Ab initio quantum chemical studies of the electronic properties of the hydrogen bonded N2HF, N2HCl, (HCN)2 and NH3HCN complexes
1987; Elsevier BV; Volume: 115; Issue: 3 Linguagem: Inglês
10.1016/0301-0104(87)80046-0
ISSN1873-4421
AutoresPeter L. Cummins, George B. Bacskay, Noel S. Hush,
Tópico(s)Quantum, superfluid, helium dynamics
ResumoThe results of ab initio self-consistent field (SCF) and configuration interaction (CI) calculations on the hydrogen bonded N2HF, N2HCl, (HCN)2 and NH3HCN complexes, using basis sets that range from double-zeta plus polarization to triple-zeta plus double polarization, are reported. The primary objective of this work has been to calculate the changes in the dipole moments and the electric field gradients (EFGs) at the quadrupolar 14N, 2H and 35Cl nuclei that are induced by H-bonding. Since the interpretation of the H-bond induced shifts requires a knowledge of the molecular dynamics in weakly H-bonded molecular complexes such as those studied in the present work, we have taken into account the effects of vibrational averaging on both the EFGs and dipole moments utilizing harmonic intermolecular force fields that were generated using ab initio SCF methods. The results of these calculations are compared with the corresponding experimental quantities that are obtained from the microwave spectra of these complexes.
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