Quantitative H_2O versus D_2O differences from first-principles quantum simulation · revision history

Revision 2

Accepted · core change · record

Changes against revision 1:

Title · changed
Revision 1: Quantitative H2O versus D2O differences from first-principles quantum simulation
Revision 2: Quantitative $\mathrm{H_2O}$ versus $\mathrm{D_2O}$ differences from first-principles quantum simulation
Plain
Heavy water, in which hydrogen is replaced by deuterium, has its density maximum near 11 C instead of 4 C and is about 23 percent more viscous. These differences come only from the quantum motion of nuclei, so they test whether simulations treat that motion correctly.
Precise · changed · core
Revision 1: Using path-integral simulations on a potential of coupled-cluster quality not fitted to isotope data, compute the H2O to D2O shifts of the temperature of maximum density (277.13 K versus about 284.3 K), the melting temperature (273.15 K versus about 276.97 K) and the viscosity ratio at 298 K (about 1.23), and decompose each into the competing quantum effects (hydrogen-bond weakening by intermolecular zero-point motion versus strengthening by O-H stretch delocalization). An answer is computed shifts within 1 K and 5 percent of experiment with the decomposition.
Revision 2: Using path-integral simulations on a potential of coupled-cluster quality not fitted to isotope data, compute the $\mathrm{H_2O}$ to $\mathrm{D_2O}$ shifts of the temperature of maximum density (277.13 K versus about 284.3 K), the melting temperature (273.15 K versus about 276.97 K) and the viscosity ratio at 298 K (about 1.23), and decompose each into the competing quantum effects (hydrogen-bond weakening by intermolecular zero-point motion versus strengthening by O-H stretch delocalization). An answer is computed shifts within 1 K and 5 percent of experiment with the decomposition.
Settled by
Converged path-integral free-energy and dynamics calculations on an ab initio-quality many-body potential compared with measured isotope shifts.
Kind
well-posed
Answer type
value
References
(empty)
Literature status
open
Status note
(empty)
Posed since
(empty)

Decisions