532.1 nm and a power level P = 5 mW was used for the spectra excitation. Spectra of the scattered radiation were col- lected by a Dilor-XY triple spectrometer and recorded by a liquid-nitrogen-cooled CCD detector (Horiba Jobin Yvon, Spectrum One CCD-3000V) with a spectral resolution of <0.5 cm−1. In our experiments we used parallel (aa, cc) and crossed (ab, ac) light polarizations. Temperature dependences of the Raman spectra were measured in a variable temperature closed cycle cryostat (Oxford/Cryomech Optistat, RT-2.8 K). 3. Phonon spectra 3.1. Group theoretical analysis and polarization rules The structure of SrNi2V2O8 is described by the space group I41cd (#110, 12 4vC ) with z = 8 formula units per unit cell [20,23]. According our knowledge, there is no evidence of structural instabilities for temperatures below room tem- perature. Due to the existence of the “rigid” ionic complexes (VO4)3− the vibrational modes may be expressed formally in terms of internal and external degrees of freedom of these extended complexes and with respect to degrees of freedom of the point ions Sr2+ and Ni2+ (see Table 1). Table 1. Representation of SrNi2V2O8 vibrational modes in terms of internal and external degrees of freedom of ionic com- plexes (VO4)3− and translations of point ions Sr2+ and Ni2+ using the space group I41cd and 8 formula units per unit cell Ions, modes Irreps Sr2+, translational 1A1+1A2+1B1+1B2+4E Ni2+, translational 3A1+3A2+3B1+3B2+6E (VO4)3−, translational 3A1+3A2+3B1+3B2+6E (VO4)3−, rotational 3A1+3A2+3B1+3B2+6E Lattice optical 9A1+10A2+10B1+10B2+21E Lattice acoustic A1+E (VO4)3−, internal ν1 (A1) 1A1+1A2+1B1+1B2+2E ν2 (E) 2A1+2A2+2B1+2B2+4E ν3 (F2) 3A1+3A2+3B1+3B2+6E ν4 (F2) 3A1+3A2+3B1+3B2+6E (VO4)3−, internal (total) 9A1+9A2+9B1+9B2+18E There are 4 Raman-active irreps A1, B1, B2, and E whose polarizability tensors in coordinates corresponding to crystallographic directions of 4mm (C4v) have the form 1, a A z a b    →       , 1 c B c    → −      , 2 d B d    →       , , e E x e    →       , ,E y e e    →       . (1) If orientations of x and y axes are not precisely determined, the above matrices, excluding fully symmetrical irrep A1, may be generally rewritten as 1 cos 2 sin 2 ( ) sin 2 cos 2 c c B c c θ θ   θ → θ − θ      , 2 sin 2 cos 2 ( ) cos 2 sin 2 d d B d d − θ θ   θ → θ θ      , (2) cos , ( ) sin cos sin e E x e e e θ   θ → θ   θ θ  , sin , ( ) cos sin cos e E y e e e − θ   θ → θ   − θ θ  , where θ is an angle between real crystallographic direction and arbitrary direction in the basal plane of the crystal. Ac- cording to (2) the uncertainty in the orientation leads to a mix- ing of the polarization selection rules for Raman lines which belong to phonons with B1 and B2 symmetry. On the one hand, such mixing makes B1 and B2 modes unresolved, but, on the other hand, it helps to resolve A1 and B1 (and/or B2) ones. Polarization zz is “pure” for A1 modes, all other are for- bidden. It seems that this property is useful for the identifica- tion of A1 type modes and their selection in other polariza- tions. But here we face some peculiarity: the polar character of the A1 modes leads to a splitting of their longitudinal (LO) and transversal (TO) components. In opaque crystals the observation of LO and TO compo- nents of polar phonons in Raman spectra depends on specifics of experimental back scattering geometry. This information is collected in Table 2. Experimental Raman data were obtained using two sample orientations so that plane of incident light reflec- tion contained c4 axis of the crystal, or was perpendicular to it. Table 2 shows, for instance, that in zz polarization only A1 modes are present (and only TO components), while in x′x′ polarization, besides B1 and B2 phonons, A1 modes are present (LO components). So, for A1 modes possessing large LO−TO splitting zz and x′x′ polarized spectra are different in the positions of the lines. 