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Relativistic and correlation effects on molecular properties: The interhalogens ClF, BrF, BrCl, IF, ICl, and IBr

The effect of relativity on the properties of the interhalogens ClF, BrF, BrCl, IF, IBr, and IBr is studied by comparing relativistic and nonrelativistic calculations. Bond lengths, harmonic frequencies, and dissociation energies show that the bond is weakened in the relativistic formalism. Relativity increases the electric dipole moment whereas the electric quadrupole moment and dipole polarizability display an irregular behavior. The relativistic contributions to the electric dipole and quadrupole moment of the iodine containing molecules are 10%–20% of the total value, whereas the contributions in the other molecules cannot be neglected. The value of the electric quadrupole moment is dominated by the relativistic contributions.