Alkanes; Clumped isotope effects; Path integral calculations; Site-specific isotope effects; Stable isotope fractionations; Geochemistry and Petrology
Abstract :
[en] 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.
Disciplines :
Chemistry
Author, co-author :
Korol, Roman ; Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, United States ; Present Address: Department of Chemistry, University of Rochester, Rochester, United States
Turner, Andrew C. ; Department of Earth and Planetary Science, University of California, Berkeley, United States ; Energy Geosciences Division, Lawrence Berkeley National Laboratory, Berkeley, United States ; Present address: U.S. Geological Survey, Central Energy Resources Science Center, Denver, United States
NANDI, Apurba ; University of Luxembourg > Faculty of Science, Technology and Medicine (FSTM) > Department of Physics and Materials Science (DPHYMS) ; Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, United States
Bowman, Joel M.; Department of Chemistry and Cherry L. Emerson Center for Scientific Computation, Emory University, Atlanta, United States
Goddard, William A.; Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, United States ; Materials and Process Simulation Center, California Institute of Technology, Pasadena, United States
Stolper, Daniel A.; Department of Earth and Planetary Science, University of California, Berkeley, United States ; Energy Geosciences Division, Lawrence Berkeley National Laboratory, Berkeley, United States
External co-authors :
yes
Language :
English
Title :
Stable isotope equilibria in the dihydrogen-water-methane-ethane-propane system. Part 1: Path-integral calculations with CCSD(T) quality potentials
Office of Science National Science Foundation Division of Chemical Bioengineering Environmental and Transport Systems Chemical Sciences, Geosciences, and Biosciences Division Basic Energy Sciences Resnick Sustainability Institute for Science, Energy and Sustainability, California Institute of Technology U.S. Department of Energy National Science Foundation
Funding text :
DAS acknowledges support from the US Department of Energy, Office of Science, Office of Basic Energy Sciences, Chemical Sciences, Geosciences, and Biosciences Division, under Award Numbers DE-AC02-05CH11231 and DE-SC0022949. WGIII acknowledges support from the National Science Foundation under award number CBET-2311117 The computations presented here were conducted in the Resnick High Performance Computing Center, a facility supported by Resnick Sustainability Institute at the California Institute of Technology. RK thanks Dr. Tomislav Begu\u0161i\u0107 for helpful discussions.
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