Application of the QTAIM / CCTDP model and machine learning for the forecast of chemical reactivities

• Grant number: 18/08861-9
• Support Opportunities: Regular Research Grants
• Start date: August 01, 2018
• End date: July 31, 2019
• 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
• Associated researchers: Arnaldo Fernandes da Silva Filho ; Wagner Eduardo Richter

Abstract

Transition states are the pillars that underpin the study of chemical reactivities, allowing chemists to infer reaction mechanisms, to calculate activation energies, enthalpies, and other physical-chemical parameters. This project proposes a new methodology, based on quantum topology and machine learning, to obtain transition states and predict reactivity parameters. To achieve these objectives, we will work on three independent high-impact fronts in the areas of Chemistry, Physics and Data Science: 1) Obtaining reactivity parameters based on the Quantum Chemical Topology for organic reactions 2) Using Machine Learning to predict, through of a training set of known and/or theoretically calculated reactions, enthalpies, velocity constants and activation energies for unknown reactions 3) Practical application of both topics above, through: (i) Study of the effect of substituents on benzene rings by means of Hammett constants; ii) Study of the enhancement of absorption Infrared intensities caused by hydrogen bonds and iii) Study of the reverse acidity of boron trihalides. (AU)

Scientific publications

(15)

(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)

DUARTE, LEONARDO J.; BRUNS, ROY. E.. Energetic Origins of Force Constants: Adding a New Dimension to the Hessian Matrix via Interacting Quantum Atoms. Journal of Physical Chemistry A, v. 126, n. 48, p. 10-pg., 2022-12-08. (18/08861-9, 17/22741-3)

RICHTER, WAGNER E.; DUARTE, LEONARDO J.; BRUNS, ROY E.. Atomic charge and atomic dipole modeling of gas-phase infrared intensities of fundamental bands for out-of-plane CH and CF bending vibrations. SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, v. 251, APR 15 2021. (17/22741-3, 18/08861-9)

DUARTE, LEONARDO J.; BRUNS, ROY E.. br Electronic Distribution of S(N)2 IRC and TS Structures: Infrared Intensities of Imaginary Frequencies. JOURNAL OF CHEMICAL THEORY AND COMPUTATION, v. 18, n. 4, p. 11-pg., 2022-04-12. (17/22741-3, 18/08861-9)

DUARTE, LEONARDO J.; RICHTER, WAGNER E.; BRUNS, ROY E.; POPELIER, PAUL L. A.. Electrostatics Explains the Reverse Lewis Acidity of BH3 and Boron Trihalides: Infrared Intensities and a Relative Energy Gradient (REG) Analysis of IQA Energies. Journal of Physical Chemistry A, v. 125, n. 39, p. 8615-8625, OCT 7 2021. (18/24844-7, 18/08861-9, 17/22741-3)

DUARTE, LEONARDO J.; RICHTER, WAGNER E.; SILVA, ARNALDO F.; BRUNS, ROY E.. Quantum chemical intensity determinations of overlapped gas phase infrared bands. SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, v. 230, APR 5 2020. (18/08861-9, 18/24844-7)

RICHTER, WAGNER E.; DUARTE, LEONARDO J.; DA SILVA, ARNALDO F.; BRUNS, ROY E.. Revisiting the negative dipole moment derivatives of HNgX molecules. THEORETICAL CHEMISTRY ACCOUNTS, v. 139, n. 3, MAR 23 2020. (18/08861-9, 18/24844-7)

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)

RICHTER, WAGNER E.; DUARTE, LEONARDO J.; BRUNS, ROY E.. Are ``GAPT Charges{''} Really Just Charges?. JOURNAL OF CHEMICAL INFORMATION AND MODELING, v. 61, n. 8, p. 3881-3890, AUG 23 2021. (18/24844-7, 18/08861-9)

DUARTE, LEONARDO J.; SILVA, ARNALDO F.; RICHTER, WAGNER E.; BRUNS, ROY E.. Infrared Intensification and Hydrogen Bond Stabilization: Beyond Point Charges. Journal of Physical Chemistry A, v. 123, n. 30, p. 6482-6490, AUG 1 2019. (18/08861-9, 14/21241-9, 17/22741-3)

RICHTER, WAGNER E.; DUARTE, LEONARDO J.; VIDAL, LUCIANO N.; BRUNS, ROY E.. AC/DC Analysis: Broad and Comprehensive Approach to Analyze Infrared Intensities at the Atomic Level. Journal of Physical Chemistry A, v. 125, n. 15, p. 11-pg., 2021-04-13. (18/24844-7, 18/08861-9)

DUARTE, LEONARDO J.; RICHTER, WAGNER E.; BRUNS, ROY E.. Characteristic Substituent Effect Model for the Infrared Intensities of the X2CY (X = H, F, Cl, Br; Y = O, S) Molecules. Journal of Physical Chemistry A, v. N/A, p. 9-pg., 2023-04-03. (18/08861-9, 17/22741-3)

RICHTER, WAGNER E.; DUARTE, LEONARDO J.; BRUNS, ROY E.. navoidable failure of point charge descriptions of electronic density changes for out-of-plane distortion. SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY, v. 271, APR 15 2022. (17/22741-3, 18/08861-9)

DUARTE, LEONARDO J.; BRUNS, ROY E.. QTAIM Atomic Charge and Polarization Parameters and Their Machine-Learning Transference among Boron-Halide Molecules. Journal of Physical Chemistry A, v. 124, n. 17, p. 3407-3416, APR 30 2020. (18/24844-7, 18/08861-9)

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)

DUARTE, LEONARDO J.; RICHTER, WAGNER E.; BRUNS, ROY E.. Characteristic Substituent Effect Model for the Infrared Intensities of the X2CY (X = H, F, Cl, Br; Y = O, S) Molecules. Journal of Physical Chemistry A, v. 127, n. 14, p. 9-pg., 2023-04-13. (18/08861-9, 17/22741-3)