Structures, energetics, and spectra of aqua-cesium (I) complexes: An <i>ab initio</i> and experimental study

Kołaski, Maciej; Lee, Han Myoung; Choi, Young Cheol; Kim, Kwang S.; Tarakeshwar, P.; Miller, Dorothy J.; Lisy, James M.

doi:10.1063/1.2426339

Cited by 59 publications

(32 citation statements)

References 69 publications

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“…Our estimated d and E of 2.830 (3.013) Å and 14.7 (13.2) kcal/mol for Rb + H 2 O (Cs + H 2 O), respectively, agree well with the corresponding estimate of 2.763 (2.962) Å and 16.3 (13.5) kcal/mol made with a standard quantum chemistry method at the MP2 level of theory. 27,28 Our Rb + and Cs + aqueous solution systems are similar to the ones used in our former studies. 10 boundary conditions were applied.…”

mentioning

confidence: 79%

Communication: Hydration structure and polarization of heavy alkali ions: A first principles molecular dynamics study of Rb+ and Cs+

Ikeda

Boero

2012

The Journal of Chemical Physics

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Hydration structure and polarization of Rb+ and Cs+ in liquid water at ambient conditions were studied by first principles molecular dynamics. Our systematic analysis of the relevant electronic structures, based on maximally localized Wannier functions, revealed that the dipole moment of H2O molecules in the first solvation shell of the ions slightly increases with increasing the atomic number. We also found that the polarization of heavy alkali ions, particularly Cs+, tends to stabilize a peculiar asymmetric hydration structure with relevant consequences in the extraction of the harmful 137Cs resulting from nuclear wastes.

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mentioning

confidence: 79%

Communication: Hydration structure and polarization of heavy alkali ions: A first principles molecular dynamics study of Rb+ and Cs+

Ikeda

Boero

2012

The Journal of Chemical Physics

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“…On the computational front, a large number of structures have to be considered for solvated metal complexes. Nonetheless, at least qualitative agreement between experiment and theory is now achievable (Kolaski et al, 2007).…”

Section: B Solvated Metal Cationsmentioning

confidence: 95%

Vibrational spectroscopy of bare and solvated ionic complexes of biological relevance

Polfer

Oomens²

2009

Mass Spectrometry Reviews

395

386

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The low density of ions in mass spectrometers generally precludes direct infrared (IR) absorption measurements. The IR spectrum of an ion can nonetheless be obtained by inducing photodissociation of the ion using a high-intensity tunable laser. The emergence of free electron lasers (FELs) and recent breakthroughs in bench-top lasers based on nonlinear optics have now made it possible to routinely record IR spectra of gas-phase ions. As the energy of one IR photon is insufficient to cause dissociation of molecules and strongly bound complexes, two main experimental strategies have been developed to effect photodissociation. In infrared multiple-photon dissociation (IR-MPD) many photons are absorbed resonantly and their energy is stored in the bath of vibrational modes, leading to dissociation. In the "messenger" technique a weakly bound van der Waals atom is detached upon absorption of a single photon. Fundamental, historical, and practical aspects of these methods will be presented. Both of these approaches make use of very different methods of ion preparation and manipulation. While in IR-MPD ions are irradiated in trapping mass spectrometers, the "messenger" technique is generally carried out in molecular beam instruments. The main focus of this review is the application of IR spectroscopy to biologically relevant molecular systems (amino acids, peptides, proteins). Particular issues that will be addressed here include gas-phase zwitterions, the (chemical) structures of peptides and their collision-induced dissociation (CID) products, IR spectra of gas-phase proteins, and the chelation of metal-ligand complexes. Another growing area of research is IR spectroscopy on solvated clusters, which offer a bridge between the gas-phase and solution environments. The development of state-of-the-art computational approaches has gone hand-in-hand with advances in experimental techniques. The main advantage of gas-phase cluster research, as opposed to condensed-phase experiments, is that the systems of interest can be understood in detail and structural effects can be studied in isolation. It will be shown that IR spectroscopy of mass-selected (bio)molecular systems is now well-placed to address specific questions on the individual effect of charge carriers (protons and metal ions), as well as solvent molecules on the overall structure.

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“…For Cu þ (NH 3 ) n , the IRMPD spectra where n ¼ 4 and 5 indicate the existence of multiple isomers with coordination numbers of 2, 3, and 4, while at higher n, the dicoordinated inner shell becomes more important (Inoue et al, 2007). Cs þ (H 2 O) n systems show significant amounts of hydrogen bonded O-H stretching features with solvation as low as 3 (Kolaski et al, 2007) and a full solvation shell is unlikely after n ¼ 2. Studies of alkali metal cation bound dimers (Vaden & Lisy, 2005) and trimers (Vaden & Lisy, 2006) of phenol show that Li þ prefers strong ion-p bonding, that intermolecular hydrogen bonding becomes important for the larger alkali metal ions, and that the relatively tight hydrogen-bonded structures are far more prevalent at lower temperatures.…”

Section: Solvated Metal Ionsmentioning

confidence: 99%

Infrared consequence spectroscopy of gaseous protonated and metal ion cationized complexes

Fridgen

2009

Mass Spectrometry Reviews

197

176

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In this article, the new and exciting techniques of infrared consequence spectroscopy (sometimes called action spectroscopy) of gaseous ions are reviewed. These techniques include vibrational predissociation spectroscopy and infrared multiple photon dissociation spectroscopy and they typically complement one another in the systems studied and the information gained. In recent years infrared consequence spectroscopy has provided long-awaited direct evidence into the structures of gaseous ions from organometallic species to strong ionic hydrogen bonded structures to large biomolecules. Much is being learned with respect to the structures of ions without their stabilizing solvent which can be used to better understand the effect of solvent on their structures. This review mainly covers the topics with which the author has been directly involved in research: structures of proton-bound dimers, protonated amino acids and DNA bases, amino acid and DNA bases bound to metal ions and, more recently, solvated ionic complexes. It is hoped that this review reveals the impact that infrared consequence spectroscopy has had on the field of gaseous ion chemistry.

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Structures, energetics, and spectra of aqua-cesium (I) complexes: An ab initio and experimental study

Cited by 59 publications

References 69 publications

Communication: Hydration structure and polarization of heavy alkali ions: A first principles molecular dynamics study of Rb+ and Cs+

Communication: Hydration structure and polarization of heavy alkali ions: A first principles molecular dynamics study of Rb+ and Cs+

Vibrational spectroscopy of bare and solvated ionic complexes of biological relevance

Infrared consequence spectroscopy of gaseous protonated and metal ion cationized complexes

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