tmph_a_1290842_sm9463.txt (159.83 kB)

Quantum virial coefficients of molecular nitrogen

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posted on 09.03.2017 by Ramachandran Subramanian, Andrew J. Schultz, David A. Kofke

We report virial coefficients up to third order in density for molecular nitrogen, investigating 103 temperatures in the range (15 K, 3000 K). All calculations are based on an ab initio-based potential taken from the literature. Path-integral Monte Carlo (PIMC) is applied to account for nuclear quantum effects, and these results are compared to a more approximate but faster semiclassical treatment. Additionally, we examine a PIMC approach that employs semiclassical beads for the path-integral images, but find that it offers marginal advantage. A recently developed orientation sampling algorithm is used in conjunction with Mayer sampling to compute precise virial coefficients. We find that, within the precision of our calculations of the second-order coefficient (B2), semiclassical methods are adequate for temperatures greater than 250 K, and are needed to correct classical behaviour for temperatures as high as 800 K. For the third-order coefficient (B3), the semiclassical methods are adequate above 150 K, and are required up to the highest temperature examined (3000 K) in order to correct the classical treatment within the precision of the calculations. However, three-body contributions to the potential are much more significant than nuclear quantum effects for the evaluation of B3.