Mechanism of nuclear spin initiated para-H2 to ortho-H2 conversion.

In this paper a quantitative explanation for a diamagnetic ortho/para H2 conversion is given. The description is based on the quantum-mechanical density matrix formalism originally developed by Alexander and Binsch for studies of exchange processes in NMR spectra. Only the nuclear spin system is treated quantum-mechanically. Employing the model of a three spin system, the reactions of the hydrogen gas with the catalysts are treated as a phenomenological rate process, described by a rate constant. Numerical calculations reveal that for nearly all possible geometrical arrangements of the three spin system an efficient spin conversion is obtained. Only in the chemically improbable case of a linear group H-X-H no spin conversion is obtained. The efficiency of the spin conversion depends strongly on the lifetime of the H-X-H complex and on the presence of exchange interactions between the two hydrogens. Even moderate exchange couplings cause a quench of the spin conversion. Thus a sufficiently strong binding of the dihydrogen to the S spin is necessary to render the quenching by the exchange interaction ineffective.