Gas-phase reactions of atomic lanthanide cations with methyl fluoride: periodicities reactivity

Koyanagi, Gregory K.; Zhao, Xiang; Blagojevic, Voislav; Jarvis, Michael J. Y.; Böhme, Diethard K.

doi:10.1016/j.ijms.2004.11.017

Cited by 43 publications

(53 citation statements)

References 31 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Furthermore, the elements Sc, Y, La, Ti, Zr, Hf, Nb, Ta, W, B, C, As, Cl, Ce, Gd, Tb, and Lu could form (MF 2 ) + type product ions with a percentage of over 10%. Some of the element affinities to fluorine had been reported based on the reaction in the reaction cell of a selected ion flow tube type ICP-MS, 7,8,14 which covered fewer elements than the present work. It is notable that there are many more elements showing affinities to oxygen than those to sulfur and fluorine, which may be one of the reasons for oxygen as a common reaction gas.…”

Section: ¹1mentioning

confidence: 86%

Classification of Chemical Elements in the Reaction Cell of ICP-MS Based on the Affinities with Sulfur, Oxygen, and Fluorine

Zhu

2018

Chem. Lett.

View full text Add to dashboard Cite

Classification of chemical elements in the reaction cell of an inductively coupled plasma mass spectrometer (ICP-MS) was first reported based on the affinities with multiple elements, i.e. sulfur, oxygen, and fluorine. The data were summarized in the periodic table based on the affinity with each of the three elements mentioned above. An example of the application of the present results was illustrated by analyzing Y and La in the matrix of Sr and Ba, offering apparently improved background equivalent concentration (BEC) and detection limits (DL). Keywords: Classification | Chemical element | Reaction cellSeparation of spectral interferences is one of the key issues for elemental measurement by using an inductively coupled plasma mass spectrometer (ICP-MS), which is a well-developed instrument capable of simultaneous measurement of multiple elements in a wide linearity range up to nine orders of magnitude. Reaction cell technique offers an effective approach for the separation of spectral interferences in the measurement by ICP-MS. 15 In order to achieve specific separations of various spectral interferences, some kinds of gases had been explored as the reaction gas in the reaction cell of ICP-MS, including H 2 , O 2 , NH 3 , CH 3 F, N 2 H 6 , N 2 O, CO, NO, and SF 6 .5 A systematic investigation of the ion-molecule reactions in the reaction cell will provide useful information for the development of a method for separating spectral interferences. However, it was difficult to elucidate the ion-molecule reactions by using a traditional ICP-MS instrument with a single quadrupole mass spectrometer (QMS) since the ionic species entering the reaction cell were extremely complicated, including polyatomic ions from the matrix of the sample, the solvent, the argon plasma gas, and the constituents of air.Detailed work on multiple elements in the periodic table had been carried out regarding the reactions with oxygen and fluoromethane, respectively, based on laboratory-developed selected ion flow tube (SIFT) ICP-MS. 68 In these studies, both atom attachment and molecule attachment have been observed with oxygen and fluoromethane, respectively, as the reaction cell gas. High-order reactions with attachment of multiple molecules had also been observed for some elements. Such kinds of information benefit the built up of spectral separation strategies in ICP-MS measurement. It is notable that SIFT-ICP-MS was developed in the Bohme group and was not commercially available for common ICP-MS users.In recent years, the commercial availability of ICP-QMS/ QMS, i.e. ICP-MS with a pair of QMS and an octapole reaction cell (ORC), makes it possible to investigate in detail ionmolecule reactions in the reaction cell by common ICP-MS users. The first QMS (QMS1) of the ICP-QMS/QMS instrument permits the ions with selected mass-to-charge (m/z) ratio to enter the ORC and to react with the reaction gas molecules so as to exclude the interferences from ionic species with unwanted m/z ratios, which were problematic when a traditional ICP-MS...

show abstract

Section: ¹1mentioning

confidence: 86%

Classification of Chemical Elements in the Reaction Cell of ICP-MS Based on the Affinities with Sulfur, Oxygen, and Fluorine

Zhu

2018

Chem. Lett.

View full text Add to dashboard Cite

show abstract

“…In this context, C-F bond activation using lanthanide cations has recently attracted a great deal of interest. Many experimental and theoretical studies have shown that bare lanthanide mono-cations are able to activate C-F bond efficiently using small model organometallic systems [6][7][8][9][10][11][12][13][14][15][16][17][18].…”

Section: Introductionmentioning

confidence: 99%

“…Several researchers have experimentally studied the detail of the reaction mechanism with recent advances in gas phase laser spectroscopic techniques [11,12]. The first report on this issue was that of by Cohrnel et al who applied Fourier transform ion cyclotron resonance mass spectroscopy to the study of reactions in which Ln = Ce, Pr, Sm, Ho, Tm, and Yb [11].…”

