Hunting for Complex Organic Molecules in the Interstellar Medium: The Role of Accurate Low-Cost Theoretical Geometries and Rotational Constants

A new approach to computation at affordable cost of accurate geometrical structures and rotational constants for medium-sized molecules in the gas phase is further improved and applied to a large panel of interstellar complex organic molecules. The most distinctive feature of the new model is the effective inclusion of core-valence correlation and vibrational averaging effects in the framework of density functional theory (DFT). In particular, a double-hybrid functional in conjunction with a quadruple-zeta valence/triple-zeta polarization basis set is employed for geometry optimizations, whereas a cheaper hybrid functional in conjunction with a split-valence basis set is used for the evaluation of vibrational corrections. A thorough benchmark based on a wide range of prototypical systems shows that the new scheme approaches the accuracy of state-of-the-art wave function methods with the computational cost of the standard methods (DFT or MP2) routinely employed in the interpretation of microwave spectra. Since the whole computational workflow involves the postprocessing of the output of standard electronic structure codes by a new freely available web utility, the way is paved for the accurate yet not prohibitively expensive study of medium- to large-sized molecules also by nonspecialists.

Automated summary

This study presents a new approach for cost-effective computation of accurate geometrical structures and rotational constants for medium-sized molecules in the gas phase, which is applied to a large number of interstellar complex organic molecules. The new model effectively incorporates core-valence correlation and vibrational averaging effects using density functional theory (DFT). Benchmark tests show that the new scheme achieves the accuracy of state-of-the-art wave function methods, while maintaining the computational cost of standard methods routinely used in interpreting microwave spectra.