A simple heuristic approach to estimate the thermochemistry of condensed-phase molecules based on the polarizable continuum model.

Clicks: 135
ID: 19607
2019
Article Quality & Performance Metrics
Overall Quality
Not rated
Combines reader engagement with the AI quality analysis. This article has not been analysed, so there is no overall score — reader engagement is measured and shown alongside.
AI Quality Assessment
Not analyzed
Readership in this journal
Steady

Ranked #128 of 184 articles by views in Physical chemistry chemical physics : PCCP

Most read Least read

Bar heights use a square-root scale. Only the 120 most-read articles are drawn; the journal has 184 in total.

Mint this article as an NFT
Not yet minted

Create a permanent, verifiable on-chain record of this article on the Scimatic Network. The NFT is held in your Journament account, and you can withdraw it to your own wallet at any time.

5 SUSD one-off · no wallet required
Sign in to mint
Abstract
A simple model based on a quantum chemical approach with polarizable continuum models (PCMs) to provide reasonable translational and rotational entropies for liquid phase molecules was developed. A translational term was evaluated with free-volume compensation for the Sackur-Tetrode equation. We assumed that the free-volume corresponds to the cavity volume in the PCM. A rotational term was modeled as restricted rotation of a dipole in the electrostatic field. Entropies were assessed for twenty species in the liquid-phase using the proposed model, and the computed values were compared with experimental values. Quantum chemistry calculations were conducted at the ωB97X-D/6-311++G(d,p) level with the conductor-like PCM method. Predicted entropies were in good agreement with the experimental entropies, and the root mean square deviation was 17.2 J mol-1 K-1. The standard enthalpy change of formation was then investigated for eleven specific species. The CBS-QB3//ωB97X-D method provides a reasonable standard enthalpy of formation for gasified species; however, improvement of the accuracy is required for liquid species. Finally, the dependence of the Gibbs energy on temperature was investigated for the eleven specific species. When the ideal gas treatment is used, the Gibbs energy trends for the gaseous and liquid phases are quasi-parallel for all of the species, although the Gibbs energy trends for liquids based on the proposed model intersected the gaseous trend (i.e. the intersection is the boiling point). However, the model significantly under or overestimated the experimental boiling points. The error of the boiling points was predominantly due to the inaccuracy of the enthalpy.
Reference Key
izato2019aphysical Use this key to autocite in the manuscript while using SciMatic Manuscript Manager or Thesis Manager
Authors Izato, Yu-Ichiro;Matsugi, Akira;Koshi, Mitsuo;Miyake, Atsumi;
Journal Physical chemistry chemical physics : PCCP
Year 2019
DOI
10.1039/c9cp03226f
URL
Keywords Keywords not found

Citations

No citations found. To add a citation, contact the admin at info@scimatic.org

Comments

No comments yet. Be the first to comment on this article.