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Infrared spectroscopy of RG–Co+(H2O) complexes (RG = Ar, Ne, He): The role of rare gas “tag” atoms

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/5.0041069· OSTI ID:1852691
 [1];  [2];  [3]
  1. Univ. of Georgia, Athens, GA (United States); Univ. of Georgia, Athens, GA (United States)
  2. Auburn Univ., AL (United States)
  3. Univ. of Georgia, Athens, GA (United States)
+ Show Author Affiliations
RGn–Co+(H2O) cation complexes (RG = Ar, Ne, He) are generated in a supersonic expansion by pulsed laser vaporization. Here, complexes are mass-selected using a time-of-flight spectrometer and studied with infrared laser photodissociation spectroscopy, measuring the respective mass channels corresponding to the elimination of the rare gas “tag” atom. Spectral patterns and theory indicate that the structures of the ions with a single rare gas atom have this bound to the cobalt cation opposite the water moiety in a near-C2v arrangement. The O–H stretch vibrations of the complex are shifted compared to those of water because of the metal cation charge-transfer interaction; these frequencies also vary systematically with the rare gas atom attached. The efficiencies of photodissociation also vary with the rare gas atoms because of their widely different binding energies to the cobalt cation. The spectrum of the argon complex could only be measured when at least three argon atoms were attached. In the case of the helium complex, the low binding energy allows the spectra to be measured for the low-frequency H–O–H scissors bending mode and for the O–D stretches of the deuterated analog. The partially resolved rotational structure for the antisymmetric O–H and O–D stretches reveals the temperature of these complexes (6 K) and establishes the electronic ground state. The helium complex has the same 3B1 ground state as the tag-free complex studied previously by Metz and co-workers (2013), but the A rotational constant is contaminated by vibrational averaging from the bending motion of the helium.
Research Organization:
Univ. of Georgia, Athens, GA (United States)
Sponsoring Organization:
USDOE Office of Science (SC); National Science Foundation (NSF)
Grant/Contract Number:
SC0018835
OSTI ID:
1852691
Alternate ID(s):
OSTI ID: 1765399
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 6 Vol. 154; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

References (88)

Ions in Solution and their Solvation book June 2015
Hydrated metal ions in the gas phase journal January 2007
Metal Cation Coordination and Solvation Studied with Infrared Spectroscopy in the Gas Phase book August 2019
Unimolecular and hydrolysis channels for the detachment of water from microsolvated alkaline earth dication (Mg2+, Ca2+, Sr2+, Ba2+) clusters journal February 2014
Binding energies of first and second shell water molecules in the Fe( H2 O)2+, Co( H2 O)2+ and Au( H2 O)2+ cluster ions journal April 2001
Structures of [Mg·(H2O)1,2]+ and [Al·(H2O)1,2]+ ions studied by infrared photodissociation spectroscopy: evidence of [HO–Al–H]+ ion core structure in [Al·(H2O)2]+ journal May 2004
Threshold collision-induced dissociation of hydrated cadmium (II): Experimental and theoretical investigation of the binding energies for Cd2+(H2O)n complexes (n=4–11) journal February 2010
Coordinatively unsaturated cobalt ion in Co+(H2O)n (n=4–6) probed with infrared photodissociation spectroscopy journal May 2011
Infrared spectroscopy of V2+(H2O) complexes journal March 2012
Infrared spectroscopy of the Ti(H2O)Ar+ ion–molecule complex: Electronic state switching induced by argon journal June 2016
Optical spectroscopy and photodissociation dynamics of multiply charged ions journal July 2004
Formation of hydrated triply charged metal ions from aqueous solutions using nanodrop mass spectrometry journal July 2006
Fifty years of ion and neutral thermochemistry by mass spectrometry journal February 2015
PGOPHER: A program for simulating rotational, vibrational and electronic spectra journal January 2017
Cationic Noncovalent Interactions: Energetics and Periodic Trends journal March 2016
Persistence of Dual Free Internal Rotation in NH 4 + (H 2 O)·He n =0–3 Ion–Molecule Complexes: Expanding the Case for Quantum Delocalization in He Tagging journal April 2015
Microsolvation in V + (H 2 O) n Clusters Studied with Selected-Ion Infrared Spectroscopy journal January 2020