3.2. Structure of the Raman spectrum and molecular vibrations of (VO4)3− The free ion (VO4)3− is a tetrahedral complex and de- scribed within the Td point group. It possesses 9 internal degrees of freedom, which are grouped into 4 modes trans- formed as A1(ν1)+E(ν2)+2F2(ν3+ν4) irreps of Td. Two of them belong to so-called symmetric A1(ν1) and asymmetric F2(ν3) stretchings of V−O valence bonds. They have a priori the highest vibrational frequency. Two remaining 1762 Low Temperature Physics/Fizika Nizkikh Temperatur, 2017, v. 43, No. 12 Phonon excitations in the quasi-one-dimensional Haldane phase of SrNi2V2O8 vibrational modes of the (VO4) tetrahedron are the symmet- ric E(ν2) and asymmetric F2(ν4) bendings of the valence angles. Their frequencies are very close in the free complex and are more than twice less than the frequency of stretching mode ν1. In crystals the characteristic frequency ranges of these modes are: A1(ν1) — 800–900, E(ν2) — 300–450, F2(ν3) — 700–900, F2(ν4) — 300–450 см–1 [24–30]. In aqueous solutions of (VO4)3− containing salts the frequen- cies are: A1(ν1) — 826±1, F2(ν3) — (804±4) см–1, E(ν2) and F2(ν4) — (336±2) см–1 [31]. The O2– ion has a large enough ionic radius of ~1.38 Å [32], so oxides structures often may be described like a lattice of these close packed ions, voids between which are occupied by “small” metallic ions. SrNi2V2O8 has quite such structure, where the octahedral surrounding of every Ni2+ ion consists of the same O2– ions that belong to six different (VO4)3– complexes. Octahedral oxygen com- plexes of transitional metals are very popular units repre- senting metal-oxide crystal structures too. The internal vibrations of (NiO6) octahedrons reach frequencies of about 550 cm−1 [33–35], so the individuality of all internal modes of (VO4)3− tetrahedra becomes doubtful. Looking on the Raman spectra of SrNi2V2O8 one can divide them into two ranges: 50–500 and 700–950 cm–1 (Fig. 1). It is clear that the high-frequency region is occupied by vibra- tions that originate from A1(ν1) and F2(ν3) internal modes of 8 (VO4)3− tetrahedra contained in the primitive cell. Only these modes keep their individuality and are well isolated from the low-frequency “lattice” vibration region. In contrast the bending modes of (VO4)3− tetrahedra merge with other modes of the crystal, producing the so-called “lattice” region. According to the Table 1, high-frequency region of the SrNi2V2O8 Raman spectrum must contain lines corresponding to 4A1+4B1+4B2+8E irreps (4A2 irreps are silent). The lattice range corresponds to 14A1+15B1+15B2+31E Raman-active vibrational modes, accordingly. Let us consider the spectral features of the high- frequency region: Spectra in all experimental polarizations at low temperature are presented in Fig. 2. The decomposi- tion into the series of Lorentz-shape-like spectral lines is presented ibid. At low temperatures the most intensive A1 lines show an appreciable asymmetry on the high- frequency