Sensitivity of Intra- and Intermolecular Interactions of Benzo[h]quinoline from Car–Parrinello Molecular Dynamics and Electronic Structure Inspection
| Autor: | Bartłomiej M. Szyja, Aneta Jezierska, Jarosław J. Panek, Joanna Zasada, Beata Kizior |
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| Rok vydání: | 2021 |
| Předmět: |
O-H stretching envelope
Car–Parrinello molecular dynamics Materials science Proton QH301-705.5 CDFT Electrons Electronic structure Molecular Dynamics Simulation 010402 general chemistry Vibration solvent 01 natural sciences Article Catalysis Inorganic Chemistry Molecular dynamics benzo[h]quinoline 1D and 2D Pmf Biology (General) Physics::Chemical Physics Physical and Theoretical Chemistry QD1-999 Molecular Biology Density Functional Theory Spectroscopy Fourier Analysis Molecular Structure 010405 organic chemistry Organic Chemistry Intermolecular force Hydrogen Bonding Resorcinols General Medicine Acceptor Electron localization function 0104 chemical sciences Computer Science Applications Chemistry ELF crystalline phase Chemical physics Quinolines Density functional theory Gases gas phase CPMD |
| Zdroj: | International Journal of Molecular Sciences, Vol 22, Iss 5220, p 5220 (2021) International Journal of Molecular Sciences Volume 22 Issue 10 |
| ISSN: | 1422-0067 |
| DOI: | 10.3390/ijms22105220 |
| Popis: | The O-H...N and O-H...O hydrogen bonds were investigated in 10-hydroxybenzo[h]quinoline (HBQ) and benzo[h]quinoline-2-methylresorcinol complex in vacuo, solvent and crystalline phases. The chosen systems contain analogous donor and acceptor moieties but differently coupled (intra- versus intermolecularly). Car–Parrinello molecular dynamics (CPMD) was employed to shed light onto principle components of interactions responsible for the self-assembly. It was applied to study the dynamics of the hydrogen bonds and vibrational features as well as to provide initial geometries for incorporation of quantum effects and electronic structure studies. The vibrational features were revealed using Fourier transformation of the autocorrelation function of atomic velocity and by inclusion of nuclear quantum effects on the O-H stretching solving vibrational Schrödinger equation a posteriori. The potential of mean force (Pmf) was computed for the whole trajectory to derive the probability density distribution and for the O-H stretching mode from the proton vibrational eigenfunctions and eigenvalues incorporating statistical sampling and nuclear quantum effects. The electronic structure changes of the benzo[h]quinoline-2-methylresorcinol dimer and trimers were studied based on Constrained Density Functional Theory (CDFT) whereas the Electron Localization Function (ELF) method was applied for all systems. It was found that the bridged proton is localized on the donor side in both investigated systems in vacuo. The crystalline phase simulations indicated bridged proton-sharing and transfer events in HBQ. These effects are even more pronounced when nuclear quantization is taken into account, and the quantized Pmf allows the proton to sample the acceptor area more efficiently. The CDFT indicated the charge depletion at the bridged proton for the analyzed dimer and trimers in solvent. The ELF analysis showed the presence of the isolated proton (a signature of the strongest hydrogen bonds) only in some parts of the HBQ crystal simulation. The collected data underline the importance of the intramolecular coupling between the donor and acceptor moieties. |
| Databáze: | OpenAIRE |
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