Abstract
By taking the IR spectra of several cyclotriphosphates of a resolved structure, has subsequently shown that it is possible to characterize the P3O9 ring by its IR spectrum and, in some favorable cases, to make them Predicted symmetry of the cycle by examining the number, profile and position of the observed infrared bands in the symmetric valence vibration of the POP (νs POP) groups. He identified criteria for each type of symmetry and discussed, using concrete examples, the limits of the infrared method in determining the symmetry of the cycle (all the possible symmetries that a P3O9 cycle can have). Recently, at the Laboratory, studies have been undertaken by A. ABOUIMRANE et al. [1] for the calculation of the normal IR frequencies of the P3O9 cycle for the ideal and real symmetries: D3h, Cs and C3 (Tables 1,2 and 3).
Published by Elsevier Inc. This is an open access article under the CC BY license https://doi.org/10.1080/10426507.2017.1333507.
Keywords: Infrared, Raman, Vibration spectroscopy, Cyclotriphosphates
Specifications Table
| Subject area | Chemistry |
| More specific subject area | Spectroscopy |
| Type of data | Table |
| How data was acquired | Infrared and Raman spectroscopy |
| Data format | analyzed, calculated |
| Experimental factors | These calculations were conducted using the semi-empirical method, Modified Neglect of Differential Overlap |
| Experimental features | The calculation of the frequencies was carried out first of all for the highest symmetry that the P3O9cycle can have, that of its molecular group D3h, then it was carried out for lower symmetries. |
| Data source location | Laboratory of Physical Chemistry of Materials LCPM, Faculty of Sciences Ben M'sik, B.P. 7955. Bd Cdt Driss El Harti. Hassan II University of Casablanca. Morocco |
| Data accessibility | With this article |
| Related research article | S. Zerraf, M. Belhabra, A.Kheireddine, R. Lamsatfi, M.Tridane, H. Moutaabbid,B. Baptiste, M. Moutaabbid, and S. Belaaouad, Reinvestigation of the crystal structure of barium cesium Cyclotriphosphate dihydrate and vibrational study, Phosphorus Sulfur Silicon Relat Elem., 192, 2017, 1286–1293[2]. |
Value of the data
|
1. Data
The dataset shows how to determine different types of spectral vibration, as shown in Fig. 1. Table 1, Table 2, Table 3 refer to the frequencies to be calculated using different simulations in infrared and Raman spectroscopy. The comparison between the experimental and calculated vibration frequencies shows a total of 30 normal vibration patterns were identified for the isolated symmetry cycle D3h.The normal frequency calculation of the P3O9 cycle makes it possible to calculate the values of the internal vector component corresponding to the displacement of each atom of the cycle (see Fig. 2, Fig. 3, Fig. 4).
Fig. 1.
Infrared radiation.
Table 1.
Calculated IR frequencies for symmetry D3h.
Table 2.
Calculated IR frequencies for symmetry Cs.
| υcal (cm−1) | (%) de participation | mode | υcal (cm−1) | (%) de participation | mode | ||
|---|---|---|---|---|---|---|---|
| 1299 | υas PO2 [98] | A′ | 427 | δ′ POP [24] | δ′ PO2 [76] | A″ | |
| 1280 | υas PO2 [100] | A′ | 420 | δ′ POP [44] | δ′ PO2 [56] | A′ | |
| 1280 | υas PO2 [100] | A″ | 415 | γW PO2 [77] | A″ | ||
| 1200 | υas POP [98] | υsPO2 [2] | A″ | 305 | δ POP [11] | δ PO2 [89] | A′ |
| 1188 | υa POP [96] | υs(PO2) [4] | A′ | 303 | γ′ POP [16] | γ T PO2 [84] | A″ |
| 1155 | υs PO2 [98] | A′ | 297 | δ′ POP [30] | γ W PO2 [70] | A′ | |
| 1099 | υas POP [18] | υs PO2 [82] | A″ | 287 | γ′ POP [14] | γ T PO2 [86] | A′ |
| 1095 | υas POP [21] | υsPO2 [79] | A′ | 268 | δ′ POP [33] | γ W PO2 [67] | A″ |
| 1032 | υas POP [94] | A″ | 255 | δ′ POP [24] | γ W PO2 [76] | A″ | |
| 794 | υs POP [77] | δ PO2 [23] | A″ | 252 | δ′ POP [20] | γW PO2 [80] | A′ |
| 792 | υs POP [76] | δ PO2 [24] | A′ | 214 | γ T PO2 [99] | A″ | |
| 698 | υs POP [64] | δ PO2 [36] | A′ | 104 | γ POP [22] | γ R PO2 [78] | A′ |
| 563 | δ POP [71] | δ PO2 [29] | A′ | 89 | γ′ POP [31] | γ R PO2 [69] | A″ |
| 513 | γ POP [63] | γ R PO2 [37] | A′ | 59 | γ′ POP [31] | γR PO2 [69] | A′ |
| 447 | γ′ POP [62] | γT PO2 [38] | A″ | ||||
| 447 | γ′ POP [49] | γ T PO2 [51] | A′ | ||||
Table 3.