slope. The high-temperature spectra don’t reveal such features due to a temperature induced broadening of the lines. The nature of such asymmetry is not in the center of the present paper. As a suitable hypothesis we propose, that it may be a result of the combination of intensive opti- cal modes with acoustical modes. Asymmetry in this case reflects a difference between the probabilities to excite and annihilate acoustic phonons, which is larger at low temper- atures. High temperature equalizes the probabilities and makes the wings of the line symmetrical. Table 2. Raman selection rules for phonons of a different symmetry in the quasi-back scattering geometry utilized in the experi- ments. Symbols: q is direction of phonon wave-vector, ei and es are polarizations of an incident and scattered light, respectively, α = cos θ, β = sin θ. Intensities of a scattering are evaluated using the tensor components from (1) q ei es A1 E B1 B2 (0,0,1) (α,β,0) (α,β,0) a2 (LO) (α2−β2)2c2 4(αβ)2d2 (0,0,1) (α,β,0) (β,−α,0) 4(αβ)2c2 (α2−β2)2d2 (α,β,0) (0,0,1) (0,0,1) b2 (TO) (α,β,0) (β,−α,0) (0,0,1) e2 (TO) Fig. 1. (Color online) Raman spectra of SrNi2V2O8 single crystal at T = 7 K in four polarizations. Irreps of Raman-active phonon excitations for every polarization are indicated. Low Temperature Physics/Fizika Nizkikh Temperatur, 2017, v. 43, No. 12 1763 V. Kurnosov, V. Gnezdilov, P. Lemmens, Yu. Pashkevich, A.K. Bera, A.T.M.N. Islam, and B. Lake All identified lines are collected in Table 3. The spectrum in zz polarization with A1(TO) consists of 5 lines, four of which are the Davydov components of ν1(A1) and ν3(F2) stretching modes of the (VO4)3− tetrahedron (Fig. 2(a), (b)). Note, that triple degeneracy of ν3(F2) mode is lifted due to crystal field effect. The most intense line at 857.5 cm−1 must be attributed to the ν1 mode according to frequency position. So, the highest-frequency line at 914 cm−1 most likely refers to some kind of two-particle excitation. The identical line is situated in x′x′ spectrum and has zero LO−TO splitting (Fig. 2(c), (d)). This spectrum contains a set of lines belonging to A1(LO), B1, and B2 modes. B modes may be identified by means of a y′x′ polarized spec- trum (Fig. 2(e), (f)). Remaining spectrum of x′z polariza- tion contains lines related to E(TO) modes. The most intense line (ν1) is observed in diagonal po- larizations zz and x′x′. It demonstrates a so-called “invert- ed” LO−TO splitting (see Table 3). Originally, in the frame of Td symmetry of a free (VO4)3− complex, this mode is nonpolar. It is in agreement with a small observed LO−TO splitting. Inversion is a result of a fall of its energy into a wide, forbidden gap of some strong dipolar mode. The same “inversion”, but with smaller splitting is inherent in the other intensive line (ν3) at 788 cm−1. Most probably the dipole mode with great oscillator strength originates from a polar ν3 mode of a (VO4)3– tetrahedron and pos- sesses 778.2 (TO)–890.2 (LO) cm−1 splitting that covers the greater part of discussed spectral range. As was mentioned above, every internal degree of freedom, taking into account its degeneracy, produces 4 different one-dimensional irreps Fig. 2. (Color online) High-frequency Raman spectra of SrNi2V2O8 in the range of ν1(A1) and ν3(F2) vibrational modes of (VO4)3− complex. Polarization and corresponding symmetry of the modes are marked. Intensity scales on left and right panels differ in 10 times. 