Applying a Smolyak collocation method to Cl2CO

作者：Castro Eduardo; Avila Gustavo^*; Manzhos Sergei^*; Agarwal Jay; Schaefer Henry F; Carrington Tucker Jr^*

来源：Molecular Physics, 2017, 115(15-16): 1775-1785.

DOI：10.1080/00268976.2016.1271153

• Vibrational spectroscopy
• collocation
• phosgene
• neural networks

Phosgene (Cl-2 C=O) is extremely poisonous, underscoring the importance of accurate infrared detection. Here, the computed vibrational energy levels of phosgene are reported for the first time from a six-dimensional potential energy surface (PES) that was constructed from 25,000 single-point energy computations at the CCSD(T)/cc-pVTZ level of theory. The computed points were fit using a neural network method, and the resulting PES was employed in the determination of vibrational energies and wave functions. Bond coordinates were utilised in conjunction with a collocation method to minimise problems that arise from the complicated nature of the kinetic energy operator. The collocation method makes possible the computation of energy levels without integral evaluation, and without the need to solve a generalised eigen value problem. Moreover, it is built on a nondirect productpruned basis that is much smaller than the direct product basis that would be required to obtain the same accuracy.

• 出版日期2017