Hydrogen-bonding effects on infrared spectra from anharmonic computations: uracil-water complexes and uracil dimers.

Hydrogen-bonding interactions lead to significant changes in the infrared (IR) spectrum, like frequency shifts of the order of magnitude of hundreds of cm(-1) and increases of IR intensity for bands related to vibrational modes of functional groups directly involved in the hydrogen-bonded bridges. We are actively developing a comprehensive and robust computational protocol aimed at the quantitative reproduction of the spectra of bio-organic and hybrid organic/inorganic molecular systems with a proper account of the variety of intra- and intermolecular interactions. We have resorted to fully anharmonic quantum mechanical computations within the generalized second-order vibrational perturbation theory (GVPT2) approach, combined with the B3LYP-D3 method, in conjunction with basis sets of double-ζ plus polarization quality. Such an approach has been validated in a previous work ( Phys. Chem. Chem. Phys. 2014 , 16 , 10112 - 10128 ) for simulating the IR spectra of the monomers of nucleobases and some of their dimers. In the present contribution we have extended our computational protocol toward hybrid models, with the harmonic part computed at the B2PLYP level, in conjunction with the maug-cc-pVTZ basis set, or by a cost-effective ONIOM B2PLYP:B3LYP focused model, where only part of the molecular system forming the hydrogen bonds is treated at the B2PLYP level of theory. In this work experimental frequencies available for a set of four uracil-water complexes have been considered as references for the computational methodologies applied to the simulation of hydrogen-bonding effects on the infrared spectrum, obtaining average uncertainties of about 22 cm(-1) for B3LYP-D3/N07D and improved description within 10 cm(-1) by hybrid B2PLYP/B3LYP-D3 approaches. The same computational schemes have been next applied to simulate fully anharmonic IR spectra of six different hydrogen-bonded uracil dimers, providing reliable support for future experimental investigations on hydrogen-bonded systems.