A nuclear quadrupole resonance investigation of the effect of pressure on molecular rotation in K2PtCl6

1969 ◽  
Vol 47 (10) ◽  
pp. 1095-1100 ◽  
Author(s):  
R. L. Armstrong ◽  
K. R. Jeffrey

The pressure dependences of the 35Cl quadrupolar relaxation rate and nuclear quadrupole resonance frequency in K2PtCl6 are measured for hydrostatic pressures up to 5000 kg cm−2 at six temperatures. The temperatures were selected so that the effects of pressure on the rotation of PtCl6 groups could be investigated. The relaxation resulting from the molecular rotation is discussed in terms of the simple classical model of an activated process. An activation volume ΔV* = 25.6 cm3 mole−1 for the rotation is deduced. The effect of the onset of the rotation on the nuclear quadrupole resonance frequency is noted. The results are shown to be consistent with earlier measurements on the 14N resonance in (CH2)6N4. The activation energy ΔE* for the rotation is shown to have a value between 12.6 and 18.8 kcal mole−1.

2009 ◽  
Vol 78 (12) ◽  
pp. 123704 ◽  
Author(s):  
Michiyasu Mori ◽  
Navid Afzal Shooshtary ◽  
Takami Tohyama ◽  
Sadamichi Maekawa

1971 ◽  
Vol 49 (19) ◽  
pp. 2381-2388 ◽  
Author(s):  
Douglas F. Cooke ◽  
Robin L. Armstrong

Measurements of the temperature and pressure variation of the 35Cl nuclear quadrupole resonance (NQR) frequency in Rb2PtCl6 and Cs2PtCl6 are reported. The resonance frequency is measured at atmospheric pressure for temperatures from 4 to 500 K and at four temperatures between 290 and 380 K for pressures to 5000 kg cm−2. Previously published data for K2PtCl6 are also included in the analysis. Static lattice NQR frequencies are deduced. The differences between the static lattice frequencies are compared with the calculations of Smith and Stoessiger. Thermal averaging of the electric field gradient at a chlorine site is assumed to be dominated by the Q3, Q4, Q5, and Q6 internal modes of the PtCl6 octahedra and by the rotary lattice mode. The rotary mode frequencies are deduced; they are of similar magnitude and increase in the same sequence as the frequencies deduced from infrared and Raman data. An analysis of the pressure dependence of the NQR frequencies leads to pressure coefficients for the rotary mode frequencies. The influence of the cage of R atoms surrounding a PtCl6 octahedron is shown to increase through the series K2PtCl6, Rb2PtCl6, Cs2PtCl6. Finally, a thermodynamic analysis of the NQR data is presented which shows the importance of taking specific volume effects into account.


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