Calculated spectroscopic and electric properties of the alkali metal-ammonia complexes from K-n-NH3 to Fr-n-NH3 (n=0,+1)

摘要

The newly developed Stuttgart small-core scalar relativistic pseudopotentials for the alkali metals are used to study spectroscopic and electric properties of the heavier alkali metal-ammonia complexes from K-n-NH3 to Fr-n-NH3 (n=0,+1) at the second-order Moller-Plesset (MP2) and coupled cluster [CCSD(T)] levels of theory. Equilibrium geometries and dissociation energies computed at the MP2 level are in reasonable agreement with their CCSD(T) counterparts, whereas for the dipole polarizabilities MP2 is not performing well overestimating significantly electron correlation effects. The bond distances increase monotonically with increasing mass of the metal atom as relativistic effects are small in these systems. However, the dipole polarizabilities are more sensitive to such effects and we find a decrease in this property from Cs-NH3 to Fr-NH3. Combination of CCSD(T) harmonic frequencies and MP2 anharmonic corrections obtained from a perturbative vibrational treatment leads to fundamental frequencies in good agreement with experimental results obtained by Suzer and Andrews [J. Am. Chem. Soc. 109, 300 (1986)]. We also present the results of variational calculations with a three-dimensional vibrational Hamiltonian, making use of CCSD(T) potential energy and electric dipole moment surfaces. Complexation of NH3 to the metal causes a strong infrared intensification of the symmetric NH3 stretching mode in the neutral complexes, which is absent in the charged species.