Study of dynamics in pentachlorophenol in the solid state by 1D Nuclear Quadrupole Resonance exchange spectroscopy

Abstract

The paper reports studies of the dynamic process in pentachlorophenol (PCP) in the solid state by one-dimensional Nuclear Quadrupole Resonance (NQR) exchange spectroscopy employing shaped rf pulses. Pentachlorophenol exhibits intramolecular hydrogen bonding between the hydroxyl proton and one of the o-chlorines. Reorientation of the hydrogen bond with migration of the hydroxyl proton from one o-chlorine to the other is possible in a wide temperature range. In this process the two o-chlorines are exchanged; at the same time this implies the exchange of the two m-chlorines as well, which we have chosen to monitor, modeling it as a two-site exchange process. A detailed analysis of the appropriate Bloch-McConnell equation is performed to formulate the relevant kinetic matrix. The exchange pulse sequence implemented by us involves suitably modulated shaped RF pulses to achieve simultaneous on-resonance excitation of the two exchanging sites. This approach results in a clear definition of the exchange time window and requires only a short experiment time. Kinetic parameters, namely, the spin-lattice relaxation rate and the exchange rate are deduced from the experimental signal intensities. Variable temperature measurements in the range 213 K–318 K have been carried out to extract the activation parameters as well.