Calculated IR frequencies for symmetry C3.
Fig. 2.
IR spectra of cyclotriphosphates. (a) CoK4(P3O9)2.7H2O, (b) NiK4(P3O9)2.7H2O.
Fig. 3.
IR spectra of cyclotriphosphates. (a) SrNH4P3O9.3H2O, (b) SrRpP3O9.3H2O, (c) SrKP3O9.3H2O.
Fig. 4.
IR spectra of cyclotriphosphates. (a) ZnK4(P3O9)2.6H2O, (b) ZnRb4(P3O9)2.6H2O, (c) NiRb4(P3O9)2.6H2O.
For each frequency, the percentage of participation of the vibrations that contributed to it was specified. The percentages of the two groups, P-Oi-P and POe2 of the ring, were calculated from the successive isotopic substitutions 31P–33P, 16Oi-18Oi and 16Oe-18Oe. It has been assumed that internal oxygens are not involved in POe2 movements and that oxygens outside the cycle are not involved in POiP movements. The behavior of the eigenvectors, the displacement of the atoms with respect to their equilibrium position, and therefore of the relative movements at each normal frequency, with respect to the elements of symmetry of the group of the isolated P3O9 cycle, makes it possible to specify their symmetry and consequently the normal modes Corresponding. The assignment of the cycle frequencies is made without any a priori hypothesis and without vibrational spectra [1].
These allocations (Table 1, Table 2, Table 3) of the frequencies calculated for the corresponding modes for the symmetries D3h, Cs and C3 respectively were confirmed by the IR and Raman vibrational spectra of the compounds containing the P3O9 cycles of symmetry Cs (Table 5). This table shows how the normal modes change from the symmetry D3h to the symmetry Cs of the isolated cycle. It shows the concordance between the values of the calculated frequencies and the experimental frequencies observed. Indeed, the IR spectra (Table 4) and those of Raman microspectrometry (Table 6) confirm the proposed assignments of both the valence frequencies and the deformation frequencies of the P3O9 cycle.
Table 5.
Assignment of the calculated frequencies to the corresponding modes for the Cs symmetry of the P3O9 cycle.
Table 4.
IR and far IR frequencies (in cm−1) observed in cyclotriphosphates with a P3O9 cycle of symmetry Cs: SrRbP3O9.3H2O (I), SrNH4P3O9.3H2O (II), SrKP3O9.3H2O (III),CoK4(P3O9)2.7H2O (IV), NiK4(P3O9)2.7H2O (V), ZnK4(P3O9)2.6H2O (VI), ZnRb4(P3O9)2.6H2O (VII) et NiRb4(P3O9)2.6H2O (VIII).
| (I) | (II) | (III) | (IV) | (V) | (VI) | (VII) | (VIII) |
|---|---|---|---|---|---|---|---|
| 1296 (F) 1255 (F) |
1289 (F) 1265 (F) 1249(m) |
1306 (F) 1274 (F) |
1302 (F) | 1302 (F) | 1284 (F) 1255 (F) |
1278 (F) 1267 (F) |
1281 (F) 1267 (ép) |
| 1203 (f) | 1237 (F) | 1238 (F) | 1196 (f) | 1196 (f) | 1195 (f) | ||
| 1157 (F) | 1160 (F) | 1162 (m) | 1155(m) | 1155 (m) | 1155 (m) | 1154 (m) | 1159 (m) |
| 1093 (F) | 1094 (F) | 1122 (F) 1097 (F) |
1102 (F) | 1102 (F) 1091 (F) |
1096 (F) | 1100 (F) | 1096 (F) |
| 1061 (f) 989 (F) 966 (F) |
995 (ép) 974 (F) |
1009 (F) 972 (F) |
1002 (F) | 1002 (F) | 1031 (F) 1014 (F) |
1021 (F) | 1015 (F) |
| 862 (f) 826 (f) |
860 (ép) | 861 (f) | 849 (f) | 879 (f) | 881 (f) | 923 (ép) 826 (f) |
|
| 766 (F) 721 (f) |
769 (F) | 767 (F) 735 (F) |
770 (ép) 744 (F) |
767 (F) 738 (F) |
779 (ép) 744 (F) |
08 (m) 741 (F) |
743 (F) |
| 700 (f) 652 (f) |
700 (F) 662 (f) 651 (m) |
682 (m) 638 (f) |
667 (f) | 690 (f) 662 (m) |
641 (m) | 679 (ép) 641 (f) |
|
| 606 (f) | |||||||
| 528 (F) | 538 (F) | 537 (F) | 540 (m) | 543 (F) 537 (ép) 529 (ép) |
520 (ép) | 548 (ép) | 541 (ép) |
| 517 (m) | 516 (F) | 512 (m) 510 (F) |
521 (ép) 512 (F) |
514 (F) | 514 (F) 506 (ép) |
514 (F) | 504 (F) |
| 498 (f) 457 (f) |
