Infrared Spectroscopy of Cr+(H2O) and Cr2+(H2O): The Role of Charge in Cation Hydration

Carnegie, P. D.; Bandyopadhyay, Biswajit; Duncan, M. A.

doi:10.1021/jp803086v

Cited by 60 publications

(126 citation statements)

References 142 publications

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“…As shown in Figure 6, the spectrum computed for the O h singlet configuration matches the position of the single main band perfectly, confirming that this is the structure and ground state for this complex. This is consistent with previous work, in which the Mn(CO) 6 ϩ ground state was determined to be a singlet by various methods [53,56,57]. The weak features in the Mn(CO) 6 ϩ spectrum in Figure 6 were found to increase in intensity when the laser plasma was hotter, and these bands could be eliminated entirely under our coldest conditions.…”

supporting

confidence: 92%

“…This trend is somewhat surprising, because vibrational motion next to a charge often enhances the IR oscillator strength. For example, we have recently found much stronger O-H stretches in cation-water complexes than in the free water molecule, and the doubly charged complexes were found to have much stronger transitions than those of the singly charged complexes [56]. Apparently, the trend for carbonyl ligands is reversed, at least in these two examples.…”

mentioning

confidence: 91%

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Infrared spectroscopy and structures of manganese carbonyl cations, Mn(CO)_n⁺ (n = 1−9)

Reed

Duncan

2010

J. Am. Soc. Mass Spectrom.

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supporting

confidence: 92%

mentioning

confidence: 91%

Infrared spectroscopy and structures of manganese carbonyl cations, Mn(CO)_n⁺ (n = 1−9)

Reed

Duncan

2010

J. Am. Soc. Mass Spectrom.

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“…10 It is also a popular model to explain the interaction of RG atoms with metal surfaces and metal ion complexes. 14,17,29 Avoidance of the symmetrical axis for binding was also found for the Mn + Á(H 2 O) complex. 15 Interaction between Si 7 TM + with TM = Cr, Mn, Cu, Zn and Ar, Xe atoms…”

Section: Moreover the Rg Atom Inmentioning

confidence: 69%

Nature of the interaction between rare gas atoms and transition metal doped silicon clusters: the role of shielding effects

Ngân

Janssens

Claes

et al. 2015

Phys. Chem. Chem. Phys.

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Mass spectrometry experiments show an exceptionally weak bonding between Si 7 Mn + and rare gas atoms as compared to other exohedrally transition metal (TM) doped silicon clusters and other Si n Mn + (n = 5-10) sizes. The Si 7 Mn + cluster does not form Ar complexes and the observed fraction of Xe complexes is low. The interaction of two cluster series, Si n Mn + (n = 6-10) and Si 7 TM + (TM = Cr, Mn, Cu, and Zn), with Ar and Xe is investigated by density functional theory calculations. The cluster-rare gas binding is for all clusters, except Si 7 Mn + and Si 7 Zn + , predominantly driven by short-range interaction between the TM dopant and the rare gas atoms. A high s-character electron density on the metal atoms in Si 7 Mn + and Si 7 Zn + shields the polarization toward the rare gas atoms and thereby hinders formation of short-range complexes.Overall, both Ar and Xe complexes are similar except that the larger polarizability of Xe leads to larger binding energies.Atomic clusters emerge as interesting materials in the size regime between single atoms and nanoparticles, whose properties are strongly influenced by confinement effects. Understanding of their size and composition dependent structures and properties is primordial for further usage. The interactions between clusters and rare gas (RG) atoms are of crucial importance in many experimental techniques. For example, RG complexes are used for action spectroscopy in cluster science due to the inherent weak interaction, 1 Ar titration and tagging have been used to obtain isomer-specific photoelectron spectra for 2D and 3D gold clusters 2,3 and isomer selective infrared (IR) spectra of niobium clusters. 4 In most experimental studies, it has been assumed that the RG atoms do not significantly influence the intrinsic structure and properties of the bare clusters, and are therefore called messenger or spectator atoms. A negligible influence of the RG atoms is inferred from their low adsorption energies and from insignificant differences in measured IR spectra of elemental clusters and their Ar-complexes, such as for V n + , 5 Nb n + , 6 Ta n + (n = 6-20), 7 Si n + (n = 6-21), 8 as well as for binary Si n V + and Si n Cu + (n = 6-11) clusters. 9 Nevertheless, such an assumption is not always applicable. Stronger cluster-RG interactions, which cause discernible changes in the IR spectra of the bare clusters, were observed for some Co n + , Au n , and doped Au n Y clusters. 10-12 Moreover, the RG tagging of some oxide clusters changes the energetic ordering of the isomers, in which case a low-energetic structural isomer, and thus not the ground state structure of the bare cluster, is probed in the experiment. 13 A simple electrostatic picture was put forward to explain the stronger influence of the RG atom, analogous to models often used to interpret the interaction of RG atoms with metal surfaces 14 or metal complexes. 15 Much effort has been devoted to reveal the nature of interaction between RG and metal surfaces 12,16 or metal-atom complexes. 14,17 There are a...

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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 Cr⁺(H₂O) and Cr²⁺(H₂O): The Role of Charge in Cation Hydration

Cited by 60 publications

References 142 publications

Infrared spectroscopy and structures of manganese carbonyl cations, Mn(CO)_n⁺ (n = 1−9)

Infrared spectroscopy and structures of manganese carbonyl cations, Mn(CO)_n⁺ (n = 1−9)

Nature of the interaction between rare gas atoms and transition metal doped silicon clusters: the role of shielding effects

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

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Infrared Spectroscopy of Cr+(H2O) and Cr2+(H2O): The Role of Charge in Cation Hydration

Cited by 60 publications

References 142 publications

Infrared spectroscopy and structures of manganese carbonyl cations, Mn(CO)n+ (n = 1−9)

Infrared spectroscopy and structures of manganese carbonyl cations, Mn(CO)n+ (n = 1−9)

Nature of the interaction between rare gas atoms and transition metal doped silicon clusters: the role of shielding effects

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

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Infrared Spectroscopy of Cr⁺(H₂O) and Cr²⁺(H₂O): The Role of Charge in Cation Hydration

Infrared spectroscopy and structures of manganese carbonyl cations, Mn(CO)_n⁺ (n = 1−9)

Infrared spectroscopy and structures of manganese carbonyl cations, Mn(CO)_n⁺ (n = 1−9)