Section: Introductionmentioning

confidence: 99%

“…In 2005, Koyanagi et al reinvestigated the same C-F cleavage reaction of CH 3 F by lanthanide mono-cations using inductively-coupled plasma/selected-ion flow tube (ICP/SIFT) tandem mass spectrometry [12]. By broadly applying their experimental technique to the whole range of lanthanide reactions (excluding Pm + ), they found that there are several lanthanide systems that do not satisfy the proportional relationship between the 2nd IPs of the lanthanide elements and their relative reactivities.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Theoretical study of lanthanide mono cation-mediated C–F bond activation

Matsuda

Mori

2011

Chemical Physics

View full text Add to dashboard Cite

“…4 Accordingly, gas-phase reactions of various organic compounds with lanthanide cations have been extensively investigated by spectroscopic experiments [5][6][7][8][9][10] and computational studies [11][12][13] for decades. Among these molecular systems, H 2 O as the simplest molecule having the O-H bond, serves as a good model to understand the O-H bond activation by lanthanide cations.…”

mentioning

confidence: 99%

Theoretical Investigation of the Reaction of Ce⁺with Water in the Gas Phase: Density Functional Theory Calculations

Hong

Kim

Kim³

2013

Bulletin of the Korean Chemical Society

View full text Add to dashboard Cite

The importance of rare earth elements is growing in many areas, especially chemical catalysis, 1,2 metallurgy 3 and industrial field.4 Accordingly, gas-phase reactions of various organic compounds with lanthanide cations have been extensively investigated by spectroscopic experiments 5-10 and computational studies [11][12][13] 20,21In addition, the intersystem crossing (ISC) point is estimated by the single-point energy calculations along the reaction pathway. These results correlated to the recent experimental findings. 7,15We calculated the doublet and quartet PESs for the ionmolecule reaction of Ce + with H 2 O using DFT method, since these two states are very close in energy and may interconvert during the reaction. All molecular structures of the reaction species (reactants, intermediates, products, and transition states) were fully optimized using PBE0 hybrid DFT functional, 22 which are frequently used and gives reasonable results for lanthanide molecular systems.23-25 The unrestricted formalism (UPBE0) was used for all spin states. In particular, an open shell structure was used for the singlet spin states. We used the relativistic effective core potential (RECP) to treat the scalar relativistic effect for the lanthanide ion, Ce + . The small-core Stuttgart ECP28MWB 26,27 with the large atomic natural orbital (ANO) valence basis set ([6s6p5d4f 3g]) and 6-311++G(d,p) basis sets were used for the lanthanide ion (Ce + ) and other atoms (H and O), respectively. We also carried out the harmonic vibrational frequency calculation. All transition states were identified by one imaginary frequency and confirmed by using the intrinsic reaction coordinate (IRC) method.28,29 All relative energies included the zero-point energy (ZPE) correction for all reaction species. We also used the natural population analysis (NPA) 30 for characterizing atomic charge and electronic structure. All calculations were carried out using the Gaussian 03 program. 31All optimized geometries of both doublet and quartet spin states and the reaction PESs regarding to the reactions of Ce + with H 2 O are shown in Figures 1 and 2, respectively. The initiation step of the reaction is the association complex formation in both spin states. As shown in Figure 1, Ce + moves toward the electron rich oxygen atom of the water to form an initial intermediate, IM 1 in both spin states. This result can be readily expected due to the electronegativity of

show abstract

Gas-phase reactions of atomic lanthanide cations with methyl fluoride: periodicities reactivity

Cited by 43 publications

References 31 publications

Classification of Chemical Elements in the Reaction Cell of ICP-MS Based on the Affinities with Sulfur, Oxygen, and Fluorine

Classification of Chemical Elements in the Reaction Cell of ICP-MS Based on the Affinities with Sulfur, Oxygen, and Fluorine

Theoretical study of lanthanide mono cation-mediated C–F bond activation

Theoretical Investigation of the Reaction of Ce⁺with Water in the Gas Phase: Density Functional Theory Calculations

Contact Info

Product

Resources

About

Gas-phase reactions of atomic lanthanide cations with methyl fluoride: periodicities reactivity

Cited by 43 publications

References 31 publications

Classification of Chemical Elements in the Reaction Cell of ICP-MS Based on the Affinities with Sulfur, Oxygen, and Fluorine

Classification of Chemical Elements in the Reaction Cell of ICP-MS Based on the Affinities with Sulfur, Oxygen, and Fluorine

Theoretical study of lanthanide mono cation-mediated C–F bond activation

Theoretical Investigation of the Reaction of Ce+with Water in the Gas Phase: Density Functional Theory Calculations

Contact Info

Product

Resources

About

Theoretical Investigation of the Reaction of Ce⁺with Water in the Gas Phase: Density Functional Theory Calculations