TY - JOUR
T1 - Conformational equilibria in butane-1,4-diol
T2 - A benchmark of a prototypical system with strong intramolecular H-bonds
AU - Kozuch, Sebastian
AU - Bachrach, Steven M.
AU - Martin, Jan M.L.
N1 - Lise Meitner-Minerva Center for Computational Quantum Chemistry; Helen and Martin Kimmel Center for Molecular Design; Trinity University; Weston T. BordenJ.M.L.M. is the Baroness Thatcher Professor of Chemistry at the Weizmann Institute of Science and acknowledges partial financial support from the Lise Meitner-Minerva Center for Computational Quantum Chemistry and the Helen and Martin Kimmel Center for Molecular Design. S.R.B. is the D. R. Semmes Distinguished Professor of Chemistry and acknowledges financial support from Trinity University. S.K. acknowledges the support of Weston T. Borden.
PY - 2014/1/9
Y1 - 2014/1/9
N2 - Explicitly correlated CCSD(T) valence basis limit relative energies were obtained for the 65 conformers of butane-1,4-diol, a prototypical system with a strong internal hydrogen bond. The performance of a variety of ab initio and DFT methods (with and without empirical dispersion corrections) was assessed in detail. Consideration of all pairwise conformer energies provides a performance gauge for both H-bonds and van der Waals interactions, aside from internal strain of angles and bonds. In the post-HF realm, it was found that SCS(MI)CCSD-F12/cc-pVDZ-F12 can be a cost-effective alternative to CCSD(T)/CBS, almost without any loss in accuracy. In the DFT arena, the double-hybrid DSD-PBEP86-D3BJ surpasses the accuracy of all other methods (except for SCS(MI)CCSD, but at a small fraction of its cost). Several hybrid functionals provide an acceptable accuracy with the def2-QZVP basis set, especially BMK, M06, LC-ωPBE-D3, and TPSS0-D3. With the more modest 6-311+G(d,p) basis set, the H-bonds are far from basis set completeness and, due to error compensation, the inclusion of a dispersion correction is generally counterproductive. Some functionals that represent "Pauling points" at this level are LC-ωPBE, TPSS0, B1B95, BMK, TPSSh, PBE0, TPSS, and ωB97X.
AB - Explicitly correlated CCSD(T) valence basis limit relative energies were obtained for the 65 conformers of butane-1,4-diol, a prototypical system with a strong internal hydrogen bond. The performance of a variety of ab initio and DFT methods (with and without empirical dispersion corrections) was assessed in detail. Consideration of all pairwise conformer energies provides a performance gauge for both H-bonds and van der Waals interactions, aside from internal strain of angles and bonds. In the post-HF realm, it was found that SCS(MI)CCSD-F12/cc-pVDZ-F12 can be a cost-effective alternative to CCSD(T)/CBS, almost without any loss in accuracy. In the DFT arena, the double-hybrid DSD-PBEP86-D3BJ surpasses the accuracy of all other methods (except for SCS(MI)CCSD, but at a small fraction of its cost). Several hybrid functionals provide an acceptable accuracy with the def2-QZVP basis set, especially BMK, M06, LC-ωPBE-D3, and TPSS0-D3. With the more modest 6-311+G(d,p) basis set, the H-bonds are far from basis set completeness and, due to error compensation, the inclusion of a dispersion correction is generally counterproductive. Some functionals that represent "Pauling points" at this level are LC-ωPBE, TPSS0, B1B95, BMK, TPSSh, PBE0, TPSS, and ωB97X.
UR - http://www.scopus.com/inward/record.url?scp=84892599810&partnerID=8YFLogxK
U2 - https://doi.org/10.1021/jp410723v
DO - https://doi.org/10.1021/jp410723v
M3 - Article
C2 - 24328111
SN - 1089-5639
VL - 118
SP - 293
EP - 303
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 1
ER -