Quantum cluster equilibrium prediction of liquid ethanol

Quantum cluster equilibrium theory (QCE) has been widely used to determine the properties of pure and binary mixture of liquids. The main limitation of the application of QCE is the exploration of different possible clusters formed by the solvent molecules. Therefore, in this study, we applied the QCE theory to predict liquid properties of ethanol after thorough exploration of the potential energy surfaces (PESs) of the ethanol clusters from dimer to hexamer. The exploration started by generating possible structures using classical molecular dynamics followed by optimizations at the MP2/aug-cc-pVDZ level of theory. 484 different configurations of the ethanol clusters have been finally used in the QCE theory. The results show that the population of liquid ethanol is constituted from the contribution of hexamer, pentamer, and tetramer. In addition, we noted that the ethanol monomer, dimer and trimer do not contribute to the population of liquid ethanol. Furthermore, based on the predicted population of the liquid ethanol, we calculated its infrared spectrum at different temperatures. The calculated infrared spectrum is found to be in qualitative agreement with experiment. Some thermodynamic properties, such as the heat capacity, are also predicted to be in good agreement with experiment

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 Fermi–Dirac 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> ≤ 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): Δ<i>H</i>_0→<i>T</i> = 6.1398 kJ mol^–1 and Δ<i>G</i>_0→<i>T</i> = −26.3424 kJ mol^–1. 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 Fermi–Dirac 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> ≤ 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): Δ<i>H</i>_0→<i>T</i> = 6.1398 kJ mol^–1 and Δ<i>G</i>_0→<i>T</i> = −26.3424 kJ mol^–1. 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

Effects of hydrogen dissociation on the infrared emission spectra of naphthalene: theoretical modeling

International audienceThe IR emission spectroscopy of naphthalene and its singly- and doubly-dehydrogenated radicals has been modeled using kinetic Monte Carlo simulations, taking into account the various relaxation pathways of radiative emission and hydrogen loss. Our modeling relies on quantum chemistry ingredients that were obtained from dedicated calculations based on density functional theory, including explicitly anharmonicity contributions. Our results show that the fragmentation products significantly contribute to the overall IR emission spectrum, especially to the intensity ratios between bands. Owing to the likely presence of polycyclic aromatic hydrocarbons in the interstellar medium, these findings are particularly relevant in the astrophysical context

Visible Photodissociation Spectra of the 1- and 2‑Methylnaphthalene 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 D₂ ← D₀ electronic transition. The 1-methylnaphthalene⁺ absorption bands revealed a red shift of 808 cm^–1, relative to those of the naphthalene cation (14 906 cm^–1), whereas for 2-methylnaphthalene⁺ a blue shift of 226 cm^–1 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 Franck–Condon factors using the cumulant Gaussian fluctuations formalism extended to include the internal rotation