The electronic spectra of Co(+)(H(2)O), Co(+)(HOD), and Co(+)(D(2)O) have been measured from 13,500 to 18,400 cm(-1) using photodissociation spectroscopy. Transitions to four excited electronic states with vibrational and partially resolved rotational structure are observed. Each electronic transition has an extended progression in the metal-ligand stretch, v(3), and the absolute vibrational quantum numbering is assigned by comparing isotopic shifts between Co(+)(H(2)(16)O) and Co(+)(H(2)(18)O). For the low-lying excited electronic states, the first observed transition is to v(3)' = 1. This allows the Co(+)-(H(2)O) binding energy to be determined as D(0)(0 K)(Co(+)-H(2)O) = 13730 ± 90 cm(-1) (164.2 ± 1.1 kJ/mol). The photodissociation spectrum shows a well-resolved K(a) band structure due to rotation about the Co-O axis. This permits determination of the spin rotation constants ε(aa)" = -6 cm(-1) and ε(aa)' = 4 cm(-1). However, the K(a) rotational structure depends on v(3)'. These perturbations in the spectrum make the rotational constants unreliable. From the nuclear spin statistics of the rotational structure, the ground state is assigned as (3)B(1). The electronic transitions observed are from the Co(+)(H(2)O) ground state, which correlates to the cobalt ion's (3)F, 3d(8) ground state, to excited states which correlate to the (3)F, 3d(7)4s and (3)P, 3d(8) excited states of Co(+). These excited states of Co(+) interact less strongly with water than the ground state. As a result, the excited states are less tightly bound and have longer metal-ligand bonds. Calculations at the CCSD(T)/aug-cc-pVTZ level also predict that binding to Co(+) increases the H-O-H angle in water from 104.1° to 106.8°, as the metal removes electron density from the oxygen lone pairs. The O-H stretching frequencies of the ground electronic state of Co(+)(H(2)O) and Co(+)(HOD) have been measured by combining IR excitation with visible photodissociation in a double resonance experiment. In Co(+)(H(2)O) the O-H symmetric stretch is ν(1)" = 3609.7 ± 1 cm(-1). The antisymmetric stretch is ν(5)" = 3679.5 ± 2 cm(-1). These values are 47 and 76 cm(-1), respectively, lower than those in bare H(2)O. In Co(+)(HOD) the O-H stretch is observed at 3650 cm(-1), a red shift of 57 cm(-1) relative to bare HOD.

Vibrational spectra are measured for Fe(+)(CH(4))(n) (n = 1-4) in the C-H stretching region (2500-3200 cm(-1)) using photofragment spectroscopy. Spectra are obtained by monitoring CH(4) fragment loss following absorption of one photon (for n = 3, 4) or sequential absorption of multiple photons (for n = 1, 2). The spectra have a band near the position of the antisymmetric C-H stretch in isolated methane (3019 cm(-1)), along with bands extending >250 cm(-1) to the red of the symmetric C-H stretch in methane (2917 cm(-1)). The spectra are sensitive to the ligand configuration (η(2) vs η(3)) and to the Fe-C distance. Hybrid density functional theory calculations are used to identify possible structures and predict their vibrational spectra. The IR photodissociation spectrum shows that the Fe(+)(CH(4)) complex is a quartet, with an η(3) configuration. There is also a small contribution to the spectrum from the metastable sextet η(3) complex. The Fe(+)(CH(4))(2) complex is also a quartet with both CH(4) in an η(3) configuration. For the larger clusters, the configuration switches from η(3) to η(2). In Fe(+)(CH(4))(3), the methane ligands are not equivalent. Rather, there is one short and two long Fe-C bonds, and each methane is bound to the metal in an η(2) configuration. For Fe(+)(CH(4))(4), the calculations predict three low-lying structures, all with η(2) binding of methane and very similar Fe-C bond lengths. No single structure reproduces the observed spectrum. The approximately tetrahedral C(1) ((4)A) structure contributes to the spectrum; the nearly square-planar D(2d) ((4)B(2)) and the approximately tetrahedral C(2) ((4)A) structure may contribute as well.