FTIR and dispersive gas phase absolute infrared intensities of hydrocarbon fundamental bands

Autor(es)

Duarte, Leonardo J. ^[1] ; Bruns, Roy E. ^[1]

Afiliação do(s) autor(es)

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

• Tipo de documento: Artigo Científico
• Fonte: SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY; v. 214, p. 1-6, MAY 5 2019.
• Citações Web of Science: 0

Resumo

Newexperimental intensity results obtained by band integration fromthe PNNL (PacificNorthwest National Laboratory) spectral library are reported for 26 CH vibrations of methane, acetylene, ethylene, ethane, allene, propyne and cyclopropane. The PNNL intensity values range from 3.1 to 185.4 km mol(-1) and are in excellent agreement, rms difference of 3.1 km mol(-1), with earlier low resolution intensity results. QCISD/6-311++ G (3d, 3p) and QCISD/cc-pVTZ theoretical results are in good agreement with the PNNL intensity values with rms differences of 4.4 and 4.9 km mol(-1), respectively. Charge-charge transfer-dipolar polarizationmodel parameters at both quantum levels indicate that the charge transfer-dipolar polarization contributions to the intensities are much larger than those owing to the movements of static equilibrium charges on hydrogen for these vibrations except for the CH vibrations of acetylene that is known to contain very acidic hydrogen atoms. The main effect of the static chargemovement comes fromits interactionwith charge transfer-dipolar polarization owing to the relatively large parameter values of this dynamic electronic contribution. The sumof the charge transfer-dipolar polarization parameters with their interaction with the charge accurately describes the variations in the intensity values of these hydrocarbon vibrations. (C) 2019 Elsevier B.V. All rights reserved. (AU)

• Processo FAPESP: 18/08861-9 - Aplicação do modelo QTAIM / CCTDP e machine learning para a previsão de reatividades químicas
• Beneficiário: Roy Edward Bruns
• Modalidade de apoio: Auxílio à Pesquisa - Regular
• Processo FAPESP: 17/22741-3 - Uso de multipolos atômicos e desenvolvimento de modelos de machine learning na investigação de estados de transição
• Beneficiário: Leonardo José Duarte
• Modalidade de apoio: Bolsas no Brasil - Doutorado Direto
• Processo FAPESP: 09/09678-4 - Investigação de regras de soma de intensidades fundamentais no infravermelho usando o modelo CCFDF/QTAIM
• Beneficiário: Roy Edward Bruns
• Modalidade de apoio: Auxílio à Pesquisa - Regular