화학공학소재연구정보센터
Journal of Chemical Physics, Vol.106, No.1, 1-10, 1997
Quantum-Mechanical Exchange in a Transition-Metal Hydride Complex - NMR Data for (CP(Pph(3))Irh3)(+) Fitted by a 2-Dimensional Model
A two-dimensional model for hydrogen pair exchange in transition metal trihydrides is used to interpret NMR data observed for [cp(PPh(3))IrH3](+). Inspired by quantum chemical results for [cp(PH3)IrH3](+), the model describes a combined process of rotational tunneling and IrH2 bending that merges into an H-2 "lift-off" motion at a small proton-proton distance. The condensed environment with which the tunneling system interacts is represented by a heat bath. A second-order perturbation treatment yields a master equation for the populations of the vibrational states within each of-the rotational symmetry species A and B and for the respective AB coherences. A theoretical basis is provided for the evolution of the tunneling (AB) coherence as a damped oscillation in agreement with an independent treatment very recently published by Szymanski [J. Chem. Phys. 104, 8216 (1996)]. A simplified model assumption, containing one adjustable parameter, is made for the system-bath interaction. The temperature-dependent frequency of the tunneling process is found to be close to the Boltzmann average of the tunnel frequencies in the individual vibrational states. Both the calculated temperature-dependent coherence damping-rate constant and the tunnel frequency fit the experimental data after adjustment of three parameters describing the potential energy surface and of the parameter representing the system-bath interaction strength.