Nuclear quantum effects of light and heavy water studied by all-electron first principles path integral simulations

Masahiko Machida, Koichiro Kato, Motoyuki Shiga

Research output: Contribution to journalArticlepeer-review

9 Citations (Scopus)

Abstract

The isotopologs of liquid water, H2O, D2O, and T2O, are studied systematically by first principles PIMD simulations, in which the whole entity of the electrons and nuclei are treated quantum mechanically. The simulation results are in reasonable agreement with available experimental data on isotope effects, in particular, on the peak shift in the radial distributions of H2O and D2O and the shift in the evaporation energies. It is found that, due to differences in nuclear quantum effects, the H atoms in the OH bonds more easily access the dissociative region up to the hydrogen bond center than the D (T) atoms in the OD (OT) bonds. The accuracy and limitation in the use of the current density-functional-theory-based first principles PIMD simulations are also discussed. It is argued that the inclusion of the dispersion correction or relevant improvements in the density functionals are required for the quantitative estimation of isotope effects.

Original languageEnglish
Article number102324
JournalJournal of Chemical Physics
Volume148
Issue number10
DOIs
Publication statusPublished - Mar 14 2018

All Science Journal Classification (ASJC) codes

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry

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