A Comparative Study of the Bonding Character in the P₄O_n (n = 6−10) Series by Means of a Vibrational Analysis

Abstract

In the present work the bonding situation within the P4O n (n = 6−10) series is studied using a combination of experimental and theoretical vibrational analysis. A correlation between the spectra of the compounds is undertaken, and the shifts of the vibrational frequencies within the series are analyzed. Our study shows that the frequencies of the most modes involving cage motions increase, when more oxygen atoms are added to the phosphorus centers. This reflects the reinforcement of the cage bonds along the P4O n (n = 6−10) series. For a few bands the frequencies decrease within the series, and this fact results from the reduced masses, which become larger with the increasing number of the substituents.

P8O12·2BH3 − The Borane Adduct of a New Molecular Phosphorus Oxide

“…Thus, absorptions at 431, 655, 666, 757, 1119, 2343, and 2363 cm Ϫ1 are observed in both, IR and Raman spectra ( Figure 7; Table 6). As expected, the spectra are very similar to those of P 4 O 6 [49] and P 4 O 7 , [3] for which strong bands around 950 cm Ϫ1 in the IR spectrum (broad) and around 620 cm Ϫ1 in the Raman spectrum (sharp) are quite characteristic. The vibrational frequencies of 1 are shifted by up to 20 cm Ϫ1 compared to (Table 6).…”

The First Ozonide of a Phosphorus Oxide—Preparation, Characterization, and Structure of P4O18

“…The Raman spectrum of 1 recorded at À80 8C shows besides the expected bands for the adamantane cage [9] the three prominent bands at 901, 887, and 870 cm À1 that were assigned by Dimitrov and Seppelt as the characteristic Raman bands of the PO 3 ring. [3] The Raman spectrum measured at À30 8C shows that the decrease in the intensity of these bands occurs simultaneously with the vigorous liberation of O 2 and the formation of phosphorus(v) oxide P 4 O 10 .…”

Phosphorene oxides: Bandgap engineering of phosphorene by oxidation

“…For the surface forms (s-P 4 O 2 and s-P 4 O 4 ) in which only dangling oxygens are present, there are indeed no vibrational modes between 500 cm −1 and 1000 cm −1 . In the high frequency region, the vibrational spectrum instead only involves P=O stretching modes; these modes are decoupled from the other vibrations because the P=O bonds are much stronger than P-O bridges, as in the case of the molecular (bulk) phosphorus oxides 49,50 . The P=O stretching modes are separated from the other modes by at least 200 cm −1 for all oxygen concentrations, and there are as many as the number of dangling oxygen in the PO.…”