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Schlagwörter:
DENSITY-FUNCTIONAL THEORY; ADAPTED PERTURBATION-THEORY; CORRELATED MOLECULAR CALCULATIONS; BASIS-SET CONVERGENCE; GAUSSIAN-BASIS SETS; KOHN-SHAM ORBITALS; HYDROGEN HALIDES; INTERMOLECULAR INTERACTIONS; INTERACTION ENERGIES; ROTATIONAL SPECTRUM
Zusammenfassung:
Here the interactions of furan with HZ (Z = CCH, CCF, CN, Cl, and F) are studied using a variety of electron correlation methods (MP2, CCSD(T), DFT-SAPT) and correlation-consistent triple- and quadruple-ζ basis sets including complete basis set (CBS) extrapolation. For Fu–HF all methods agree that a n-type structure with a hydrogen bridge between the oxygen lone-pair of furan and the hydrogen atom of HF is the global minimum structure. It is found to be significantly more stable than a π-type structure where the hydrogen atom of HF points toward the π system of furan. For the other four dimers MP2 and DFT-SAPT predict the π-type structure to be somewhat more stable, while CCSD(T) favors the n-type structure as the global minimum for Fu–HCl and predicts both structures as nearly isoenergetic for Fu–HCCH and Fu–HCCF. From a geometrical point of view, the Fu–HCN dimer structures are more related to those of the Fu–HCl complex than to Fu–HCCH. The different behavior of HCCF and HF upon complexation with furan evidence the effect of the presence of a π system in the aggregation of fluorine derivatives. It is shown that aggregates of furan cannot be understood by means of dipole–dipole and electrostatic analysis only. Yet, through a combined and detailed analysis of DFT-SAPT energy contributions and resonance effects on the molecular charge distributions a consistent explanation of the aggregation of furan with both π electron rich molecules and halogen hydrides is provided.
