An ab initio theory and density functional theory (DFT) study of conformers of tetrahydro-2H-pyran

Fillmore Freeman, Marc Kasner, Warren J. Hehre

Research output: Contribution to journalArticle

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Abstract

Ab initio theory with the 3-21G, 6-31G(d), 6-31G(d,p), 6-311G(d,p), 6-31+G(d), and 6-311+G(d,p) basis sets and density functional theory (SVWN, pBP, BLYP), including the hybrid density functional methods B3LYP, B3PW91, and B3P86, have been used to calculate the energies of the chair, half-chair, sofa, twist, and boat conformers of tetrahydro-2H-pyran (oxacyclohexane, oxane, pentamethylene oxide, tetrahydropyran, THP). The enthalpies (ΔH°), entropies (ΔS°), and free energies (ΔG°) of the conformers were also determined. The energy difference (°E, kcal/mol) between the chair and the 2,5-twist conformer is 5.92 to 6.10 (HF), 5.78 to 6.10 (MP2), 6.71 to 6.82 (SVWN), 6.04 to 6.12 (pBP), and 5.84 to 5.95 (BLYP, B3LYP, B3PW91, B3P86). The energy difference (°E, kcal/mol) between the chair and the 1,4-boat conformer is 6.72 to 7.05 (HF), 6.76 to 7.16 (MP2), 6.97 to 7.20 (SVWN), 6.26 to 6.36 (pBP), and 6.23 to 6.46 (BLYP, B3LYP, B3PW91, B3P86). The transition state between the chair conformation and the 2,5-twist conformation is 11 kcal/mol higher in energy than the chair conformer.

Original languageEnglish
Pages (from-to)10123-10132
Number of pages10
JournalJournal of Physical Chemistry A
Volume105
Issue number44
DOIs
StatePublished - 8 Nov 2001

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Pyrans
Boats
seats
Density functional theory
Conformations
density functional theory
Oxides
Free energy
Enthalpy
Entropy
boats
energy
enthalpy
free energy
entropy
oxides

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title = "An ab initio theory and density functional theory (DFT) study of conformers of tetrahydro-2H-pyran",
abstract = "Ab initio theory with the 3-21G, 6-31G(d), 6-31G(d,p), 6-311G(d,p), 6-31+G(d), and 6-311+G(d,p) basis sets and density functional theory (SVWN, pBP, BLYP), including the hybrid density functional methods B3LYP, B3PW91, and B3P86, have been used to calculate the energies of the chair, half-chair, sofa, twist, and boat conformers of tetrahydro-2H-pyran (oxacyclohexane, oxane, pentamethylene oxide, tetrahydropyran, THP). The enthalpies (ΔH°), entropies (ΔS°), and free energies (ΔG°) of the conformers were also determined. The energy difference (°E, kcal/mol) between the chair and the 2,5-twist conformer is 5.92 to 6.10 (HF), 5.78 to 6.10 (MP2), 6.71 to 6.82 (SVWN), 6.04 to 6.12 (pBP), and 5.84 to 5.95 (BLYP, B3LYP, B3PW91, B3P86). The energy difference (°E, kcal/mol) between the chair and the 1,4-boat conformer is 6.72 to 7.05 (HF), 6.76 to 7.16 (MP2), 6.97 to 7.20 (SVWN), 6.26 to 6.36 (pBP), and 6.23 to 6.46 (BLYP, B3LYP, B3PW91, B3P86). The transition state between the chair conformation and the 2,5-twist conformation is 11 kcal/mol higher in energy than the chair conformer.",
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An ab initio theory and density functional theory (DFT) study of conformers of tetrahydro-2H-pyran. / Freeman, Fillmore; Kasner, Marc; Hehre, Warren J.

In: Journal of Physical Chemistry A, Vol. 105, No. 44, 08.11.2001, p. 10123-10132.

Research output: Contribution to journalArticle

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AB - Ab initio theory with the 3-21G, 6-31G(d), 6-31G(d,p), 6-311G(d,p), 6-31+G(d), and 6-311+G(d,p) basis sets and density functional theory (SVWN, pBP, BLYP), including the hybrid density functional methods B3LYP, B3PW91, and B3P86, have been used to calculate the energies of the chair, half-chair, sofa, twist, and boat conformers of tetrahydro-2H-pyran (oxacyclohexane, oxane, pentamethylene oxide, tetrahydropyran, THP). The enthalpies (ΔH°), entropies (ΔS°), and free energies (ΔG°) of the conformers were also determined. The energy difference (°E, kcal/mol) between the chair and the 2,5-twist conformer is 5.92 to 6.10 (HF), 5.78 to 6.10 (MP2), 6.71 to 6.82 (SVWN), 6.04 to 6.12 (pBP), and 5.84 to 5.95 (BLYP, B3LYP, B3PW91, B3P86). The energy difference (°E, kcal/mol) between the chair and the 1,4-boat conformer is 6.72 to 7.05 (HF), 6.76 to 7.16 (MP2), 6.97 to 7.20 (SVWN), 6.26 to 6.36 (pBP), and 6.23 to 6.46 (BLYP, B3LYP, B3PW91, B3P86). The transition state between the chair conformation and the 2,5-twist conformation is 11 kcal/mol higher in energy than the chair conformer.

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