B. J. Knurr

Solvent-Driven Reductive Activation of Carbon Dioxide by Gold Anions

Catalytic activation and electrochemical reduction of CO(2) for the formation of chemically usable feedstock and fuel are central goals for establishing a carbon neutral fuel cycle. The role of solvent molecules in catalytic processes is little understood, although solvent-solute interactions can strongly influence activated intermediate species. We use vibrational spectroscopy of mass-selected Au(CO(2))(n)(-) cluster ions to probe the solvation of AuCO(2)(-) as a model for a reactive intermediate in the reductive activation of a CO(2) ligand by a single-atom catalyst. For the first few solvent molecules, solvation of the complex preferentially occurs at the CO(2) moiety, enhancing reductive activation through polarization of the excess charge onto the partially reduced ligand. At higher levels of solvation, direct interaction of additional solvent molecules with the Au atom diminishes reduction. The results show how the solvation environment can enhance or diminish the effects of a catalyst, offering design criteria for single-atom catalyst engineering.

Solvent-Mediated Reduction of Carbon Dioxide in Anionic Complexes with Silver Atoms

The development of efficient routes toward sustainable fuel sources by electrochemical reduction of CO2 is an important goal for catalysis research. While these processes usually occur in the presence of solvent, solvation effects in catalysis are largely not understood or even characterized. In this work, mass-selected clusters of silver anions with CO2 serve as a model system for reductive activation of CO2 by a catalyst in the presence of a well-controlled number of solvent molecules. Vibrational spectroscopy and electronic structure calculations are used to obtain molecular-level information on the interaction of solvent with the catalyst-CO2 complex and the effects of solvation on one-electron reductive activation of CO2. Charge transfer from the silver catalyst to CO2 increases with increasing cluster size. We observe the coexistence of catalyst-ligand complexes with CO2 monomer and dimer anions, indicating that CO2-based charge carriers can exist in the presence of a silver atom.

Infrared Spectra and Structures of Anionic Complexes of Cobalt with Carbon Dioxide Ligands

We present infrared photodissociation spectra of [Co(CO2)n](-) ions (n = 3-11) in the wavenumber region 1000-2400 cm(-1), interpreted with the aid of density functional theory calculations. The spectra are dominated by the signatures of a core ion showing bidentate interaction of two CO2 ligands with the Co atom, each forming C-Co and O-Co bonds. This structural motif is very robust and is only weakly affected by solvation with additional CO2 solvent molecules. The Co atom is in oxidation state +1, and both CO2 ligands carry a negative charge.

Interaction of Nickel with Carbon Dioxide in [Ni(CO2)n]− Clusters Studied by Infrared Spectroscopy

We present infrared photodissociation spectra of [Ni(CO2)n](-) clusters (n = 2-8) in the wavenumber region of 1000-2400 cm(-1) using the antisymmetric stretching vibrational modes of the CO2 units in the clusters as structural probes. We use density functional theory to aid in the interpretation of our experimental results. The dominant spectral signatures arise from a core ion composed of a nickel atom and two CO2 ligands bound to the Ni atom in a bidentate fashion, while the rest of the CO2 molecules in the cluster play the role of solvent. Other core structures are observed as well but as minor contributors. The results for [Ni(CO2)n](-) clusters are discussed in the context of other anionic transition- metal complexes with CO2.

Structural Diversity of Copper–CO2 Complexes: Infrared Spectra and Structures of [Cu(CO2)n]− Clusters

We  present infrared spectra of  [Cu(CO2)n](-) (n = 2-9) clusters in the wavenumber range 1600-2400 cm(-1). The CO stretching modes in this region encode the structural nature of the cluster core and are interpreted with the aid of density functional theory. We find a variety of core species in [Cu(CO2)n](-) clusters, but the dominant core structure is a [Cu(CO2)2](-) core where the two CO2 ligands are bound to the Cu atom in a bidentate fashion. We compare the results of [Cu(CO2)n](-) clusters to those of other [M(CO2)n](-) clusters (M = Au, Ag, Co, Ni) to establish trends of how the metal-CO2 interaction depends on the metal partner.

