A theoretical rotationally resolved infrared spectrum for H2O+ (X 2B1)

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Abstract
Three-dimensional potential energy and electric dipole moment functions for the electronic ground state of H2O+ have been calculated from highly correlated multiconfiguration reference configuration interaction (MRCI) electronic wave functions. The analytic representations of these functions have been used in vibrational and perturbational calculations of the rovibrational absorption spectrum of H2O+. The quartic force fields in normal coordinates have been employed in the evaluation of the equilibrium spectroscopic constants in H2O+, D2O+, and HDO+ by perturbation theory. The equilibrium structure, vibrational band origins, centrifugal distortion constants and rotational energy levels agree very well with the available experimental data. Absolute vibrational band intensities have been calculated from the dipole moment functions and are compared with theoretical integrated band intensities. The radiative lifetimes of excited vibrational states exhibit mode specific variations. The rotationally resolved room temperature absorption spectra have been evaluated ab initio for the pure rotational and the ν2, 2ν2, ν1, ν3, and 3ν2 transitions. The rovibrational electric dipole transition matrix elements and absolute line intensities are given for the most intense transitions. These data take full account of anharmonicity effects and vibration–rotation coupling.