Infrared spectroscopy of V+(H2O) and V+(D2O) complexes: Solvent deformation and an incipient reaction

Walker, Nicholas R.; Walters, Richard; Pillai, E. D.; Duncan, M. A.

doi:10.1063/1.1625370

Cited by 71 publications

(95 citation statements)

References 41 publications

(22 reference statements)

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“…Such coupling has been observed previously for other M-H 2 O type of complexes. [25][26][27][28] The calculated barrier for the water rotation in the MnOH(H 2 O) + ÁD 2 complex is only B15 cm À1 , making it feasible to give rise to the progression observed here.…”

Section: Results and Analysismentioning

confidence: 92%

Charge transfer in MOH(H₂O)⁺ (M = Mn, Fe, Co, Ni, Cu, Zn) complexes revealed by vibrational spectroscopy of mass-selected ions

Marsh

Zhou

Garand

2015

Phys. Chem. Chem. Phys.

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Charge transfer between a metal and its ligand is fundamental for the structure and reactivity of a metal complex as it directly dictates the distribution of electron density within the complex. To better understand such charge transfer interactions, we studied the vibrational spectra of mass-selected MOH(H2O)(+) (M = Mn, Fe, Co, Ni, Cu, or Zn) complexes, acquired using cryogenic ion infrared predissociation spectroscopy. We find that there is a partial charge transfer from the hydroxide anion to the metal center for these first-row transition metals, the extent of which is in the order of Mn < Fe < Co < Ni < Cu > Zn, dictated by the 2nd ionization energy of the bare metal. This gradual change across the metal series points to the complexity in the electronic structures of these transition metal complexes. Interestingly, the hydroxide ligand in these complexes can serves as a sensitive in situ probe of this charge transfer. Its vibrational frequency varies by >150 cm(-1) for different metal species, and it is dependent on the electric field produced by the charged metal center. This dramatic vibrational Stark shift is further modulated by the charge present on the hydroxide itself, providing a well-defined relationship between the observed hydroxide frequency and the effective electric field.

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Section: Results and Analysismentioning

confidence: 92%

Charge transfer in MOH(H₂O)⁺ (M = Mn, Fe, Co, Ni, Cu, Zn) complexes revealed by vibrational spectroscopy of mass-selected ions

Marsh

Zhou

Garand

2015

Phys. Chem. Chem. Phys.

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“…Since weakly bound cluster systems can be fragmented with relatively few (or even single) photon absorption, commercially available benchtop laser systems can be used in IRMPD spectroscopic studies. Consequently, clusters that contain (or are intentionally tagged with), for example, solvent molecules or rare gas atoms are regularly studied with off-the-shelf optical parametric oscillator/amplifier or difference frequency-mixing laser systems [38]. Figure 2 shows a portion of the IRMPD spectrum that was recorded for the [Ag(I)•B 12 F 12 ] − cluster at the Centre Laser Infrarouge d'Orsay FEL facility [39,51].…”

Section: Infrared Multiple Photon Dissociation (Irmpd)mentioning

confidence: 99%

Determining the properties of gas-phase clusters

Hopkins

2015

Molecular Physics

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As our understanding of clusters has improved, we have found that rather than being models for surface and condensed phase phenomena, clusters often display chemical and physical properties that are quite distinct from those of their atomic constituents or associated bulk materials. Indeed, identifying and utilising the unique properties of dimensionally confined species is a major theme in nanotechnology. Consequently, numerous experimental and computational methods have been employed to investigate the structures and properties of cluster systems. In this article, the techniques of infrared multiple photon dissociation and differential mobility spectrometry are discussed using the examples of [Ag·B 12 F 12 ] − and tetraalkylammonium/solvent ionic clusters, respectively.

