In this work we present the extended two-dimensional torsion (E2DT) method and use it to analyze the performance of several methods that incorporate torsional anharmonicity more approximately for calculating rotational-vibrational partition functions. Twenty molecules having two hindered rotors were studied for temperatures between 100 and 2500 K. These molecules present several kinds of situations; they include molecules with nearly separable rotors, molecules in which the reduced moments of inertia change substantially with the internal rotation, and molecules presenting compound rotation. Partition functions obtained by the rigid-rotor harmonic oscillator approximation, a method involving global separability of torsions and the multistructural methods without explicit potential coupling [MS-T(U)] and with explicit potential coupling [MS-T(C)] of torsions, are compared to those obtained with a quantized version - called the extended two-dimensional torsion (E2DT) method - of the extended hindered rotor approximation of Vansteenkiste et al. (Vansteenkiste et al. J. Chem. Phys. 2006, 124, 044314). In the E2DT method, quantum effects due to the torsional modes were incorporated by the two-dimensional nonseparable method, which is a method that is based on the solution of the torsional Schrödinger equation and that includes full coupling in both the kinetic and potential energy. By comparing other methods to the E2DT method and to experimental thermochemical data, this study concludes that the harmonic approximation yields very poor results at high temperatures; the global separation of torsions from the rest of the degrees of freedom is not justified even when an accurate method to treat the torsions is employed; it is confirmed that methods based on less complete potential energy coupling of torsions, such as MS-T(U), are not accurate when dealing with rotors with different barrier heights, and more complete inclusion of torsional coupling to the method in MS-T(C) improves substantially the results in such a way that it could be used in cases where the E2DT method is unaffordable.
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