A CCFDF/QTAIM model investigation of fundamental infrared intensity sum rules

• Grant number: 09/09678-4
• Support Opportunities: Regular Research Grants
• Start date: October 01, 2009
• End date: September 30, 2011
• Field of knowledge: Physical Sciences and Mathematics - Chemistry - Physical-Chemistry
• Principal Investigator: Roy Edward Bruns
• Grantee: Roy Edward Bruns
• Host Institution: Instituto de Química (IQ). Universidade Estadual de Campinas (UNICAMP). Campinas , SP, Brazil

Abstract

The Charge - Charge Flux - Dipole Flux (CCFDF) model recently proposed by our research group has been applied to several groups of molecules using electronic densities obtained at the MP2/6-311++G(3d,3p) level and atomic charges and dipoles of the Quantum Theory of Atoms in Molecules (QTAIM). In this project the CCFDF model will be applied to the vibrations of the X2CY ( X = F,Cl; Y = O,S ) molecules and the fluorochloromethanes using electronic densities obtained at the QCISD/cc-pVTZ level. Intensity and CCFDF parameter results from both theoretical levels will be compared. Intensity sum rules for each group of molecules will be transformed into charge, charge flux and dipole flux contributions. A complementary study will be made on electronegativity models for each of these molecular groups. The charge, charge flux and dipole flux contributions provide a common basis for understanding more profoundly why the sum rules and electronegativity models work so well and for clarifying the relations between both approaches. The atomic contributions of charge, charge flux and dipole flux of these molecules will be subjected to chemometric analyses in order to determine their potentialities for predicting intensity values of other molecules. (AU)

Scientific publications

(9)

(References retrieved automatically from Web of Science and SciELO through information on FAPESP grants and their corresponding numbers as mentioned in the publications by the authors)

RICHTER, WAGNER E.; SILVA, ARNALDO F.; VIDAL, LUCIANO N.; BRUNS, ROY E.. Characteristic infrared intensities of carbonyl stretching vibrations. Physical Chemistry Chemical Physics, v. 18, n. 26, p. 17575-17585, JUL 14 2016. (14/21241-9, 09/09678-4)

SILVA, ARNALDO F.; DUARTE, LEONARDO J.; BRUNS, ROY E.. QTAIM-Based Characteristic Group Infrared Intensities of Amino Acids and Their Transference to Peptides. Journal of Physical Chemistry A, v. 120, n. 42, p. 8387-8399, OCT 27 2016. (14/21241-9, 16/07411-4, 09/09678-4)

DUARTE, LEONARDO J.; BRUNS, ROY E.. FTIR and dispersive gas phase absolute infrared intensities of hydrocarbon fundamental bands. SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, v. 214, p. 1-6, MAY 5 2019. (18/08861-9, 17/22741-3, 09/09678-4)

WAGNER E. RICHTER; LEONARDO J. DUARTE; ARNALDO F. SILVA; ROY E. BRUNS. Review of Experimental GAPT and Infrared Atomic Charges in Molecules. Journal of the Brazilian Chemical Society, v. 27, n. 6, p. 979-991, 2016-06-00. (14/21241-9, 09/09678-4)

AFONSO, SABRINA; SILVA, FABIANO B.; SILVA, ARNALDO F.; SCARMINIO, IEDA S.; BRUNS, ROY E.. Infrared spectral evidence and DFT calculations of hydrogen-bonding and molecular structures of acetogenins. Journal of Molecular Structure, v. 1130, p. 174-180, FEB 15 2017. (14/21241-9, 09/09678-4)

DUARTE, LEONARDO J.; BRUNS, ROY E.. Atomic Polarizations, Not Charges, Determine CH Out-of-Plane Bending Intensities of Benzene Molecules. Journal of Physical Chemistry A, v. 122, n. 51, p. 9833-9841, DEC 27 2018. (09/09678-4, 18/08861-9, 17/22741-3)

SILVA, ARNALDO F.; RICHTER, WAGNER E.; BASSI, ADALBERTO B. M. S.; BRUNS, ROY E.. Dynamic atomic contributions to infrared intensities of fundamental bands. Physical Chemistry Chemical Physics, v. 17, n. 45, p. 30378-30388, 2015. (14/21241-9, 09/09678-4)

RICHTER, WAGNER E.; BRUNS, ROY E.. Revisiting the integrated infrared intensities and atomic polar tensors of the boron trihalides. SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, v. 164, p. 123-127, JUL 5 2016. (09/09678-4)

SILVA, ARNALDO F.; RICHTER, WAGNER E.; MENESES, HELEN G. C.; BRUNS, ROY E.. Atomic charge transfer-counter polarization effects determine infrared CH intensities of hydrocarbons: a quantum theory of atoms in molecules model. Physical Chemistry Chemical Physics, v. 16, n. 42, p. 23224-23232, NOV 14 2014. (09/09678-4)