1764 Low Temperature Physics/Fizika Nizkikh Temperatur, 2017, v. 43, No. 12 Phonon excitations in the quasi-one-dimensional Haldane phase of SrNi2V2O8 (A1, A2, B1, B2) and 2 two-dimensional ones (E) in the crys- tal. So, there are 4 groups of lines, each belongs to one de- gree of freedom, and must be presented by A1+B1+B2+2E symmetry. Figure 2 and Table 3 reveal detection of all 4 A1 lines, 6 B1+B2 lines versus 8 allowed, and 4 E lines versus 8 allowed. 3.3. Low-frequency Raman spectra of SrNi2V2O8 The low-frequency “lattice” range of Raman spectra does not show noticeable anomalies in their temperature dependence. Spectra in four polarizations belonging to phonons of different symmetry are presented in Fig. 3. The temperature dependences of the frequencies of all detected lines are shown in Fig. 4. A list of all detected phonon lines at lowest temperature with the indication of their symmetry and related polarization rules are given in Table 4. The total number of observed and detected low-temperature lines is essentially smaller than the group theory predicts. Only 11 from 14 A1, 15 from 30 (B1+B2), and 16 from 31 E of al- lowed phononic lines are detected. The cause of such a deficit is probably the big number of formula units in the crystal unit cell that leads to small Raman intensities of some modes due to practically full interferential quench- ing. These aspects are considered in the following section. 4. Symmetry aspects of the phonon excitations intensity in the Raman spectrum of SrNi2V2O8 Intensity of the Raman scattering originates from a polarizability induced by an appropriate mode in the crys- tal. Group theoretical analysis gives the total number of the modes based on the symmetry positions of the ions in the structure. Symmetry of some complexes (dimensions, an- gles, etc.) of a crystal structure sometimes appears higher than their Wyckoff positions. It may lead to the extremely weak intensity of some Raman signals. The following sec- tions cover these issues. Table 3. Frequencies, integral intensities and assignment of Raman lines observed in the spectral range of ν1(A1) and ν3(F2) vibrational modes of (VO4)3− complex in SrNi2V2O8 Frequency, cm−1 Integral intensity, arb. units Irreps Polarization Mode 717.0 1991 A1(TO) zz ν3 761.6 7832 A1(LO) x′x′ 731.5 451 B1+B2 x′x′ 201 B1+B2 y′x′ 747.2 16606 E(TO) x′z 778.2 12734 A1(TO) zz ν3 890.2 33888 A1(LO) x′x′ 782.7 1271 E(TO) x′z 793.2 958 E(TO) x′z 793.4 7188 B1+B2 x′x′ 1236 B1+B2 y′x′ 788.0 80697 A1(LO) x′x′ ν3 788.4 138057 A1(TO) zz 817.9 14509 B1+B2 x′x′ 17922 B1+B2 y′x′ 821.7 387 E(TO) x′z 827.5 5594 B1+B2 x′x′ 9116 B1+B2 y′x′ 851.9 282998 A1(LO) x′x′ ν1 857.5 196273 A1(TO) zz 881.9 24959 B1+B2 x′x′ 11177 B1+B2 y′x′ 896.3 445 B1+B2 x′x′ 1585 B1+B2 y′x′ 914.0 2902 A1(TO) zz two-particle 912.9 2241 A1(LO) x′x′ Low Temperature Physics/Fizika Nizkikh Temperatur, 2017, v. 43, No. 12 1765 V. Kurnosov, V. Gnezdilov, P. Lemmens, Yu. Pashkevich, A.K. Bera, A.T.M.N. Islam, and B. Lake 4.1. (VO4)3− modes In the structure of SrNi2V2O8 the (VO4)3– complexes occupy general positions, but their local second order axes in the Td symmetry notation are oriented close to the prin- cipal axes of the crystal. More precisely, there are two groups of the tetrahedra whose second order axes are prac- tically parallel to x and y crystallographic directions. Fur- thermore, the tetrahedra are slightly rotated around these preferred axes as can be seen