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“…These systems have been revisited in a guided-ion beam (GIB) measurement by Dalleska, Honma, Sunderlin, and Armentrout, who have obtained a binding energy of 9900 ± 500 cm −1 , making Mn + (H 2 O) the most weakly bound first-row transition metal water complex. 4 In fact, along the periodic 14 V, 15 Cr, 16 Mn, 17 Fe, 18 Ni, 19 Cu, 20 Zn 21 ) and M 2+ (H 2 O) (M = Sc, 14 V, 22 Cr, 16 Mn 17 ) in the O−H stretching region. Likewise, Nishi and co-workers measured vibrational spectra of M + (H 2 O) n for M = V, 23 Co, 24 Cu and Ag, 25 while Zhou and co-workers measured the vibrational spectra of Au + (H 2 O) n (n = 1-8).…”

Section: Introductionmentioning

confidence: 99%

Near ultraviolet photodissociation spectroscopy of Mn+(H2O) and Mn+(D2O)

Pearson

Copeland

Kocak

et al. 2014

The Journal of Chemical Physics

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excited states with T 0 = 30 210 and 32 274 cm −1 , respectively. Each electronic transition has partially resolved rotational and extensive vibrational structure with an extended progression in the metal−ligand stretch at a frequency of ∼450 cm −1 . There are also progressions in the in-plane bend in the 7 B 2 state, due to vibronic coupling, and the out-of-plane bend in the 7 B 1 state, where the calculation illustrates that this state is slightly non-planar. Electronic structure computations at the CCSD(T)/aug-cc-pVTZ and TD-DFT B3LYP/6-311++G(3df,3pd) level are also used to characterize the ground and excited states, respectively. These calculations predict a ground state Mn-O bond length of 2.18 Å. Analysis of the experimentally observed vibrational intensities reveals that this bond length decreases by 0.15 ± 0.015 Å and 0.14 ± 0.01 Å in the excited states. The behavior is accounted for by the less repulsive p x and p y orbitals causing the Mn + to interact more strongly with water in the excited states than the ground state. The result is a decrease in the Mn-O bond length, along with an increase in the H-O-H angle. The spectra have well resolved K rotational structure. Fitting this structure gives spin-rotation constants ε aa = −3 ± 1 cm −1 for the ground state and ε aa = 0.5 ± 0.5 cm −1 and aa = −4.2 ± 0.7 cm −1 for the first and second excited states, respectively, and A = 12.8 ± 0.7 cm −1 for the first excited state. Vibrationally mediated photodissociation studies determine the O-H antisymmetric stretching frequency in the ground electronic state to be 3658 cm −1 .

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Infrared spectroscopy of V+(H2O) and V+(D2O) complexes: Solvent deformation and an incipient reaction

Cited by 71 publications

References 41 publications

Charge transfer in MOH(H₂O)⁺ (M = Mn, Fe, Co, Ni, Cu, Zn) complexes revealed by vibrational spectroscopy of mass-selected ions

Charge transfer in MOH(H₂O)⁺ (M = Mn, Fe, Co, Ni, Cu, Zn) complexes revealed by vibrational spectroscopy of mass-selected ions

Determining the properties of gas-phase clusters

Near ultraviolet photodissociation spectroscopy of Mn+(H2O) and Mn+(D2O)

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Infrared spectroscopy of V+(H2O) and V+(D2O) complexes: Solvent deformation and an incipient reaction

Cited by 71 publications

References 41 publications

Charge transfer in MOH(H2O)+ (M = Mn, Fe, Co, Ni, Cu, Zn) complexes revealed by vibrational spectroscopy of mass-selected ions

Charge transfer in MOH(H2O)+ (M = Mn, Fe, Co, Ni, Cu, Zn) complexes revealed by vibrational spectroscopy of mass-selected ions

Determining the properties of gas-phase clusters

Near ultraviolet photodissociation spectroscopy of Mn+(H2O) and Mn+(D2O)

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Charge transfer in MOH(H₂O)⁺ (M = Mn, Fe, Co, Ni, Cu, Zn) complexes revealed by vibrational spectroscopy of mass-selected ions

Charge transfer in MOH(H₂O)⁺ (M = Mn, Fe, Co, Ni, Cu, Zn) complexes revealed by vibrational spectroscopy of mass-selected ions