Journal of Chemical Physics, Vol.121, No.15, 7187-7194, 2004
A theoretical study of the staggered and eclipsed forms of the dinuclear complex MnRe(CO)(10)
Two possible conformers of the dinuclear complex Mn Re(CO)(10), each of C-4v symmetry, with eclipsed and staggered conformations, have been analyzed theoretically. Using both the B3LYP and BP86 density functionals we find that the staggered form is lower in energy. A determination of the B3LYP potential energy surface as a function of the Mn-Re distance is presented for both conformers. The computed bond lengths, bond angles, and rotational constant for the staggered conformation compare favorably with the results from microwave experiments. The harmonic frequencies for the staggered structure have been determined using several basis sets, with both analytical and finite difference methods. These unscaled vibrational frequencies, together with their intensities for both infrared and Raman activity, are used to assign the three most intense experimental IR and Raman bands, and in particular, the nu(CO) region. The lowest A(2) vibration was calculated to occur at 41 cm-1 in the staggered conformer; this frequency becomes imaginary in the (saddle point) eclipsed form. Several fundamentals remain to be observed experimentally. (C) 2004 American Institute of Physics.