Jove
Visualize
Contact Us
JoVE
x logofacebook logolinkedin logoyoutube logo
ABOUT JoVE
OverviewLeadershipBlogJoVE Help Center
AUTHORS
Publishing ProcessEditorial BoardScope & PoliciesPeer ReviewFAQSubmit
LIBRARIANS
TestimonialsSubscriptionsAccessResourcesLibrary Advisory BoardFAQ
RESEARCH
JoVE JournalMethods CollectionsJoVE Encyclopedia of ExperimentsArchive
EDUCATION
JoVE CoreJoVE BusinessJoVE Science EducationJoVE Lab ManualFaculty Resource CenterFaculty Site
Terms & Conditions of Use
Privacy Policy
Policies

Related Experiment Videos

Anharmonic effects in the quantum cluster equilibrium method.

Michael von Domaros1, Eva Perlt1

  • 1Mulliken Center for Theoretical Chemistry, University of Bonn, Beringstr. 6, D-53115 Bonn, Germany.

The Journal of Chemical Physics
|April 8, 2017
PubMed
Summary
This summary is machine-generated.

Related Concept Videos

You might also read

Related Articles

Articles linked to this work by shared authors, journal, and citation graph.

Sort by
Same author

TURBOMOLE: Modular program suite for ab initio quantum-chemical and condensed-matter simulations.

The Journal of chemical physics·2020
Same author

Effect of an external electric field on the dynamics and intramolecular structures of ions in an ionic liquid.

The Journal of chemical physics·2019
Same author

Thermodynamics and proton activities of protic ionic liquids with quantum cluster equilibrium theory.

The Journal of chemical physics·2018
Same author

Finding the best density functional approximation to describe interaction energies and structures of ionic liquids in molecular dynamics studies.

The Journal of chemical physics·2018
Same author

Predicting miscibility of binary liquids from small cluster QCE calculations.

The Journal of chemical physics·2017
Same journal

The influence of chirality on the macroscopic behavior of multiferroic smectic phases.

The Journal of chemical physics·2026
Same journal

Polaron transformed canonically consistent quantum master equation.

The Journal of chemical physics·2026
Same journal

The x-ray absorption spectrum of the propargyl radical C3H3●.

The Journal of chemical physics·2026
Same journal

Transient hydroperoxyalkyl intermediates (•QOOH) in isopentane oxidation. I. Conformer- and isomer-resolved infrared spectra.

The Journal of chemical physics·2026
Same journal

Transient hydroperoxyalkyl intermediates (•QOOH) in isopentane oxidation. II. Isomer-resolved unimolecular dynamics.

The Journal of chemical physics·2026
Same journal

Quantum state-to-state dynamics studies of the C(3P) + OH(X2Π) → CO(a3Π) + H(2S) reaction based on a new HCO(12A″) potential energy surface.

The Journal of chemical physics·2026
See all related articles

This study introduces anharmonicity into the quantum cluster equilibrium (QCE) model for liquids. Accounting for these vibrational effects improves the calculation of thermodynamic properties for liquid hydrogen chloride.

Area of Science:

  • Computational Chemistry
  • Physical Chemistry
  • Statistical Thermodynamics

Background:

  • The quantum cluster equilibrium (QCE) model uses ab initio calculations for finite clusters to model macroscopic liquid phases.
  • Previous QCE applications relied on the harmonic approximation for calculating partition functions.
  • Anharmonicity, a deviation from harmonic vibrations, is significant in molecular systems and can impact thermodynamic properties.

Purpose of the Study:

  • To incorporate anharmonic vibrational effects into the quantum cluster equilibrium (QCE) model.
  • To evaluate the impact of anharmonicity on the accuracy of calculated thermodynamic properties for liquid phases.
  • To implement an analytical approximation for the Morse partition function within the QCE framework.

Main Methods:

Related Experiment Videos

  • Implemented an analytical approximation for the Morse partition function to account for anharmonicity.
  • Calculated temperature derivatives of the logarithm of the Morse partition function.
  • Applied the anharmonic QCE approach to liquid hydrogen chloride (HCl) and its cluster distributions.

Main Results:

  • Calculated molar volume, volumetric thermal expansion coefficient, and isobaric heat capacity for liquid HCl.
  • Observed improved agreement between calculated and experimental properties when anharmonic effects were included.
  • Demonstrated the significance of anharmonicity for accurate thermodynamic predictions in liquid systems.

Conclusions:

  • The anharmonic quantum cluster equilibrium (QCE) approach provides a more accurate description of liquid properties compared to the harmonic approximation.
  • Accounting for vibrational anharmonicity is crucial for precise thermodynamic calculations of condensed phases.
  • The implemented analytical Morse partition function approximation is effective for incorporating anharmonicity into QCE models.