in Fig. 5. We also consider some uniaxial distortion of the tetrahedra along those pre- ferred axes in order to include to their polarizability some small parameters reflected the low symmetry of the po- sition. Fig. 3. (Color online) Temperature dependences of low-frequency range of SrNi2V2O8 Raman spectrum in: (a) x′z polarization corre- sponding to E(TO) modes, (b) x′x′ polarization corresponding to A1(LO)+B1+B2 modes, (c) y′x′ polarization corresponding to B1+B2 modes, and (d) zz polarization corresponding to A1(TO) modes. Insets show some spectral peculiarities in detail. 1766 Low Temperature Physics/Fizika Nizkikh Temperatur, 2017, v. 43, No. 12 Phonon excitations in the quasi-one-dimensional Haldane phase of SrNi2V2O8 Using such approach, the polarizabilities of an individual VO4 tetrahedron related with its own modes in the crystal are expressed in the following manner: 1 1mol ( ) a A a A a a + ∆   α =       , ( )1 mol 2 (1)A b E b b −   α =       , ( )1 mol 0 (2) 3 3 B b b E b b     α = δ   δ −  , ( )2 ( ) 2mol ( ) ,B x c c F x c c    α = δ   −δ  ( )( ) 2mol ( ) d E y d d F y d δ   α = δ      , ( )( ) 2mol ( ) , d E z d d F z d −δ   α =    −δ  (3) where term ∆a and difference between c and d are due to an uniaxial distortion of the tetrahedron along x axis; terms δb, δc, and δd are due to slight rotation around x axis. Us- ing these assumptions and symmetry coordinates of nondegenerated modes of the crystal, the polarizabilities arising from A1, E, and F2 modes of the tetrahedra can be expressed as follows: ___________________________________________________ 1 1cryst 2 ( ) 2 2 2 a A a a A a a + ∆   α = + ∆      , 1 1cryst ( ) 2 0 a B aA ∆   α = −∆      , ( )1 cryst (1) 2 2 A b E b b −   α = −      , ( )1 cryst (1) 3 2 0 B b E b −   α =       , Fig. 4. (Color online) Temperature dependences of frequencies of all detected Raman-active phonons in the low-frequency range in SrNi2V2O8. Table 4. Frequencies of observed Raman lines (in cm−1) of the low-frequency spectral range in SrNi2V2O8 at a temperature 7 K. A symmetry assignment is based on the polarization selection rules A1(TO) A1(LO) B1+B2 E(TO) zz x′x′ x′x′, y′x′ x′z 78.5 81.7 92.0 96.1 131.2 115.2 144.9 143.8 148.6 157.1 159.9 164.3 165.3 167.2 167.8 173.9 190.9 186.5 205.8 196.7 229.9 230.2 230.4 232.3 238.0 280.9 281.8 289.2 298.9 304.2 314.3 316.1 334.5 334.9 322.7 356.6 358.0 370.5 368.4 374.0 394.3 395.3 394.3 402.3 411.3 403.3 417.2 431.1 433.2 441.5 483.7 439.2 Low Temperature Physics/Fizika Nizkikh Temperatur, 2017, v. 43, No. 12 1767 V. Kurnosov, V. Gnezdilov, P. Lemmens, Yu. Pashkevich, A.K. Bera, A.T.M.N. Islam, and B. Lake ( )1 cryst (2) 6 2 A b E b b    α =    −  , ( )1 cryst (2) 6 0 B b E b    α = −      , ( )1 2cryst ( ) 2 2 c A c c F x δ   α = δ   − δ  , ( )1 2cryst ( ) 2 0 c B cF x −δ   α = δ      , ( )2 2cryst ( ) 2 2 d B dF y δ   α = δ      , ( )2 2cryst ( ) 2 2B d F z d    α =       . (4) Here the upper indices mark irreps of the crystal modes while symbols in parentheses belong to the internal modes of tet- rahedron. Twice-degenerated modes of the crystal have xz and yz components of polarizability tensor only. That is why they can on- ly originate from those modes of an individual molecule, whose polarizabilities contain such components. It follows from (3) that appreciable Raman intensity of twice degenerated modes in the crystal arises from the modes related to E(2), F2(x), F2(y), and F2(z) molecular vibrations