All-dimensional H2-CO potential: Validation with fully quantum second virial coefficients.
We use a new high-accuracy all-dimensional potential to compute the cross second virial coefficient B12(T) between molecular hydrogen and carbon monoxide. The path-integral method is used to fully account for quantum effects. Values are calculated from 10 K to 2000 K and the uncertainty of the potential is propagated into uncertainties of B12. Our calculated B12(T) are in excellent agreement with most of the limited experimental data available, but cover a much wider range of temperatures and have lower uncertainties. Similar to recently reported findings from scattering calculations, we find that the reduced-dimensionality potential obtained by averaging over the rovibrational motion of the monomers gives results that are a good approximation to those obtained when flexibility is fully taken into account. Also, the four-dimensional approximation with monomers taken at their vibrationally averaged bond lengths works well. This finding is important, since full-dimensional potentials are difficult to develop even for triatomic monomers and are not currently possible to obtain for larger molecules. Likewise, most types of accurate quantum mechanical calculations, e.g., spectral or scattering, are severely limited in the number of dimensions that can be handled.
European Centre for Theoretical Studies in Nuclear Physics and Related Areas (ECT*-FBK), via Sommarive 18, I-38123 Trento, Italy.
Giovanni
0000000292012716
G
Garberoglio
Faculty of Chemistry, Nicolaus Copernicus University in Torun, Gagarina 7, PL-87-100 Torun, Poland.
Piotr
P
Jankowski
Department of Physics and Astronomy, University of Delaware, Newark, Delaware 19716, USA.
Krzysztof
K
Szalewicz
Applied Chemicals and Materials Division, National Institute of Standards and Technology, 325 Broadway, Boulder, Colorado 80305-3337, USA.
Allan H
AH
Harvey