Quantum theory of atoms in molecules/charge-charge flux-dipole flux models for fundamental vibrational intensity changes on H-bond formation of water and hydrogen fluoride

Autor(es)

Silva, Arnaldo F. ^[1] ; Richter, Wagner E. ^[1] ; Terrabuio, Luiz A. ^[2] ; Haiduke, Roberto L. A. ^[2] ; Bruns, Roy E. ^[1]

Afiliação do(s) autor(es)

^[1] Univ Estadual Campinas, Inst Quim, BR-13083970 Campinas, SP - Brazil

^[2] Univ Sao Paulo, Inst Quim Sao Carlos, Dept Quim & Fis Mol, BR-13560970 Sao Carlos, SP - Brazil

• Tipo de documento: Artigo Científico
• Fonte: Journal of Chemical Physics; v. 140, n. 8 FEB 28 2014.
• Citações Web of Science: 7

Resumo

The Quantum Theory of Atoms In Molecules/Charge-Charge Flux-Dipole Flux (QTAIM/CCFDF) model has been used to investigate the electronic structure variations associated with intensity changes on dimerization for the vibrations of the water and hydrogen fluoride dimers as well as in the water-hydrogen fluoride complex. QCISD/cc-pVTZ wave functions applied in the QTAIM/CCFDF model accurately provide the fundamental band intensities of water and its dimer predicting symmetric and antisymmetric stretching intensity increases for the donor unit of 159 and 47 km mol(-1) on H-bond formation compared with the experimental values of 141 and 53 km mol(-1). The symmetric stretching of the proton donor water in the dimer has intensity contributions parallel and perpendicular to its C-2v axis. The largest calculated increase of 107 km mol(-1) is perpendicular to this axis and owes to equilibrium atomic charge displacements on vibration. Charge flux decreases occurring parallel and perpendicular to this axis result in 42 and 40 km mol(-1) total intensity increases for the symmetric and antisymmetric stretches, respectively. These decreases in charge flux result in intensity enhancements because of the interaction contributions to the intensities between charge flux and the other quantities. Even though dipole flux contributions are much smaller than the charge and charge flux ones in both monomer and dimer water they are important for calculating the total intensity values for their stretching vibrations since the charge-charge flux interaction term cancels the charge and charge flux contributions. The QTAIM/CCFDF hydrogen-bonded stretching intensity strengthening of 321 km mol(-1) on HF dimerization and 592 km mol(-1) on HF: H2O complexation can essentially be explained by charge, charge flux and their interaction cross term. Atomic contributions to the intensities are also calculated. The bridge hydrogen atomic contributions alone explain 145, 237, and 574 km mol(-1) of the H-bond stretching intensity enhancements for the water and HF dimers and their heterodimer compared with total increments of 149, 321, and 592 km mol(-1), respectively. (C) 2014 AIP Publishing LLC. (AU)

• Processo FAPESP: 11/02807-3 - Investigação dos multipolos atômicos da teoria quântica de átomos em moléculas no estudo de propriedades moleculares
• Beneficiário: Luiz Alberto Terrabuio
• Modalidade de apoio: Bolsas no Brasil - Mestrado
• Processo FAPESP: 10/18743-1 - Uso de multipolos da teoria quântica de átomos em moléculas e estudos cinéticos em sistemas encontrados no meio interestelar
• Beneficiário: Roberto Luiz Andrade Haiduke
• Modalidade de apoio: Auxílio à Pesquisa - Regular