only. Theoretically these 4 degrees of freedom generate 8 crystal E modes, but only half of them possess nonzero Raman polarizability. In order to understand why this happens we can consider the example of F2(x) and F2(y) molecular degrees of freedom. These modes are dipolar that makes convenient their vector representation, as shown in Fig. 5. The xz components of crystal polarizability for modes shown in Fig. 5 are expressed as follows according to (4): ( )cryst 1 2 3 5 871 4 6 1( ) 2( ), 2 2 yz yz yz yzxz xz xz xz xzS c dα = α +α +α +α +α +α +α +α = + ( )cryst 2 2 3 5 871 4 6 1( ) 2( ), 2 2 yz yz yz yzxz xz xz xz xzS c dα = α +α +α +α −α −α −α −α = − ( )cryst 3 2 3 5 871 4 6 1( ) 0, 2 2 yz yz yz yzxz xz xz xz xzSα = α −α −α +α +α −α −α +α = ( )cryst 4 2 3 5 871 4 6 1( ) 0. 2 2 yz yz yz yzxz xz xz xz xzSα = α −α −α +α −α +α +α −α = (5) Fig. 5. (Color online) Patterns of y components of twice-degenerated modes in SrNi2V2O8 originating from F2 vibrational modes of tetrahedral (VO4)3− complexes. Numeration of all tetrahedra belonging to primitive cell is used in expressions (5). 1768 Low Temperature Physics/Fizika Nizkikh Temperatur, 2017, v. 43, No. 12 Phonon excitations in the quasi-one-dimensional Haldane phase of SrNi2V2O8 Modes S3 and S4 are silent due to orientation of one of the second order axes of the tetrahedra along crystallo- graphic direction in the crystal basal plane. Mode S2 is also weak because c ≈ d. All nonzero polarizability ten- sors of the crystal for twice-degenerated modes are pre- sented below: ___________________________________________________ ( )( ) cryst (2) 2 b E x b E δ   α =    δ  , ( )( ) cryst (2) 2E y b b E    α = δ   δ  , ( )( ) 2cryst ( ) 2 d E x d F z −δ   α =    −δ  , ( )( ) 2cryst ( ) 2E y d d F z    α = −δ   −δ  , ( )( ) 2cryst ( , ) 2E x d c F x y d c +   α =    +  , ( )( ) 2cryst ( , ) 2E y F x y d c d c    α = +   +  , ( )( ) 2cryst ( , ) 2E x d c F x y d c −   α =    −  , ( )( ) 2cryst ( , ) 2E y F x y d c d c    α = −   −  . (6) ______________________________________________ Results of the analysis are collected in Table 5. With regard to A1(ν1) and F2(ν3) modes of high- frequency region, only one A1(ν1), one B2(ν3), and one E(ν3) modes are expected to be intense if we assume that their polarizability is originated purely from the molecular polarizability. Taking into account small deviations from ideal form and orientation of the tetrahedra the weak A1(ν3), B1(ν1), B1(ν3), B2(ν3), and 2 E(ν3) can be added. A comparison with experiment shows partial match. So, in E spectrum one intense and three weak lines are ob- served that differ from the prediction of one weak line. It is remarkable that in the frequency range of ν1 mode no Ra- man signal of E polarization is detected, that is in agree- ment with the prediction. The analysis allows 4 B1,2 modes Table 5. Raman tensor components calculated for A1, E and F2 modes of tetrahedral (VO4)3− complexes in SrNi2V2O8 crystal. In the first column the symmetry of a free tetrahedron mode is indicated in parentheses xx yy zz A1(A1) (2a+∆a) 2 (2a+∆a) 2 2a 2 A1(F2(x)) δc 2 δc 2 −2δc 2 A1(E(1)) −b 2 −b 2 2b 2 A1(E(2)) b 6 b 6 −2b 6 B1(A1) ∆a 2 −∆a 2 B1(E(1)) −3b 2 3b 2 B1(E(2)) b 6 −b 6 B1(F2(x)) −δc 2 δc 2 xy=yx xz=zx yz=zy B2(F2(z)) 2d 2 B2(F2(y)) 2δd 2 E(E(2)) 2δb 2δb E(F2(x,y)) (d+c) 2 (d+c) 2 E(F2(x,y)) (d−c) 2 (d−c) 2 E(F2(z)) −2δd −2δd Low Temperature Physics/Fizika Nizkikh Temperatur, 2017, v. 43, No. 