A systematic study of molecular vibrational anharmonicity and vibration-rotation interaction by self-consistent-field higher-derivative methods. Linear polyatomic molecules

Abstract

The inclusion of the anharmonicity of molecular vibrations is an important aspect of the goal of making highly accurate theoreticalpredictions of the spectroscopic properties of molecules. Recently developed analytic third derivative methods for selfconsistent-field(SCF) wavefunctions have made it possible to determine the complete cubic and quartic force fields of polyatomic molecules, thus allowing the treatment of anharmonic effects. Here we continue our systematic evaluation of the performance of such theoretical methods by studying several linear molecules which are well characterized experimentally, viz., HCN, DCN, CO2, N2O, OCS, C2H2, and C2D2. A number of anharmonic molecular properties have been determined, including vibration-rotation interaction constants, vibrational anharmonic constants, fundamental vibrational frequencies, sextic centrifugal distortion constants, rotational constants which include zero-point vibrational corrections, and vibrational and rotational l-type doubling constants. These anharmonic molecular constants are not as well converged with respect to basis set enlargement as those which were previously determined for asymmetric top molecules, apparently because all the molecules considered here contain multiple bonds. However, the reported anharmonic constants at the SCF level of theory are still in reasonably good agreement with the corresponding experimental constants. Significant improvements in accuracy are achieved by incorporating electron correlation at the configuration interaction singles and doubles (CISD) level of theory. Standard spectroscopic perturbationtheory methods are used in this study, which are directly and immediately applicable to larger molecular systems than those studied here.