@article{fdi:010062034,
  title = {{E}quilibrium fractionation of {H} and {O} isotopes in water from path integral molecular dynamics},
  author = {{P}inilla, {C}. and {B}lanchard, {M}. and {B}alan, {E}tienne and {F}erlat, {G}. and {V}uilleumier, {R}. and {M}auri, {F}.},
  editor = {},
  language = {{ENG}},
  abstract = {{T}he equilibrium fractionation factor between two phases is of importance for the understanding of many planetary and environmental processes. {A}lthough thermodynamic equilibrium can be achieved between minerals at high temperature, many natural processes involve reactions between liquids or aqueous solutions and solids. {F}or crystals, the fractionation factor a can be theoretically determined using a statistical thermodynamic approach based on the vibrational properties of the phases. {T}hese calculations are mostly performed in the harmonic approximation, using empirical or ab-initio force fields. {I}n the case of aperiodic and dynamic systems such as liquids or solutions, similar calculations can be done using finite-size molecular clusters or snapshots obtained from molecular dynamics ({MD}) runs. {I}t is however difficult to assess the effect of these approximate models on the isotopic fractionation properties. {I}n this work we present a systematic study of the calculation of the {D}/{H} and {O}-18/{O}-16 equilibrium fractionation factors in water for the liquid/vapour and ice/vapour phases using several levels of theory within the simulations. {N}amely, we use a thermodynamic integration approach based on {P}ath {I}ntegral {MD} calculations ({PIMD}) and an empirical potential model of water. {C}ompared with standard {MD}, {PIMD} takes into account quantum effects in the thermodynamic modeling of systems and the exact fractionation factor for a given potential can be obtained. {W}e compare these exact results with those of modeling strategies usually used, which involve the mapping of the quantum system on its harmonic counterpart. {T}he results show the importance of including configurational disorder for the estimation of isotope fractionation in liquid phases. {I}n addition, the convergence of the fractionation factor as a function of parameters such as the size of the simulated system and multiple isotope substitution is analyzed, showing that isotope fractionation is essentially a local effect in the investigated system.},
  keywords = {},
  booktitle = {},
  journal = {{G}eochimica et {C}osmochimica {A}cta},
  volume = {135},
  numero = {},
  pages = {203--216},
  ISSN = {0016-7037},
  year = {2014},
  DOI = {10.1016/j.gca.2014.03.027},
  URL = {https://www.documentation.ird.fr/hor/fdi:010062034},
}