INHOMOGENEOUS BROADENING AND KINETIC CARBON-MONOXIDE ISOTOPE EFFECTS IN LOW-TEMPERATURE CARBON-MONOXIDE RECOMBINATION WITH MYOGLOBIN AND HEMOGLOBIN

We have analyzed the non-exponential kinetics, the temperature variation, and the CO isotope effects of the CO recombination reactions with myoglobin and single-chain hemoglobin. The analysis rests on multiphonon quantum-mechanical chemical-rate theory combined with static inhomogeneous broadening of either the reorganization free energy or the reaction Gibbs free energy. The simplest specific model which can account for all the data contains an inhomogeneous distribution function of width 0.2-0.3 eV, independent of temperature down to the tunnel transition at about 20 K, two discrete nuclear coordinates of low vibrational frequency (60-150 cm-1), representing iron-heme and CO bending motion, the CO stretching motion of frequency about 2000 cm-1, and additional inhomogeneous broadening of the protein and CO bending configuration below the tunnel transition temperature. The model appears somewhat involved but in return provides corresponding insight in the dynamics of this important class of processes.