TY - JOUR
T1 - Frequency and zero-point vibrational energy scale factors for double-hybrid density functionals (and other selected methods)
T2 - Can anharmonic force fields be avoided?
AU - Kesharwani, Manoj K.
AU - Brauer, Brina
AU - Martin, Jan M. L.
N1 - Lise Meitner-Minerva Center for Computational Quantum Chemistry; Helen and Martin Kimmel Center for Molecular DesignThe authors would like to thank Profs. Martin Suhm (U. of Gottingen, Germany) and Amir Karton (U. of Western Australia, Perth) for helpful discussions. This research was supported in part by the Lise Meitner-Minerva Center for Computational Quantum Chemistry and by the Helen and Martin Kimmel Center for Molecular Design.
PY - 2015/3/5
Y1 - 2015/3/5
N2 - We have obtained uniform frequency scaling factors λharm (for harmonic frequencies), λfund (for fundamentals), and λZPVE (for zero-point vibrational energies (ZPVEs)) for the Weigend-Ahlrichs and other selected basis sets for MP2, SCS-MP2, and a variety of DFT functionals including double hybrids. For selected levels of theory, we have also obtained scaling factors for true anharmonic fundamentals and ZPVEs obtained from quartic force fields. For harmonic frequencies, the double hybrids B2PLYP, B2GP-PLYP, and DSD-PBEP86 clearly yield the best performance at RMSD = 10-12 cm-1 for def2-TZVP and larger basis sets, compared to 5 cm-1 at the CCSD(T) basis set limit. For ZPVEs, again, the double hybrids are the best performers, reaching root-mean-square deviations (RMSDs) as low as 0.05 kcal/mol, but even mainstream functionals like B3LYP can get down to 0.10 kcal/mol. Explicitly anharmonic ZPVEs only are marginally more accurate. For fundamentals, however, simple uniform scaling is clearly inadequate.
AB - We have obtained uniform frequency scaling factors λharm (for harmonic frequencies), λfund (for fundamentals), and λZPVE (for zero-point vibrational energies (ZPVEs)) for the Weigend-Ahlrichs and other selected basis sets for MP2, SCS-MP2, and a variety of DFT functionals including double hybrids. For selected levels of theory, we have also obtained scaling factors for true anharmonic fundamentals and ZPVEs obtained from quartic force fields. For harmonic frequencies, the double hybrids B2PLYP, B2GP-PLYP, and DSD-PBEP86 clearly yield the best performance at RMSD = 10-12 cm-1 for def2-TZVP and larger basis sets, compared to 5 cm-1 at the CCSD(T) basis set limit. For ZPVEs, again, the double hybrids are the best performers, reaching root-mean-square deviations (RMSDs) as low as 0.05 kcal/mol, but even mainstream functionals like B3LYP can get down to 0.10 kcal/mol. Explicitly anharmonic ZPVEs only are marginally more accurate. For fundamentals, however, simple uniform scaling is clearly inadequate.
UR - http://www.scopus.com/inward/record.url?scp=84924311195&partnerID=8YFLogxK
U2 - 10.1021/jp508422u
DO - 10.1021/jp508422u
M3 - مقالة
SN - 1089-5639
VL - 119
SP - 1701
EP - 1714
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 9
ER -