3 research outputs found
Revision of the Thermodynamics of the Proton in Gas Phase
Proton
transfer is ubiquitous in various physical/chemical processes,
and the accurate determination of the thermodynamic parameters of
the proton in the gas phase is useful for understanding and describing
such reactions. However, the thermodynamic parameters of such a proton
are usually determined by assuming the proton as a classical particle
whatever the temperature. The reason for such an assumption is that
the entropy of the quantum proton is not always soluble analytically
at all temperatures. Thereby, we addressed this matter using a robust
and reliable self-consistent iterative procedure based on the FermiāDirac
formalism. As a result, the free proton gas can be assumed to be classical
for temperatures higher than 200 K. However, it is worth mentioning
that quantum effects on the gas phase proton motion are really significant
at low temperatures (<i>T</i> ā¤ 120 K). Although
the proton behaves as a classical particle at high temperatures, we
strongly recommend the use of quantum results at all temperatures,
for the integrated heat capacity and the Gibbs free energy change.
Therefore, on the basis of the thermochemical convention that ignores
the proton spin, we recommend the following revised values for the
integrated heat capacity and the Gibbs free energy change of the proton
in gas phase and, at the standard pressure (1 bar): Ī<i>H</i><sub>0ā<i>T</i></sub> = 6.1398 kJ mol<sup>ā1</sup> and Ī<i>G</i><sub>0ā<i>T</i></sub> = ā26.3424 kJ mol<sup>ā1</sup>. Finally,
it is important noting that the little change of the pressure from
1 bar to 1 atm affects notably the entropy and the Gibbs free energy
change of the proton
Revision of the Thermodynamics of the Proton in Gas Phase
Proton
transfer is ubiquitous in various physical/chemical processes,
and the accurate determination of the thermodynamic parameters of
the proton in the gas phase is useful for understanding and describing
such reactions. However, the thermodynamic parameters of such a proton
are usually determined by assuming the proton as a classical particle
whatever the temperature. The reason for such an assumption is that
the entropy of the quantum proton is not always soluble analytically
at all temperatures. Thereby, we addressed this matter using a robust
and reliable self-consistent iterative procedure based on the FermiāDirac
formalism. As a result, the free proton gas can be assumed to be classical
for temperatures higher than 200 K. However, it is worth mentioning
that quantum effects on the gas phase proton motion are really significant
at low temperatures (<i>T</i> ā¤ 120 K). Although
the proton behaves as a classical particle at high temperatures, we
strongly recommend the use of quantum results at all temperatures,
for the integrated heat capacity and the Gibbs free energy change.
Therefore, on the basis of the thermochemical convention that ignores
the proton spin, we recommend the following revised values for the
integrated heat capacity and the Gibbs free energy change of the proton
in gas phase and, at the standard pressure (1 bar): Ī<i>H</i><sub>0ā<i>T</i></sub> = 6.1398 kJ mol<sup>ā1</sup> and Ī<i>G</i><sub>0ā<i>T</i></sub> = ā26.3424 kJ mol<sup>ā1</sup>. Finally,
it is important noting that the little change of the pressure from
1 bar to 1 atm affects notably the entropy and the Gibbs free energy
change of the proton
Visible Photodissociation Spectra of the 1- and 2āMethylnaphthalene Cations: Laser Spectroscopy and Theoretical Simulations
The electronic absorption spectra
of the two methyl derivatives
of the naphthalene cation were measured using an argon tagging technique.
In both cases, a band system was observed in the visible range and
assigned to the D<sub>2</sub> ā D<sub>0</sub> electronic transition.
The 1-methylnaphthalene<sup>+</sup> absorption bands revealed a red
shift of 808 cm<sup>ā1</sup>, relative to those of the naphthalene
cation (14ā906 cm<sup>ā1</sup>), whereas for 2-methylnaphthalene<sup>+</sup> a blue shift of 226 cm<sup>ā1</sup> appeared. A short
vibrational progression, similar to the naphthalene cation, was also
observed for both isomers and found to involve similar aromatic ring
skeleton vibrations. Moreover, insights into the internal rotation
motion of the methyl group were inferred, although the spectral resolution
was not sufficient to fully resolve the substructure. These measurements
were supported by detailed quantum chemical calculations. They allowed
exploration of the potential energy curves along this internal coordinate,
along with a complete simulation of the harmonic FranckāCondon
factors using the cumulant Gaussian fluctuations formalism extended
to include the internal rotation