Stable isotope equilibria in the dihydrogen-water-methane-ethane-propane system. Part 1: Path-integral calculations with CCSD(T) quality potentials

Isotopic compositions of alkanes are typically assumed to be kinetically controlled, but recently it has been proposed that alkanes can isotopically equilibrate for both C and H isotopes during natural gas generation. Evaluation of this requires knowledge of the isotopic equilibrium between alkanes and other common hydrogen and carbon bearing species. Here we calculate isotopic equilibria within and between gaseous dihydrogen (H₂), water (H₂O), methane (CH₄), ethane (C₂H₆) and propane (C₃H₈), including isotope fractionation among molecules, clumped isotope effects, as well as among sites of propane (i.e., the site-specific isotope effects) from 0°C to 500°C using a path-integral method paired with high-level descriptions of molecular potentials and the diagonal correction to the Born–Oppenheimer approximation. While path-integral calculations with high-level CCSD(T) potentials are available for the isotopic equilibria involving methane, the path-integral calculations for ethane and propane have only been performed based on lower-level descriptions of the molecular potentials. We analyze the relative importance of various approximations that are commonly employed when isotopic equilibria are evaluated. We find that clumped isotope effects can be calculated to the same accuracy using computationally inexpensive combination of the Bigeleisen-Mayer-Urey model with the molecular potential from density functional theory. In contrast, fractionation and site preferences of both deuterium and carbon-13 benefit from the use of the higher level CCSD(T) potentials and accounting for anharmonic effects. Additionally, for fractionation and site preference of deuterium, corrections to Born–Oppenheimer approximation can also be important.