Theoretical studies of CO2(H2O)20,24,28 clusters: Stabilization of cages in hydrates by CO2 guest molecules

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Abstract

Theoretical studies on dodecahedral (20-mer), tetrakaidecahedral (24-mer) and hexakaidecahedral (28-mer) water clusters containing CO2 guest molecules are carried out by optimizing geometry at the Hartree-Fock (HF) level with 6-31G* basis set followed by single point energy calculations with 6-311++G** basis set and applying the Becke-3-parameter density functional theory (DFT) and Lee-Yang-Parr correlation functional (B3LYP). While the filled tetrakaidecahedral and hexakaidecahedral cage clusters are stabilized by 7.79 and 3.42 kcal/mol, respectively (relative to unfilled cage and separated CO2 molecule, SEC), the filled dodecahedral cage shows no such stabilization. The largest SEC value for tetrakaidecahedral cluster, resulting from two H-bonds between the guest and the host, explains the dominance of CO2-filled tetrakaidecahedral structures in hydrates.

Original languageEnglish (US)
Pages (from-to)237-245
Number of pages9
JournalJournal of Molecular Structure: THEOCHEM
Volume664-665
DOIs
StatePublished - Dec 15 2003

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Hydrates
hydrates
Theoretical Models
Stabilization
stabilization
Molecules
Water
Density functional theory
molecules
Geometry
density functional theory
geometry
water
energy

All Science Journal Classification (ASJC) codes

  • Biochemistry
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Cite this

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title = "Theoretical studies of CO2(H2O)20,24,28 clusters: Stabilization of cages in hydrates by CO2 guest molecules",
abstract = "Theoretical studies on dodecahedral (20-mer), tetrakaidecahedral (24-mer) and hexakaidecahedral (28-mer) water clusters containing CO2 guest molecules are carried out by optimizing geometry at the Hartree-Fock (HF) level with 6-31G* basis set followed by single point energy calculations with 6-311++G** basis set and applying the Becke-3-parameter density functional theory (DFT) and Lee-Yang-Parr correlation functional (B3LYP). While the filled tetrakaidecahedral and hexakaidecahedral cage clusters are stabilized by 7.79 and 3.42 kcal/mol, respectively (relative to unfilled cage and separated CO2 molecule, SEC), the filled dodecahedral cage shows no such stabilization. The largest SEC value for tetrakaidecahedral cluster, resulting from two H-bonds between the guest and the host, explains the dominance of CO2-filled tetrakaidecahedral structures in hydrates.",
author = "Arshad Khan",
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AU - Khan, Arshad

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N2 - Theoretical studies on dodecahedral (20-mer), tetrakaidecahedral (24-mer) and hexakaidecahedral (28-mer) water clusters containing CO2 guest molecules are carried out by optimizing geometry at the Hartree-Fock (HF) level with 6-31G* basis set followed by single point energy calculations with 6-311++G** basis set and applying the Becke-3-parameter density functional theory (DFT) and Lee-Yang-Parr correlation functional (B3LYP). While the filled tetrakaidecahedral and hexakaidecahedral cage clusters are stabilized by 7.79 and 3.42 kcal/mol, respectively (relative to unfilled cage and separated CO2 molecule, SEC), the filled dodecahedral cage shows no such stabilization. The largest SEC value for tetrakaidecahedral cluster, resulting from two H-bonds between the guest and the host, explains the dominance of CO2-filled tetrakaidecahedral structures in hydrates.

AB - Theoretical studies on dodecahedral (20-mer), tetrakaidecahedral (24-mer) and hexakaidecahedral (28-mer) water clusters containing CO2 guest molecules are carried out by optimizing geometry at the Hartree-Fock (HF) level with 6-31G* basis set followed by single point energy calculations with 6-311++G** basis set and applying the Becke-3-parameter density functional theory (DFT) and Lee-Yang-Parr correlation functional (B3LYP). While the filled tetrakaidecahedral and hexakaidecahedral cage clusters are stabilized by 7.79 and 3.42 kcal/mol, respectively (relative to unfilled cage and separated CO2 molecule, SEC), the filled dodecahedral cage shows no such stabilization. The largest SEC value for tetrakaidecahedral cluster, resulting from two H-bonds between the guest and the host, explains the dominance of CO2-filled tetrakaidecahedral structures in hydrates.

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