Benchmark calculations on the adiabatic ionization potentials of M-NH3 (M= Na, Al, Ga, In, Cu, Ag)

摘要

The ground states of the M-NH3 (M= Na, Al, Ga, In, Cu, Ag) complexes and their cations have been studied with density functional theory and coupled cluster (CCSD) (T) ] methods. The adiabatic ionization potentials (AIPs) of these complexes are calculated, and these are compared to results from high-resolution zero-electron kinetic energy photoelectron spectroscopy. By extrapolating the CCSD (T) energies to the complete basis set (CBS) limit and including the core-valence, scalar relativistic, spin-orbit, and zero-point corrections, the CCSD (T) method is shown to be able to predict the AIPs of these complexes to better than 6 meV or 0.15 kcal/ mol. 27 exchange-correlation functionals, including one in the local density approximation, 13 in the generalized gradient approximation (GGA), and 13 with hybrid GGAs, were benchmarked in the calculations of the AIPs. The B1B95, mPW1PW91, B98, B97-1, PBE1PBE, O3LYP, TPSSh, and HCTH93 functionals give an average error of 0.1 eV for all the complexes studied, with the B98 functional alone yielding a maximum error of 0.1 eV. In addition, the calculated metal-ammonia harmonic stretching frequencies with the CCSD (T) method are in excellent agreement with their experimental values, whereas the B3LYP method tends to underestimate these stretching frequencies. The metal-ammonia binding energies were also calculated at the CCSD (T)/CBS level, and are in excellent agreement with the available experimental values considering the error limits, except for Ag-NH3 and Ag+-NH3, where the calculations predict stronger bond energies than measured by about 4 kcal/ mol, just outside the experimental error bars of +/- 3 kcal/ mol. (C) 2008 American Institute of Physics.