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Electric properties of the water molecule in 1A1, 1B1, and 3B1 electronic states: Refined CASSCF and CASPT2 calculations

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The dipole moments and dipole polarizabilities of the 1A1, 1B1, and 3B1 electronic states of the water molecule have been calculated by using the CASSCF approach followed by the evaluation of the dynamic electron correlation contribution by the second-order perturbation scheme CASPT2. All calculations have been carried out in a specifically extended ANO basis set which accounts for the Rydberg character of the two excited states. In order to estimate the correctness and accuracy of the present data a scan over a variety of different active spaces for the CASSCF wave function has been made. The present results are superior to earlier CASSCF calculations, although their qualitative features remain essentially the same. The dipole moments in 1B1 and 3B1 states are predicted to be about 0.49 a.u. and 0.33 a.u., respectively, and have the opposite orientation with respect to the ground state dipole moment. The dipole polarizability tensors of the excited states are characterized by high anisotropy and are dominated by the in-plane component perpendicular to the symmetry axis. All their components are found to be about an order of magnitude larger than those of the ground state polarizability tensor. The excitation energy dependence on the choice of the active orbital space in the CASSCF reference function is also considered and the analysis of the present data concludes in the concept of what is called the mutually compatible active spaces for the two states involved in excitation. All CASPT2 results are in good agreement with the results of recent calculations carried out in the framework of the open-shell coupled cluster formalism. This agreement confirms the high efficiency of the CASSCF/CASPT2 approach to the treatment of the electron correlation effects.

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Klein, S., Kochanski, E., Strich, A. et al. Electric properties of the water molecule in 1A1, 1B1, and 3B1 electronic states: Refined CASSCF and CASPT2 calculations. Theoret. Chim. Acta 94, 75–91 (1996).

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Key words

  • Electric properties of excited states
  • Dipole moments
  • Dipole polarizabilities
  • Excitation energies
  • H2O
  • CASPT2