Prediction of spectroscopic constants for diatomic molecules in the ground and excited states using time-dependent density functional theory

Spectroscopic constants of the ground and next seven low‐lying excited states of diatomic molecules CO, N2, P2, and ScF were computed using the density functional theory SAOP/ATZP model, in conjunction with time‐dependent density functional theory (TD‐DFT) and a recently developed Slater type basis set, ATZP. Spectroscopic constants, including the equilibrium distances re, harmonic vibrational frequency ωe, vibrational anharmonicity ωexe, rotational constant Be, centrifugal distortion constant De, the vibration–rotation interaction constant αe, and the vibrational zero‐point energy E n0 were generated in an effort to establish a reliable database for electron spectroscopy. By comparison with experimental values and a similar model with an established larger Slater‐type basis set, et‐QZ3P‐xD, it was found that this model provides reliably accurate results at reduced computational costs, for both the ground and excited states of the molecules. The over all errors of all eight lowest lying electronic states of the molecules under study using the effective basis set are re(±4%), ωe(±5% mostly without exceeding ±20%), ωexe(±5% mostly without exceeding 20%, much more accurate than a previous study on this constant of ±30%), Be(±8%), De(±10%), αe(±10%), and E n0(±10%). The accuracy obtained using the ATZP basis set is very competitive to the larger et‐QZ3P‐xD basis set in particular in the ground electronic states. The overall errors in re, ωexe, and αe in the ground states were given by ±0.7, ±10.1, and ±8.4%, respectively, using the efficient ATZP basis set, which is competitive to the errors of ±0.5, ±9.2, and ±9.1%, respectively for those constants using the larger et‐QZ3P‐xD basis set. The latter basis set, however, needs approximately four times of the CPU time on the National Supercomputing Facilities (Australia). Due to the efficiency of the model (TD‐DFT, SAOP and ATZP), it will be readily applied to study larger molecular systems. © 2005 Wiley Periodicals, Inc. J Comput Chem 27: 163–173, 2006