# How Accurate Are Approximate Methods for Evaluating Partition Functions for Hindered Internal Rotations?

journal contribution

posted on 06.03.2008, 00:00 by Ching Yeh Lin, Ekaterina I. Izgorodina, Michelle L. CooteThe accuracy of several low-cost methods (harmonic oscillator approximation, CT-Cω, SR-TDPPI-HS, and
TDPPI-HS) for calculating one-dimensional hindered rotor (1D-HR) partition functions is assessed for a test
set of 644 rotations in 104 organic molecules, using full torsional eigenvalue summation (TES) as a benchmark.
For methods requiring full rotational potentials, the effect of the resolution at which the rotational potential
was calculated was also assessed. Although lower-cost methods such as Pitzer's Tables are appropriate when
potentials can be adequately described by simple cosine curves, these were found to show large errors (as
much as 3 orders of magnitude) for non-cosine curve potentials. In those cases, it is found that the TDPPI-HS method in conjunction with a potential compiled at a resolution of 60° offers the best compromise between
accuracy and computational expense. It can reproduce the benchmark values of the partition functions for an
individual mode to within a factor of 2; its average error is just of a factor of 1.08. The corresponding error
in the overall internal rotational partition functions of the molecules studied is less than a factor of 4 in all
cases. Excellent cost-effective performance is also offered by CT-Cω, which requires only the geometries,
energies, and frequencies of the distinguishable minima in the potential. With this method the geometric
mean error in individual partition functions is 1.14, the maximum error is a modest 2.98 and the resulting
error in the total 1D-HR partition function of a molecule is less than a factor of 5 in all cases.