Water dimer equilibrium constant calculation: A quantum formulation including metastable states

作者：Leforestier Claude^*

来源：Journal of Chemical Physics, 2014, 140(7): 074106.

DOI：10.1063/1.4865339

We present a full quantum evaluation of the water second virial coefficient B(T) based on the Takahashi-Imada second order approximation. As the associated trace Tr[e(-beta HAB) - e-(beta HoAB)] is performed in the coordinate representation, it does also include contribution from the whole continuum, i.e., resonances and collision pairs of monomers. This approach is compared to a Path Integral Monte Carlo evaluation of this coefficient by Schenter [J. Chem. Phys. 117, 6573 (2002)] for the TIP4P potential and shown to give extremely close results in the low temperature range (250-450 K) reported. Using a recent ab initio flexible potential for the water dimer, this new formulation leads to very good agreement with experimental values over the whole range of temperatures available. The virial coefficient is then used in the well known relation K-P(T) = -(B(T) - b(M))/RT where the excluded volume b(M) is assimilated to the second virial coefficient of pure water monomer vapor and approximated from the inner repulsive part of the interaction potential. This definition, which renders b(M) temperature dependent, allows us to retrieve the 38 cm(3) mol(-1) value commonly used, at room temperature. The resulting values for K-P(T) are in agreement with available experimental data obtained from infrared absorption spectra of water vapor.

• 出版日期2014-2-21