457 (m) 387 (f) 374 (f) 364 (m) 336 (m) 322 (m) 312 (F) 289 (F) 215 (F) 191(F) (Sr2+) 183 (F) 161 (F) 146 (m) 117(F)(NH4+) 82 (m) 71 (F) 67 (ép) 61 (m) |
452 (m) 384 (m) 366 (F) 335 (m) 323 (m) 310 (m) 283 (F) 218 (F) 205 (m) 192(F)(Sr2+) 172 (F) 125 (F) 109 (F)(K+) 105 (F) 77 (F) 65 (f) |
493 (ép) 469 (m) 412 (f) 376 (m) 354 (f) 336 (m) 323 (m) 305 (f) 295 (ép) 261 (ép) 250 (m) 229 (f) 213(f)(Co2+) 174 (F) 154 (F) 139 (m) 130 (ép) 116(m)(K+) 110(m)(K+) 93 (m) 70 (m) |
495 (ép) 471 (ép) 450 (ép) 412 (m) 375 (F) 326 (ép) 321 (F) 302 (m) 288 (f) 263 (m) 237 (m) 215(F)(Ni2+) 198 (ép) 183 (F) 157 (F) 152 (F) 120 (F)(K+) 95 (m) 80 (m) 69 (m) |
486 (ép) 465 (m) 382 (f) 338 (m) 329 (ép) 314 (f) 301 (m) 273 (f) 236 (m) 205 (ép) 190(F)(Zn2+) 161 (m) 124 (F) 110 (ép)(K+) 92 (ép) 74 (f) 72 (f) 62 (ép) |
464 (m) 400 (ép) 388 (f) 338 (m) 331 (ép) 310 (ép) 300 (m) 271 (f) 236 (m) 183(F)(Zn2+) 142 (ép) 127 (F) 95 (F)(Rb+) 75 (m) 60 (f) 55 (m) |
464 (m) 396 (f) 341 (F) 307 (F) 274 (m) 256 (f) 235 (m) 210(F)(Ni2+) 179 (f) 150 (F) 100 (F)(Rb+) 95 (F)(Rb+) 72 (f) |
Table 6.
Distribution of the normal modes of vibration of the P3O93− ion in the isolated state of the various possible symmetries.
| Groupe |
Γvib (P3O93−) | Activité |
Coïncidence | |
|---|---|---|---|---|
| Moléculaire | IR | Ra | ||
| D3h | 4 A′1 (Ra) + A″2+ 2 A′2 + 3 A″2 (IR) + 6 E’ (IR, Ra) + 4 E” (Ra) | 9 | 14 | 6 |
| *C3h | 6 A’ (Ra) + 6 E’ (IR, Ra) + 4 A” + 4 E” (Ra) | 10 | 16 | 6 |
| *∼ C3v | 7 A1 (IR, Ra) + 3 A2 + 10 E (IR, Ra) | 17 | 17 | 7 |
| *∼ C2v | 10 A1 (IR, Ra) + 5 A2 (Ra) + 7 B1 (IR, Ra) + 8 B2 (IR, Ra) | 25 | 30 | 25 |
| *C3 | 10 A (IR, Ra) + 10 E (IR, Ra) | 20 | 20 | 20 |
| *C2 | 15 A (IR, Ra) + 15 B (IR, Ra) | 30 | 30 | 30 |
| *Cs | 17 A’ (IR, Ra) + 13 A” (IR, Ra) | 30 | 30 | 30 |
| Cs | 16 A’ (IR, Ra) + 14 A” (IR, Ra) | 30 | 30 | 30 |
| *C1 | 30 A (IR, Ra) | 30 | 30 | 30 |
*: The currently known symmetries of the P3O9 ring.
(Table 7) gives the calculated IR frequencies for the symmetries D3h, Cs and C3 and specifies their variations with respect to those calculated for the highest symmetry D3h.
Table 7.
Calculated IR frequencies for the symmetries C3 and Cs and their variations with respect to those of the symmetry D3h.
2. Experimental design, materials and methods
These calculations were carried out using the semi-empirical method, Modified Neglect of Differential Overlap (MNDO) [2]. Thus, the calculation made it possible to obtain, for each of the normal frequencies of the P3O9 cycle, the values of the components of the eigenvectors corresponding to the displacements of each atom of the cycle.
For the calculated normal frequencies of the P3O9 cycle, the geometric variations of the elongations and angular deformations of the 12 P3O9 ring atoms corresponding to each were calculated. These movements made it possible to attribute the twelve fundamental valence frequencies, for which the variations of distances, P-Oe or P-Oi, are the most important at the 12 highest frequencies. Whereas for the other 18 vibrations of angular deformations the variations of the distances are zero or very small. On the basis of the atomic displacements, the valence frequencies and the deformation frequencies of the P3O9 cycle were distinguished and assigned.
References
- 1.Abouimrane A. Casablanca. Maroc; 2000. Thèse de Doctorat, Faculté des Sciences Ben M'Sik. [Google Scholar]
- 2.Zerraf S., Belhabra M., Kheireddine A., Lamsatfi R., Tridane M., Moutaabbid H., Baptiste B., Moutaabbid M., Belaaouad S. Phosphorus, Sulfur, and Silicon. 2017;192:1286–1293. [Google Scholar]