Comparison of theoretical vibrational and rotational energies of the HCP molecule with experimental values

Using the deMon density functional program, we calculated 150 points on the potential‐energy surface for the ground electronic state (X 1Σ+) of the HCP molecule. An analytical function was fitted through these points and used in two different computer programs (called triatom and dvr) to calculate the vibration‐rotational energies of the HCP and DCP molecules. The computed vibrational fundamentals of ν1, ν2, and ν3 for HCP (DCP) are 3134 (2365), 654 (509), and 1269 (1227) cm−1, respectively, in good agreement with the observed values of 3217 (2419), 675 (525), and 1278 (1231) cm−1. The calculated vibrational energies of HCP show a pronounced regularity, in accordance with the observed harmonic‐vibrational characteristic of the molecule concerned. The average energy deviation of the computed vibration‐rotational energies of HCP up to 8200 cm−1 from the 58 corresponding observations is 90±32 cm−1, thus demonstrating the deMon potential‐energy function to be of good quality.

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