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]+
TL;DR: In this paper, the authors measured the infrared spectra of [Mg·-H2O)1,2]- and [Al·−(H 2O)2]- ion and assigned a band at 3200-3800 cm−1.
About: This article is published in Chemical Physics Letters.The article was published on 2004-05-21 and is currently open access. It has received 52 citations till now. The article focuses on the topics: Ion & Infrared spectroscopy.
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TL;DR: A review of gas phase IRMPD spectroscopic investigations aiming at probing the structure and the reactivity of transition metal complexes and a special attention will be given to the infrared spectroscopy of reactive intermediates.
Abstract: Gas phase mid-infrared spectroscopy of molecular ions can nowadays be performed with high performance mass spectrometers coupled to free electron lasers (FEL). The wide and continuous tunability of highly intense FELs in the mid-infrared region can be exploited for performing infrared multiple photon dissociation (IRMPD) spectroscopy of molecular ions. This review will focus on gas phase IRMPD spectroscopic investigations aiming at probing the structure and the reactivity of transition metal complexes. The performance of infrared spectroscopy for characterizing the coordination mode of polydentate ligands and the spin state of the metal will be illustrated. Infrared spectroscopy has also been exploited to probe the reactivity of metal complexes, and a special attention will be given to the infrared spectroscopy of reactive intermediates.
274 citations
TL;DR: The data indicate that essentially all of the water molecules are in a hydrogen-bonded network by the size of n = 10, and there is no evidence for the formation of clathrate structures seen recently via IR spectroscopy of protonated water clusters.
Abstract: Infrared photodissociation spectroscopy is reported for mass-selected Ni+(H2O)n complexes in the O−H stretching region up to cluster sizes of n = 25. These clusters fragment by the loss of one or more intact water molecules, and their excitation spectra show distinct bands in the region of the symmetric and asymmetric stretches of water. The first evidence for hydrogen bonding, indicated by a broad band strongly red-shifted from the free OH region, appears at the cluster size of n = 4. At larger cluster sizes, additional red-shifted structure evolves over a broader wavelength range in the hydrogen-bonding region. In the free OH region, the symmetric stretch gradually diminishes in intensity, while the asymmetric stretch develops into a closely spaced doublet near 3700 cm-1. The data indicate that essentially all of the water molecules are in a hydrogen-bonded network by the size of n = 10. However, there is no evidence for the formation of clathrate structures seen recently via IR spectroscopy of protonat...
126 citations
TL;DR: This paper will focus on the major areas of research initiated by the Yuan T. Lee group and how these studies stimulated and influenced others in what is currently a vibrant and growing field of ionic clusters.
Abstract: Beginning in the mid-1980s, a number of innovative experimental studies on ionic clusters emerged from the laboratory of Yuan T. Lee combining infrared laser spectroscopy and tandem mass spectrometry. Coupled with modern electronic structure calculations, this research explored many facets of ionic clusters including solvation, structure, and dynamics. These efforts spawned a resurgence in gas-phase cluster spectroscopy. This paper will focus on the major areas of research initiated by the Lee group and how these studies stimulated and influenced others in what is currently a vibrant and growing field.
86 citations
TL;DR: In this paper, the authors present a review of metal-containing cluster ions to date and discuss future opportunities for infrared spectroscopy of these ion species and discuss the potential for future developments.
Abstract: Studies of gas phase M+(L)n cluster ions (where M is a metal atom and L is a ligand molecule) assist our understanding of solvation and chemical processes that involve metal ions. The recent development of pulsed, tuneable OPO (optical parametric oscillator) sources capable of generating infrared light at frequencies between 1000 and 4000 cm−1 has allowed the vibrational spectra of many species to be assigned for the first time. This perspective reviews infrared spectroscopy of metal-containing cluster ions to date and discusses future opportunities.
83 citations
TL;DR: The role played by the method of ion preparation (laser vaporization-supersonic expansion versus ion impact-evaporative cooling) in governing the internal energy of a specific species, Li(+)(H(2)O)Ar), is considered.
