TY - JOUR
T1 - Density-scaling exponents and virial potential-energy correlation coefficients for the (2n, n) Lennard-Jones system
AU - Friisberg, Ida Marie
AU - Costigliola, Lorenzo
AU - Dyre, Jeppe
N1 - Important note from the Publisher regarding the linked version of the article (arXiv). “This is a post-peer-review, pre-copyedit version of an article published in Journal of Chemical Sciences. The final authenticated version is available online at: http://dx.doi.org/10.1007/s12039-017-1307-1”
PY - 2017
Y1 - 2017
N2 - Abstract: This paper investigates the relation between the density-scaling exponent γ and the virial potential-energy correlation coefficient R at several thermodynamic state points in three dimensions for the generalized (2n, n) Lennard-Jones (LJ) system for n= 4 , 9 , 12 , 18 , as well as for the standard n= 6 LJ system in two, three, and four dimensions. The state points studied include many low-density states at which the virial potential-energy correlations are not strong. For these state points we find the roughly linear relation γ≅ 3 nR/ d in d dimensions. This result is discussed in light of the approximate “extended inverse power law” description of generalized LJ potentials (Bailey N P et al. 2008 J. Chem. Phys. 129 184508). In the plot of γ versus R there is in all cases a transition around R≈ 0.9 , above which γ starts to decrease as R approaches unity. This is consistent with the fact that γ→ 2 n/ d for R→ 1 , a limit that is approached at high densities and/or high temperatures at which the repulsive r
-
2
n term dominates the physics. Graphical Abstract: The paper presents numerical data for the density-scaling exponent γ and the virial potential-energy correlation coefficient R for generalized (2n, n) Lennard-Jones (LJ) systems. An unanticipated linear relation is observed between R and a properly scaled version of γ.[Figure not available: see fulltext.].
AB - Abstract: This paper investigates the relation between the density-scaling exponent γ and the virial potential-energy correlation coefficient R at several thermodynamic state points in three dimensions for the generalized (2n, n) Lennard-Jones (LJ) system for n= 4 , 9 , 12 , 18 , as well as for the standard n= 6 LJ system in two, three, and four dimensions. The state points studied include many low-density states at which the virial potential-energy correlations are not strong. For these state points we find the roughly linear relation γ≅ 3 nR/ d in d dimensions. This result is discussed in light of the approximate “extended inverse power law” description of generalized LJ potentials (Bailey N P et al. 2008 J. Chem. Phys. 129 184508). In the plot of γ versus R there is in all cases a transition around R≈ 0.9 , above which γ starts to decrease as R approaches unity. This is consistent with the fact that γ→ 2 n/ d for R→ 1 , a limit that is approached at high densities and/or high temperatures at which the repulsive r
-
2
n term dominates the physics. Graphical Abstract: The paper presents numerical data for the density-scaling exponent γ and the virial potential-energy correlation coefficient R for generalized (2n, n) Lennard-Jones (LJ) systems. An unanticipated linear relation is observed between R and a properly scaled version of γ.[Figure not available: see fulltext.].
KW - Lennard-Jones type liquids
KW - density scaling
KW - isomorphs
KW - virial potential-energy correlations
U2 - 10.1007/s12039-017-1307-1
DO - 10.1007/s12039-017-1307-1
M3 - Journal article
SN - 0370-0089
VL - 129
SP - 919
EP - 928
JO - Journal of Chemical Sciences
JF - Journal of Chemical Sciences
IS - 7
ER -