Calibration sets and the accuracy of vibrational scaling factors: a case study with the X3LYP hybrid functional.
A linear least-squares methodology was used to determine the vibrational scaling factors for the X3LYP density functional. Uncertainties for these scaling factors were calculated according to the method devised by Irikura et al. [J. Phys. Chem. A 109, 8430 (2005)]. The calibration set was systematically partitioned according to several of its descriptors and the scaling factors for X3LYP were recalculated for each subset. The results show that the scaling factors are only significant up to the second digit, irrespective of the calibration set used. Furthermore, multivariate statistical analysis allowed us to conclude that the scaling factors and the associated uncertainties are independent of the size of the calibration set and strongly suggest the practical impossibility of obtaining vibrational scaling factors with more than two significant digits.
Teixeira
Filipe
F
Departamento de Química e Bioquímica, REQUIMTE, Faculdade de Ciências, Universidade do Porto, Rua do Campo Alegre, 687, 4169-007 Porto, Portugal.
Melo
André
A
Cordeiro
M Natália D S
MN