Abstract: The internal energy or effective temperature of cluster ions has become an important issue in characterizing the structures observed in these species. This report considers the role played by the method of ion preparation (laser vaporization—supersonic expansion versus ion impact—evaporative cooling) in governing the internal energy of a specific species, Li+(H2O)Ar. Vibrational predissociation spectroscopy of the O–H stretch modes revealed rotational features, which were used to characterize the structure and effective rotational temperature of the cluster ion. In addition, the impact of the lithium ion on the H2O molecule was analyzed in terms of the vibrational frequency shifts, relative IR intensities, and H2O geometry.
62 citations
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TL;DR: In this article, the authors present a series on molecular spectra and molecular structure, and a large number of tables have also been included in which theoretical results are summarized, or observed data collected, for the benefit of those carrying out research work in the field of infrared and Raman spectra or related fields.
Abstract: This present volume represents the continuation of a series on Molecular Spectra and Molecular Structure. Illustrations have been included to make the reader visualize clearly the significance and meaning of results of the theory. A large number of tables have also been included in which theoretical results are summarized, or observed data collected, for the benefit of those carrying out research work in the field of infrared and Raman spectra or related fields.
3,111 citations
TL;DR: In this paper, a two color laser scheme consisting of a tunable cw infrared laser with 0.5 cm^−1 resolution used to excite the O−H stretching vibrations and a cw CO2 laser that dissociates the vibrationally excited cluster ion through a multiphoton process is presented.
Abstract: The gas phase infrared spectra of the hydrated hydronium cluster ions H3O+·(H2O)n(n=1, 2, 3) have been observed from 3550 to 3800 cm^−1. The new spectroscopic method developed for this study is a two color laser scheme consisting of a tunable cw infrared laser with 0.5 cm^−1 resolution used to excite the O–H stretching vibrations and a cw CO2 laser that dissociates the vibrationally excited cluster ion through a multiphoton process. The apparatus is a tandem mass spectrometer with a radio frequency ion trap that utilizes the following scheme: the cluster ion to be studied is first mass selected; spectroscopic interrogation then occurs in the radio frequency ion trap; finally, a fragment ion is selected and detected using ion counting techniques. The vibrational spectra obtained in this manner are compared with that taken previously using a weakly bound H2 "messenger." A spectrum of H7 O + 3 taken using a neon messenger is also presented. Ab initio structure and frequency predictions by Remington and Schaefer are compared with the experimental results.
459 citations
TL;DR: In this paper, the structure and binding energies for many of the M(H2O)n(+) and M(M 2 O n(2+) species were determined for n = 1-3 and M = Mg, Ca, or Sr.
Abstract: The structure and binding energies are determined for many of the M(H2O)n(+) and M(H2O)n(2+) species, for n = 1-3 and M = Mg, Ca, or Sr. The trends are explained in terms of metal sp or sd-sigma hybridization and core polarization. The M(NH3)n(+) systems, with M = Mg or Sr, are also studied. For the positive ions, the low-lying excited states are also studied and compared with experiment. The calculations suggest an alternative interpretation of the SrNH3(+) spectrum.
196 citations
TL;DR: In this paper, the photodissociation spectra of Mg+H2On (n=1-5) cluster ions were examined in the wavelength region from 720 to 250 nm by monitoring the total yield of the fragment ions.
Abstract: Photodissociation spectra of Mg+(H2O)n (n=1–5) cluster ions were examined in the wavelength region from 720 to 250 nm by monitoring the total yield of the fragment ions. The absorption bands exhibit redshifts as large as 17 000 cm−1 with respect to the 2P–2S resonance line of the free Mg+ ion and were explained by the shift of this transition as a result of hydration. The spectra also exhibit clear evolution of solvation shell with the first shell closing at n=3, being consistent with the theoretical prediction. The mass spectra of the fragment ions show the existence of two dissociation processes: the evaporation of water molecules and the photoinduced intracluster reaction to produce the hydrated MgOH+ ion, MgOH+(H2O)m. The branching fraction between the two processes depends strongly on the solvent number n and also on the photolysis wavelength. The energetics and the dynamics of the dissociation processes were discussed in conjunction with the results of ab initio calculations.
154 citations