Bonding in Ground-State and Excited-State A + ·Rg van der Waals Ions (A = Atom, Rg = Rare-Gas Atom):  A Model-Potential Analysis journal May 2002
Ground and Excited States of the [Fe(H 2 O) 6 ] 2+ and [Fe(H 2 O) 6 ] 3+ Clusters: Insight into the Electronic Structure of the [Fe(H 2 O) 6 ] 2+ –[Fe(H 2 O) 6 ] 3+ Complex journal March 2015
Successive H2O Binding Energies for Fe(H2O)n+ journal June 1995
Solvation of Transition Metal Ions by Water. Sequential Binding Energies of M+(H2O)x (x = 1-4) for M = Ti to Cu Determined by Collision-Induced Dissociation journal April 1994
Gas-phase water and hydroxyl binding energies for monopositive first-row transition metal ions journal May 1989
Sequential solvation of atomic transition-metal ions. The second solvent molecule can bind more strongly than the first journal May 1989
Solvation Dynamics in Ni + (H 2 O) n Clusters Probed with Infrared Spectroscopy journal November 2005
Reactivity and Infrared Spectroscopy of Gaseous Hydrated Trivalent Metal Ions journal July 2008
Infrared Action Spectra of Ca 2+ (H 2 O) 11−69 Exhibit Spectral Signatures for Condensed-Phase Structures with Increasing Cluster Size journal November 2008
Hydration of Alkaline Earth Metal Dications: Effects of Metal Ion Size Determined Using Infrared Action Spectroscopy journal September 2009
Reactivity of Sc + ( 3 D, 1 D) and V + ( 5 D, 3 F):  Reaction of Sc + and V + with Water journal January 1999
Unimolecular Reactions of Dihydrated Alkaline Earth Metal Dications M2+(H2O)2, M = Be, Mg, Ca, Sr, and Ba:  Salt-Bridge Mechanism in the Proton-Transfer Reaction M2+(H2O)2 → MOH+ + H3O+ February 1999
Reactivity of Cr + ( 6 S, 4 D), Mn + ( 7 S, 5 S), and Fe + ( 6 D, 4 F): Reaction of Cr + , Mn + , and Fe + with Water journal September 1999
Reactivity of Co + ( 3 F, 5 F), Ni + ( 2 D, 4 F), and Cu + ( 1 S, 3 D): Reaction of Co + , Ni + , and Cu + with Water journal January 2000
Metal Ion Solvation in the Gas Phase:  The Quest for Higher Oxidation States journal September 2002
Insights into the Structures, Energetics, and Vibrations of Monovalent Cation−(Water) 1 - 6 Clusters † journal April 2004
Infrared Photodissociation Spectroscopy of [Mg·(H 2 O) 1-4 ] + and [Mg·(H 2 O) 1-4 ·Ar] + journal June 2004
Infrared Photodissociation Spectroscopy of Mg + (H 2 O)Ar n Complexes:  Isomers in Progressive Microsolvation journal August 2005
Model Systems for Probing Metal Cation Hydration:  The V + (H 2 O) and ArV + (H 2 O) Complexes † journal August 2007
Zn 2+ Has a Primary Hydration Sphere of Five: IR Action Spectroscopy and Theoretical Studies of Hydrated Zn 2+ Complexes in the Gas Phase journal December 2010
Theoretical Study of [Ni (H 2 O) n ] 2+ (H 2 O) m ( n ≤ 6, m ≤ 18) journal May 2011
Infrared Spectroscopy of Mn + (H 2 O) and Mn 2+ (H 2 O) via Argon Complex Predissociation journal July 2011
Coordination Numbers of Hydrated Divalent Transition Metal Ions Investigated with IRPD Spectroscopy journal December 2011
Photodissociation Studies of the Electronic and Vibrational Spectroscopy of Ni + (H 2 O) journal January 2012
Theoretical Study of Nascent Hydration in the Fe + (H 2 O) n System journal February 2012
Reactivity of Hydrated Monovalent First Row Transition Metal Ions M + (H 2 O) n , M = V, Cr, Mn, Fe, Co, Ni, Cu, Zn, toward Molecular Oxygen, Nitrous Oxide, and Carbon Dioxide journal April 2012
Dissociation Energy and Electronic and Vibrational Spectroscopy of Co + (H 2 O) and Its Isotopomers journal August 2012
Reactions of M + (H 2 O) n , n < 40, M = V, Cr, Mn, Fe, Co, Ni, Cu, and Zn, with D 2 O Reveal Water Activation in Mn + (H 2 O) n journal October 2012
Infrared Laser Spectroscopy of Mass-Selected Carbocations journal November 2012
Coordination and Solvation of the Au + Cation: Infrared Photodissociation Spectroscopy of Mass-Selected Au(H 2 O) n + ( n = 1–8) Complexes journal October 2012
Infrared Spectroscopy of Solvation in Small Zn + (H 2 O) n Complexes journal July 2013
Insights into Gas-Phase Structural Conformers of Hydrated Rubidium and Cesium Cations, M + (H 2 O) n Ar (M = Rb, Cs; n = 3–5), Using Infrared Photodissociation Spectroscopy journal February 2014
Infrared Spectroscopy of Cr + (H 2 O) and Cr 2+ (H 2 O): The Role of Charge in Cation Hydration journal July 2008
Hydration of Copper(II): New Insights from Density Functional Theory and the COSMO Solvation Model journal September 2008
