We address the points raised by Giordano and Leporini (GL) and show that accounting properly for the nonexponential decay of the rotational correlation function leads to improved agreement with the Stokes–Einstein–Debye (SED) relation above the crossover temperature TC for those probes 3,3′-dimethyloxazolidinyl-N-oxy-2′,3-5α-cholestane (CSL), and perdeuterated 2,2′,6,6′-tetramethyl-4-methyl aminopiperidinyl-N-oxide) (MOTA) that are well-coupled to the viscous modes of o-terphenyl (OTP) when the average relaxation rate ⅙〈τ〉 is plotted versus 1/T. On the other hand, 2,2′,6,6′-tetramethyl-4-piperidine-N-oxide (PDT) shows simple Arrhenius behavior in this regime, because of weak coupling to the solvent cage, inconsistent with SED, which was clearly shown in our paper. We also suggest that the difference in chemical structure of the PDT probe, studied by us, compared to 2,2′,6,6′-tetramethylpiperidine-N-oxyl (TEMPO), studied by GL, accounts for the difference in the low-temperature relaxation behavior of the two probes.

Response to “Comment on ‘A 250 GHz ESR study of o-terphenyl dynamic cage effects above T[sub C]’ ” [J. Chem. Phys. 109, 10523 (1998)]

POLIMENO, ANTONINO;
1998

Abstract

We address the points raised by Giordano and Leporini (GL) and show that accounting properly for the nonexponential decay of the rotational correlation function leads to improved agreement with the Stokes–Einstein–Debye (SED) relation above the crossover temperature TC for those probes 3,3′-dimethyloxazolidinyl-N-oxy-2′,3-5α-cholestane (CSL), and perdeuterated 2,2′,6,6′-tetramethyl-4-methyl aminopiperidinyl-N-oxide) (MOTA) that are well-coupled to the viscous modes of o-terphenyl (OTP) when the average relaxation rate ⅙〈τ〉 is plotted versus 1/T. On the other hand, 2,2′,6,6′-tetramethyl-4-piperidine-N-oxide (PDT) shows simple Arrhenius behavior in this regime, because of weak coupling to the solvent cage, inconsistent with SED, which was clearly shown in our paper. We also suggest that the difference in chemical structure of the PDT probe, studied by us, compared to 2,2′,6,6′-tetramethylpiperidine-N-oxyl (TEMPO), studied by GL, accounts for the difference in the low-temperature relaxation behavior of the two probes.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11577/2485413
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