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Title: Understanding the anharmonic vibrational structure of the carbon dioxide dimer

Abstract

Understanding the vibrational structure of the CO 2 system is important to confirm the potential energy surface and interactions in such van der Waals complexes. In this work, we use our previously developed mbCO2 potential function to explore the vibrational structure of the CO 2 monomer and dimer. The potential function has been trained to reproduce the potential energies at the CCSD(T)-F12b/aug-cc-pVTZ level of electronic structure theory. The harmonic approximation, as well as anharmonic corrections using vibrational structure theories such as vibrational self-consistent field, vibrational second-order Moller-Plesset perturbation, and vibrational configuration interaction (VCI), is applied to address the vibrational motions. We compare the vibrational results using the mbCO2 potential function with traditional electronic structure theory results and to experimental frequencies. The anharmonic results for the monomer most closely match the experimental data to within 3 cm -1, including the Fermi dyad frequencies. The intermolecular and intramolecular dimer frequencies were treated separately and show good agreement with the most recent theoretical and experimental results from the literature. The VCI treatment of the dimer vibrational motions accounts for vibrational mixing and delocalization, such that we observe the dimer Fermi resonance phenomena, both in the intramolecular and intermolecular regions.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3]
  1. Univ. of Tampa, FL (United States)
  2. Argonne National Lab. (ANL), Argonne, IL (United States)
  3. Univ. of Tampa, FL (United States); California State Univ. (CalState), Los Angeles, CA (United States)
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
National Science Foundation (NSF); USDOE
OSTI Identifier:
1518476
Alternate Identifier(s):
OSTI ID: 1505673
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 14; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Maystrovsky, Samuel, Keçeli, Murat, and Sode, Olaseni. Understanding the anharmonic vibrational structure of the carbon dioxide dimer. United States: N. p., 2019. Web. doi:10.1063/1.5089460.
Maystrovsky, Samuel, Keçeli, Murat, & Sode, Olaseni. Understanding the anharmonic vibrational structure of the carbon dioxide dimer. United States. doi:10.1063/1.5089460.
Maystrovsky, Samuel, Keçeli, Murat, and Sode, Olaseni. Mon . "Understanding the anharmonic vibrational structure of the carbon dioxide dimer". United States. doi:10.1063/1.5089460.
@article{osti_1518476,
title = {Understanding the anharmonic vibrational structure of the carbon dioxide dimer},
author = {Maystrovsky, Samuel and Keçeli, Murat and Sode, Olaseni},
abstractNote = {Understanding the vibrational structure of the CO2 system is important to confirm the potential energy surface and interactions in such van der Waals complexes. In this work, we use our previously developed mbCO2 potential function to explore the vibrational structure of the CO2 monomer and dimer. The potential function has been trained to reproduce the potential energies at the CCSD(T)-F12b/aug-cc-pVTZ level of electronic structure theory. The harmonic approximation, as well as anharmonic corrections using vibrational structure theories such as vibrational self-consistent field, vibrational second-order Moller-Plesset perturbation, and vibrational configuration interaction (VCI), is applied to address the vibrational motions. We compare the vibrational results using the mbCO2 potential function with traditional electronic structure theory results and to experimental frequencies. The anharmonic results for the monomer most closely match the experimental data to within 3 cm-1, including the Fermi dyad frequencies. The intermolecular and intramolecular dimer frequencies were treated separately and show good agreement with the most recent theoretical and experimental results from the literature. The VCI treatment of the dimer vibrational motions accounts for vibrational mixing and delocalization, such that we observe the dimer Fermi resonance phenomena, both in the intramolecular and intermolecular regions.},
doi = {10.1063/1.5089460},
journal = {Journal of Chemical Physics},
number = 14,
volume = 150,
place = {United States},
year = {2019},
month = {4}
}

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