12 1769 V. Kurnosov, V. Gnezdilov, P. Lemmens, Yu. Pashkevich, A.K. Bera, A.T.M.N. Islam, and B. Lake with the most intense component in the frequency region of the ν3 mode. Experimentally two intense and four weak lines are detected. One of the intense lines is close to the ν1 frequency. It may mean that ∆a term of the molecular polarizability is essential enough. In diagonal zz polariza- tion (A1 modes) there are two intense enough lines close to frequencies of ν1 and ν3 modes of free VO4 tetrahedron. The analysis predicts less intense line due to δc term origi- nated from the tetrahedra tilt. Its comparable with A1(ν1) mode intensity can not be explained in the proposed simple model where crystal polarizability is originated from the molecular polarizability only. Real situation may be too different from such a rough estimation. It means, for in- stance, that some of these internal modes of the molecular complexes may strongly polarize the crystal surrounding. Nevertheless the model provides evidence that a large number of (VO4)3– complexes situated in the crystal struc- ture may lead to the interferential quenching of their polarizability, resulting in a smaller number of intense lines observed in the Raman spectra indeed. As for E(ν2) and F2(ν4) modes of the tetrahedral (VO4)3– complexes, the analysis predicts 3A1+5B1,2+4E lines in the Raman spectrum of the crystal, including those with small intensity. Remembering the group theory pre- diction for these modes, 5A1+10B1,2+10E (Table 1), we get about twice less detectable lines of this origin. 4.2. Modes related to Ni2+ and Sr2+ degrees of freedom Sr2+ ions occupy positions with local symmetry C2 in the crystal. Formally, 1A1+1A2+1B1+1B2+4E modes are caused by their degrees of freedom (Table 1). The coordi- nation of every Sr2+ ion consists of 8 oxygens. It turned out that the surrounding ligands form approximately higher symmetry, than C2 Wyckoff position for Sr2+. The sym- metry is close to C2v with principal axis along z direction. Figure 6 clearly shows permissibility of that approxima- tion. Polarizability tensors connected with the motions of Sr2+ ions in their positions are the following: ___________________________________________________ ,1,2 1( ) ,z a A b c    α =       ,1,2 1( ) ,x e B e    α =       ,1,2 2( )y B f f    α =       , ,3,4 1( ) ,z b A a c    α =       ,3,4 1( ) ,x f B f    α =       ,3,4 2( )y B e e    α =       , (7) ______________________________________________ The numeration follows Fig. 6. Symbols in parentheses relate to the C2v point group irreps. Results of summations of expressions (7) through the normal modes originating from Sr2+ degrees of freedom in the crystal are presented in Table 6. As can be seen only 1A1+1B1+2E Sr2+ modes are expected to be intense in Raman. A deficit contains 1B2+2E modes. Notably, tensors (7) do not contain xy com- ponents at all, so there are no sources to produce Raman intensity of B2 mode. This is a consequence of the actual lack of rotation around the z axis of the oxygen polyhedron surrounding the Sr2+ ion. Fig. 6. (Color online) Structure of the Sr2+ coordination envi- ronment (a), and their projection on the basal plane (b) in SrNi2V2O8 according to Refs. 20, 23. Atoms numeration and local coordinate systems are used in calculations. Table 6. Raman tensor components calculated for Sr2+ and Ni2+ degrees of freedom in the SrNi2V2O8 crystal. Labels x, y, z in the first