Simplified generalized-gradient approximation and anharmonicity: Benchmark calculations on molecules

Recent implementational improvements of the generalized-gradient approximation (GGA) have led to a simplified version which is parametrized entirely from fundamental constants, easier to use, and possibly easier to improve. We have performed detailed calculations on the geometries, atomization energies, vibrational energies, and infrared and Raman spectra of many first- and second-row dimers as well as some polyatomic molecules. For atomization and vibrational energies, we find that the simplified version of GGA leads to results similar to the original version. We comment on the fact that GGA-induced changes of hydrogenic bonding are different than for the other atoms in the periodic table but still an improvement over the local approximations to density-functional theory. In addition to a harmonic treatment of the vibrational modes we include the contributions of anharmonicity as well. With the exception of the light hydrogen containing molecules anharmonic corrections are quite small.