Infrared Spectroscopy of Mn+(H2O) and Mn2+(H2O) via Argon Complex Predissociation

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

doi:10.1021/jp203501n

Cited by 45 publications

(79 citation statements)

References 60 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…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: 99%

“…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 also a lot of experimental and theoretical results for transition metal cations interacting with RG atoms.…”

mentioning

confidence: 99%

See 1 more Smart Citation

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.

View full text Add to dashboard Cite

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...

show abstract

“…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: 99%

mentioning

confidence: 99%

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.

View full text Add to dashboard Cite

show abstract

“…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%

“…This structure has been confirmed in subsequent calculations by Trachtman et al 30 and Irigorias et al 31 who also noted that the septet Mn + ion is not likely to accept donations from the water due to the Mn + ion's highly stabilized exchange energy due to its six matching spins. Calculations by Carnegie et al 17 Although the attached argon typically only slightly perturbs the O-H stretching frequencies, it strongly affects the rotational constants. Our group used photodissociation spectroscopy and vibrationally mediated photodissociation (VMP) to measure the electronic spectra and O−H stretching frequencies of untagged Ni + (H 2 O) and Co + (H 2 O).…”

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

View full text Add to dashboard Cite

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 .

show abstract

“…Their properties have been investigated in considerable detail, with a wide range of experimental techniques, as reviewed recently [2][3][4][5][6][7]. Photodissociation in the O-H stretch region of the infrared, often coupled with tagging with a weakly bound species like Ar, is the most widely used spectroscopic method [8][9][10][11][12][13][14] [15] were characterized with infrared spectroscopy by Duncan and coworkers. For V + (H 2 O) n , n ≤ 8, a square-planar configuration was observed by Ohashi and coworkers, with four water molecules directly coordinated to V + [13].…”

Section: Introductionmentioning

confidence: 99%

Photodissociation and photochemistry of V+(H2O)n, n = 1–4, in the 360–680 nm region

Scharfschwerdt

Linde

Balaj

et al. 2012

Low Temperature Physics

View full text Add to dashboard Cite

The photodissociation and photochemistry of V + (H 2 O) n , n = 1-4, was studied in the 360-680 nm region in a Fourier transform ion cyclotron resonance mass spectrometer. The light of a high pressure mercury arc lamp was filtered with band pass filters, with center wavelengths from 360 to 680 nm in steps of 20 nm. The bandwidth of the filters, defined as full width at half maximum, was 10 nm. Photodissociation channels are loss of water molecules, as well as loss of atomic or molecular hydrogen, which may be accompanied by loss of water molecules. The most intense absorptions are red shifted with increasing hydration. Theoretical spectra are calculated with time dependent density functional theory. Calculations reproduce all features of the experimental spectra, including the red shift with increasing hydration shell and the overall pattern of strong and weak absorptions.

show abstract

Infrared Spectroscopy of Mn⁺(H₂O) and Mn²⁺(H₂O) via Argon Complex Predissociation

Cited by 45 publications

References 60 publications

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

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)

Photodissociation and photochemistry of V+(H2O)n, n = 1–4, in the 360–680 nm region

Contact Info

Product

Resources

About