IR Spectroscopy and Theory of Cu + (H 2 O)Ar 2 and Cu + (D 2 O)Ar 2 in the O−H (O−D) Stretching Region: Fundamentals and Combination Bands journal April 2009
Hydration Energies of Zinc(II): Threshold Collision-Induced Dissociation Experiments and Theoretical Studies journal December 2009
Generation, Stability, and Reactivity of Small, Multiply Charged Ions in the Gas Phase journal September 1999
Revisiting Li + (H 2 O) 3–4 Ar 1 Clusters: Evidence of High-Energy Conformers from Infrared Spectra journal May 2011
Frontiers in the infrared spectroscopy of gas phase metal ion complexes journal January 2005
Infrared spectroscopy of the Li+(H2O)Ar complex: the role of internal energy and its dependence on ion preparation journal January 2006
Elucidating the mechanism behind the stabilization of multi-charged metal cations in water: a case study of the electronic states of microhydrated Mg2+, Ca2+ and Al3+ journal January 2014
MN15: A Kohn–Sham global-hybrid exchange–correlation density functional with broad accuracy for multi-reference and single-reference systems and noncovalent interactions journal January 2016
Reflectron time‐of‐flight mass spectrometer for laser photodissociation journal April 1992
Structures, energies, and spectra of aqua-silver (I) complexes journal October 2003
Infrared spectroscopy of V+(H2O) and V+(D2O) complexes: Solvent deformation and an incipient reaction journal November 2003
Photodissociation spectroscopy of Zn+(H2O) and Zn+(D2O) journal February 2005
Why the hydration energy of Au+ is larger for the second water molecule than the first one: Skewed orbitals overlap journal August 2005
Infrared spectroscopy of Cu+(H2O)n and Ag+(H2O)n: Coordination and solvation of noble-metal ions journal May 2007
Threshold collision-induced dissociation of Sr2+(H2O)x complexes (x=1–6): An experimental and theoretical investigation of the complete inner shell hydration energies of Sr2+ journal January 2010
Infrared spectroscopy of Sc + (H 2 O) and Sc 2+ (H 2 O) via argon complex predissociation: The charge dependence of cation hydration journal January 2011
Electronic spectroscopy of CoNe + via mass-selected photodissociation journal September 2011
Invited Review Article: Laser vaporization cluster sources journal April 2012
The binding energies of one and two water molecules to the first transition‐row metal positive ions journal June 1989
Resonant photodissociation of CoAr + and CoKr + : Analysis of vibrational structure journal June 1989
Theoretical study of metal noble‐gas positive ions journal October 1989
Vibrational structure of an electrostatically bound ion–water complex journal October 1990
Absorption spectra of size‐selected solvated metal cations: Electronic states, symmetries, and orbitals in Sr + (NH 3 ) 1,2 and Sr + (H 2 O) 1,2 journal March 1991
A theoretical study of the positive and dipositive ions of M(NH 3 ) n and M(H 2 O) n for M=Mg, Ca, or Sr journal March 1992
Photodissociation spectroscopy of Mg + –H 2 O and Mg + –D 2 O journal December 1992
Photodissociation spectroscopy of Ca + –H 2 O and Ca + –D 2 O journal March 1996
Photodissociation study on Ca + (H 2 O) n , n =1–6: Electron structure and photoinduced dehydrogenation reaction journal June 1996
Structures and binding enthalpies of M+(H2O)n clusters, M=Cu, Ag, Au journal January 1999
Ortho-para interconversion in cation-water complexes: The case of V + (H 2 O) and Nb + (H 2 O) clusters journal June 2017
Infrared Spectroscopy of Solvation and Isomers in Fe+(H2O)1,2Arm Complexes journal January 2004
How many molecules make a solution? journal April 2002
Size-dependent reactivity in open shell metal-ion polar solvent clusters: spectroscopic probes of electronic-vibration coupling, oxidation and ionization journal October 2003
Spectroscopy and structure of solvated alkali-metal ions journal July 1997
Recent advances in the visible and UV spectroscopy of metal dication complexes journal September 2010
Ion Thermochemistry and Solvation From Gas Phase Ion Equilibria journal October 1977
SPECTROSCOPY OF METAL ION COMPLEXES: Gas-Phase Models for Solvation journal October 1997
Ions in Solution book January 1999

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
complete-active space self-consistent field
correlation-consistent basis sets
density functional theory
infrared spectroscopy
mass spectrometry
photodissociation spectroscopy
rotational spectra