column represent directions of the ions shifts xx yy zz A1, z (a+b) 2 (a+b) 2 c2 2 B1, z (a−b) 2 −(a−b) 2 xy=yx xz=zx yz=zy E, x (e+f) 2 E, y (e+f) 2 E, x (e−f) 2 E, y (e−f) 2 1770 Low Temperature Physics/Fizika Nizkikh Temperatur, 2017, v. 43, No. 12 Phonon excitations in the quasi-one-dimensional Haldane phase of SrNi2V2O8 Oxygen surroundings of Ni2+ in the structure of SrNi2V2O8 looks like slightly distorted octahedron [20,23] as shown in Fig. 7. Similarly to Sr2+ we will describe the symmetry of the Ni2+ coordination environment as C2v in the first approximation. Eight complexes are divided into two groups 1, 4, 6, 7 and 2, 3, 5, 8 which possess polarizability tensors analogous to (7). And the results are obtained in the same manner as for Sr2+ degrees of free- dom. In spite of twice greater number of Ni2+ ions in the crystal structure, symmetry limitations in the described model do reduce effectively this number, so the expected number of intense Raman lines proves to be the same as for the case of Sr2+ ions (Table 6). Effective symmetry rise in this case leads to a bigger deficit of intense Raman lines. It contains for Ni2+ degrees of freedom 2A1+2B1+3B2+4E. Summing up the total proposed deficit of Raman lines in the “lattice” frequency region, we obtain 4A1+11B1,2+12E. This result is in a good agreement with experimental observa- tions which estimate a lack of Raman lines in this region as 3A1+15B1,2+15E. Notice, that the proposed analysis does not include exploration of the rotational and translational degrees of freedom of VO4 tetrahedra which probably may produce extremely weak Raman signals too. 5. Summary Vibrational Raman spectra of SrNi2V2O8 are investigated in the 10–1000 cm−1 frequency range at various temperatures 7–300 K. There is no evidence of a structural phase transition in the investigated temperature range. Vibrational spectrum of the crystal naturally divides into two frequency ranges, name- ly “lattice” (50−500 cm−1) and internal ν1,3 modes of (VO4)3− tetrahedral complex (700−900 cm−1). In the low-frequency range 11A1+15B1,2+16E modes are detected versus 14A1+30B1,2+31E allowed by the symmetry. In the high- frequency range there are 4A1+6B1,2+4E modes observed versus 4A1+8B1,2+8E allowed. 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Lake, Magnetic Excitations in the Symmetry Protected Topological Quasi-One-Dimensional Haldane Phase of SrNi2V2O8, to be published. 1772 Low Temperature Physics/Fizika Nizkikh Temperatur, 2017, v. 43, No. 12 http://dx.doi.org/%2010.1021/ic051740h http://dx.doi.org/%2010.1002/jrs.2906 http://dx.doi.org/%2010.1016/j.jssc.2011.02.018 http://dx.doi.org/%2010.1103/PhysRevB.84.024111 http://dx.doi.org/%20JMES-88-2011-Rghioui.pdf http://dx.doi.org/%2010.1039/J19660001087 http://dx.doi.org/%2010.1039/J19660001087 http://dx.doi.org/%2010.1107/S0567739476001551 http://dx.doi.org/%2010.1016/0038-1098(92)90723-M http://dx.doi.org/%2010.1103/PhysRevB.84.144101 http://dx.doi.org/%2010.1103/PhysRevB.84.144101 http://dx.doi.org/%2010.1007/s11581-012-0671-6 1. Introduction 2. Experimental 3. Phonon spectra 3.1. Group theoretical analysis and polarization rules 3.2. Structure of the Raman spectrum and molecular vibrations of (VO4)3( 3.3. Low-frequency Raman spectra of SrNi2V2O8 4. Symmetry aspects of the phonon excitations intensity in the Raman spectrum of SrNi2V2O8 4.1. (VO4)3( modes 4.2. Modes related to Ni2+ and Sr2+ degrees of freedom 5. Summary