Key Role of Some Specific Occupied Molecular Orbitals of Short Chain n-Alkanes in Their Surface Tension and Reaction Rate Constants with Hydroxyl Radicals: DFT Study — Oak Academic Publishing
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Key Role of Some Specific Occupied Molecular Orbitals of Short Chain n-Alkanes in Their Surface Tension and Reaction Rate Constants with Hydroxyl Radicals: DFT Study
Department of Physical and Quantum Chemistry, Institute of Chemistry, Academy of Sciences of Moldova, Kishinev, Republic of Moldova
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Department of Physical and Quantum Chemistry, Institute of Chemistry, Academy of Sciences of Moldova, Kishinev, Republic of Moldova
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Department of Physical and Quantum Chemistry, Institute of Chemistry, Academy of Sciences of Moldova, Kishinev, Republic of Moldova
1 Department of Physical and Quantum Chemistry, Institute of Chemistry, Academy of Sciences of Moldova, Kishinev, Republic of Moldova
2 Department of Physical and Quantum Chemistry, Institute of Chemistry, Academy of Sciences of Moldova, Kishinev, Republic of Moldova
3 Department of Physical and Quantum Chemistry, Institute of Chemistry, Academy of Sciences of Moldova, Kishinev, Republic of Moldova
Basing on the DFT calculations we propose the new theoretical model which describes both the surface tension σ of the short chain n-alkanes at their normal boiling points and their reaction rate constants with hydroxyl radicals OH • (at 297 ± 2 K) on the basis of their molecular orbital electronic characteristics. It has been shown that intermolecular dispersion attraction within the surface liquid monolayer of these compounds, as well as their reaction rate constants k with OH • radicals are determined by the energies E orb of the specific occupied molecular orbitals which are the same in the determination of both the above physico-chemical characteristics of the studied n-alkanes. The received regression equations confirm the theoretically found dependences between the quantities of σ and k and the module | E orb |. For the compounds under study this fact indicates the key role of their electronic structure particularities in determination of both the physical (surface tension) and the chemical (reaction rate constants) properties.
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