Electronic spectrum of AuF: Hyperfine structure of the [17.7]1 state

The [17.7]1-X(1)Sigma(+) (0,0) band of AuF at 566 nm has been studied by laser excitation spectroscopy. The molecule was prepared in a dc electric discharge by flowing a dilute mixture of SF(6) in argon through a hollow gold cathode. The rotational structure of the band has been analyzed for the first time, yielding accurate values for the rotational and Omega-type doubling constants of the upper state. Hyperfine splittings arising from both the (197)Au and (19)F nuclei have been resolved by recording the spectrum at sub-Doppler resolution using the technique of intermodulated fluorescence spectroscopy. The hyperfine structure is dominated by the (197)Au magnetic dipole interaction in the [17.7]1 state, with the (197)Au magnetic hyperfine constant determined to be h(1) = -543(4) MHz. It is demonstrated that the negative value of this constant implies that the [17.7]1 state has significant (3)Delta(1) character and that spin-orbit mixing with a (1)Pi(1) state may be providing the transition intensity to the ground electronic state.

Structures of [CoO(CO2)n]− and [NiO(CO2)n]− Clusters Studied by Infrared Spectroscopy

We present infrared spectra of [CoO(CO2)n](-) and [NiO(CO2)n](-) clusters and interpret them in the framework of computational results employing density functional theory. We find that both [CoO(CO2)n](-) and [NiO(CO2)n](-) clusters are generally composed of the same core isomers. The dominant isomers consist of an η(2) CO2 ligand and a CO3 moiety that can be bound to the metal atom with monodentate (η(1)) or bidentate (η(2)) connectivity. Minor structural isomers observed are composed of a C2O4 moiety with a lone oxygen atom or a CO3 unit.

Excited Electronic States of AuF

We have recorded laser excitation spectra of transitions from the ground X(1)Sigma(+) state of gaseous gold fluoride (AuF) into three excited electronic states in the visible region. We prepared the sample in a dc electric discharge by flowing a dilute mixture of SF(6) in argon through a hollow gold cathode. Two of these electronic states give rise to the previously reported yellow bands of the molecule, for which a rotational analysis is given here for the first time. We have analyzed the (0,0), (1,1), (0,1), and (1,2) bands of these two transitions, which we identify as [17.8]0(+)-X(1)Sigma(+) and [17.7]1-X(1)Sigma(+); their red-degraded (0,0) band heads lie at 563.0 and 566.2 nm, respectively. The (0,0) band of a new, red-degraded [14.0]1-X(1)Sigma(+) transition at 715.1 nm has also been recorded and analyzed. An accurate set of molecular constants of the three excited states as well as the ground state has been determined by least-squares fitting all of the optical data together with measurements made by other workers of the pure rotational spectrum of AuF in its ground state. These constants include the electronic term energies, vibrational frequencies, rotational constants, and Omega-doubling constants. We discuss the nature of these three excited electronic states in terms of the ionic Au(+)F(-) electronic configurations from which they are derived.

Infrared spectroscopy of hydrated naphthalene cluster anions

We present infrared spectra of mass-selected C(10)H(8)(-)·(H(2)O)(n)·Ar(m) cluster anions (n = 1-6) obtained by Ar predissociation spectroscopy. The experimental spectra are compared with predicted spectra from density functional theory calculations. The OH groups of the water ligands are involved in H-bonds to other water molecules or to the π system of the naphthalene anion, which accommodates the excess electron. The interactions in the water network are generally found to be more important than those between water molecules and the ion. For 2 ≤ n ≤ 4 the water molecules form single layer water networks on one side of the naphthalene anion, while for n = 5 and 6, cage and multilayer structures become more energetically favorable. For cluster sizes with more than 3 water molecules, multiple conformers are likely to be responsible for the experimental spectra.

Vibrationally induced charge transfer in a bimolecular model complex in vacuo

We report vibrationally induced charge transfer from nitromethane anion to methyliodide in a molecular complex. Excitation of a CH stretching vibrational transition in either of the molecular constituents results in dissociative electron transfer to the CH3I molecule, resulting in I(-) product anions. Solvation of the pre-reactive complex with more than two Ar atoms leads to complete quenching of the reaction and can be used to estimate the barrier for this reaction. We discuss the results in the framework of electronic structure calculations and compare the intra-complex electron transfer with vibrationally mediated electron emission in bare nitromethane anion.