State-resolved UV photofragmentation spectrum of the metal dication complex [Zn(pyridine)4]2+

Wu, Guohua; Norris, Caroline; Stewart, Hamish; Cox, Hazel; Stace, A. J.

doi:10.1039/b806469e

Cited by 13 publications

(19 citation statements)

References 32 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…However, neither pyridine-N-oxide ion (D above) (m/z 95) nor C 5 H 5 NH + (m/z 80) was observed in Figure 1a, which clearly demonstrates that the ion selected and injected into the ion trap was ionized pyridine (B) and not expected to react with water under these experimental conditions. Confirmation that H 2 O is present as a background gas has been established in other experiments we have reported [38,52,53], and also in this study. where it is seen to react with the 2-acetylpyridine ion (see below).…”

Section: Resultssupporting

confidence: 67%

Activation of Methane by the Pyridine Radical Cation and its Substituted Forms in the Gas Phase

Stewart

Liu

et al. 2015

J. Am. Soc. Mass Spectrom.

Self Cite

View full text Add to dashboard Cite

Abstract. We present an experimental study of methane activation by pyridine cation and its substituents in the gas phase. Mass spectrometric experiments in an ion trap demonstrate that pyridine cation and some of its substituent cations are able to react with methane. The deuterated methane experiment has confirmed that the hydrogen atom in the ionic product of reaction does come from methane. The collected information about kinetic isotope effects has been used to distinguish the nature of the bond activation as a hydrogen abstraction. Furthermore, experimental results demonstrated that the substituent groups on the pyridine ring can crucially influence their reactivity in methane bond activation processes. Density functional calculation (DFT) was employed to study the electronic structures of the complex and reaction mechanism of CH 4 +C 5 H 5 N + . The calculations confirmed the hypothesis from the experimental observation, namely, the reaction is rapid with no energy barrier.

show abstract

Section: Resultssupporting

confidence: 67%

Activation of Methane by the Pyridine Radical Cation and its Substituted Forms in the Gas Phase

Stewart

Liu

et al. 2015

J. Am. Soc. Mass Spectrom.

Self Cite

View full text Add to dashboard Cite

show abstract

“…Furthermore, there is a need to ensure methods remain competitive with the increasingly accurate experimental work, for example, on molecular spectra. 2 There are several examples in the recent literature that advance these approximations, to name just a few, see the work by Cederbaum, 3 Sutcliffe, 4 regarding going beyond the standard B-O approximation and the work by Gill et al 5 attempting to provide a "universally accurate and efficient approach" to electron correlation.…”

Section: Introductionmentioning

confidence: 99%

“…Hill 24 proved that all symmetric (m 1 = m 2 )systemsarestable against dissociation into a two-particle system and a free particle, but no such formal proof exists for atoms and molecules of the general form {m 2 and, in fact, such systems are only stable within a certain range of particle mass. 19 Martin et al 13 estimated the lower bound of this stability region by deriving a function, δ(a 3 ), defined in Eq.…”

Section: Introductionmentioning

confidence: 99%

The stability of S-states of unit-charge Coulomb three-body systems: From H− to H2+

King

Longford

Cox

2013

The Journal of Chemical Physics

Self Cite

View full text Add to dashboard Cite

High accuracy non-relativistic quantum chemical calculations of the ground state energies and wavefunctions of symmetric three-particle Coulomb systems of the form {m ± 1 m ± 2 m ∓ 3 }, m 1 = m 2 , are calculated using an efficient and effective series solution method in a triple orthogonal Laguerre basis set. These energies are used to determine an accurate lower bound to the stability zone of unit-charge three-particle Coulomb systems using an expression for the width of the stability band in terms of g,t h ef r a c t i o n a la d d i t i o n a lb i n d i n gd u et oat h i r dp a r t i c l e .T h er e s u l t sa r ep r e s e n t e di nt h ef o r mo f areciprocalmassfractionternarydiagramandtheenergiesusedtoderi veaparameterisedfunction g(a 3 ), where a 3 = m 3 )isthereciprocalmassoftheuniquelychargedparticle. It is found that the function is not minimal at a 3 = 0whichcorrespondsto∞H − nor is it minimal at the positronium negative ion (Ps − )t h es y s t e mw i t ht h el e a s ta b s o l u t ee n e r g e t i cg a i nb ya s s o c iation with a third particle; the function g(a 3 )i sm i n i m a la tm 1 /m 3 = 0.49, and a possible physical interpretation in terms of the transition from atomic-like to molecular-like is provided. ©2013AIP Publishing LLC. [http://dx.doi.org/10.1063/1.4834036]

show abstract

“…50 A similar competition between coulomb explosion processes and the loss of neutral fragments has also been reported for the reactions between Y 2+ and small alkanes. 42 For ethane both the dehydrogenation process (reaction (15)) and the hydride-transfer (reaction (16) Doubly charged species are also readily formed by direct ionization of neutral molecules or clusters of neutral molecules, either by photoionization techniques 193,194 or by collision with fast highly charged ions. [195][196][197][198] The latter techniques are actually a promising therapy for the treatment of malignant tumors through the induction of DNA damage.…”

Section: Unimolecular Reactivity Of [Ml] 2+ Doubly Charged Molecular ...mentioning

confidence: 99%

[MLn]2+ doubly charged systems: modeling, bonding, life times and unimolecular reactivity

Corral

Yáñez

2011

Phys. Chem. Chem. Phys.

View full text Add to dashboard Cite

Doubly charged species in the gas phase have been an oddity for many years, but the possibility of generating and detecting them with the new available experimental techniques has faced the scientific community with challenging questions regarding their stability, bonding and reactivity. In this paper we analyze, mainly from a theoretical perspective, these questions for the particular subset of [ML(n)](2+) dications, where M is a metal and L an organic or inorganic ligand. Special attention is devoted to the challenges associated with their theoretical description, in particular as far as their bonding and their life times are concerned. A survey of their unimolecular reactivity is also presented as well as a discussion of the information available on dication affinities, and how they correlate with proton affinities or monocation affinities in general.

show abstract

State-resolved UV photofragmentation spectrum of the metal dication complex [Zn(pyridine)4]2+

Abstract: A combined theoretical and experimental study of electronic transitions in the complex [Zn(pyridine)(4)](2+) provides the first example of a state-resolved electronic spectrum to be recorded for a dication complex in the gas phase.

Cited by 13 publications

References 32 publications

Activation of Methane by the Pyridine Radical Cation and its Substituted Forms in the Gas Phase

Activation of Methane by the Pyridine Radical Cation and its Substituted Forms in the Gas Phase

The stability of S-states of unit-charge Coulomb three-body systems: From H− to H2+

[MLn]2+ doubly charged systems: modeling, bonding, life times and unimolecular reactivity

Contact Info

Product

Resources

About