Electronic spectra of C4H3Cl+ isomers

Chakrabarty, Satrajit; Rudnev, V.; Fulara, Jan; Dietsche, Rainer; Nagy, Ádám; Garkusha, Iryna; Mazzotti, Fabio; Rice, Corey A.; Maier, John P.

doi:10.1080/00268976.2012.697584

Cited by 2 publications

(1 citation statement)

References 17 publications

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“…The path length, E1 mm, is lower than that in absorption. 46 3 Results and discussion + is an abundant fragment from a number of organic precursors; it is also formed in ion-molecule reactions. 47,48 Its m/z = 115 peak is seen in the mass spectra of naphthalene and dihydro-naphthalene, 49 biphenyl, from a mixture of linear hydrocarbons, 30 and others.…”

Section: Methodsmentioning

confidence: 99%

Electronic spectroscopy of transient species in solid neon: the indene-motif polycyclic hydrocarbon cation family C9Hy+ (y = 7–9) and their neutrals

Nagy

Garkusha

Fulara

et al. 2013

Phys. Chem. Chem. Phys.

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In this Perspective the development and application of a mass-selective matrix isolation approach, employed with success over the last two decades in the spectroscopic characterization of numerous ions and neutral reactive species, is illustrated with original data for hydrocarbon cations and neutrals with a six- and a five-membered carbon ring fused. The setup allows for the electronic and vibrational assessment of these isolated molecules and ions in the inert neon environment. The transient species of interest are chosen due to their astrophysical relevance, and the role they play in flames, plasmas, combustion, organic reactions and atmospheric chemistry. Electronic absorption and fluorescence spectra of indene-related polycyclic aromatic hydrocarbon derivatives, C9Hy(+) (y = 7-9) cations, are presented. The ions were produced in a discharge source and investigated by means of absorption and emission spectroscopies after selectively trapping them in 6 K neon matrices. Photoconversion between the two C9H8(+) indenylium isomers and, upon irradiation, H2 loss from C9H9(+) were observed. Corresponding neutral species C9Hy are identified by photobleaching the matrices containing the cations.

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Section: Methodsmentioning

confidence: 99%

Electronic spectroscopy of transient species in solid neon: the indene-motif polycyclic hydrocarbon cation family C9Hy+ (y = 7–9) and their neutrals

Nagy

Garkusha

Fulara

et al. 2013

Phys. Chem. Chem. Phys.

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Cryogenic Ion Chemistry and Spectroscopy

et al. 2013

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The use of mass spectrometry in macromolecular analysis is an incredibly important technique and has allowed efficient identification of secondary and tertiary protein structures. Over 20 years ago, Chemistry Nobelist John Fenn and co-workers revolutionized mass spectrometry by developing ways to non-destructively extract large molecules directly from solution into the gas phase. This advance, in turn, enabled rapid sequencing of biopolymers through tandem mass spectrometry at the heart of the burgeoning field of proteomics. In this Account, we discuss how cryogenic cooling, mass selection, and reactive processing together provide a powerful way to characterize ion structures as well as rationally synthesize labile reaction intermediates. This is accomplished by first cooling the ions close to 10 K and condensing onto them weakly bound, chemically inert small molecules or rare gas atoms. This assembly can then be used as a medium in which to quench reactive encounters by rapid evaporation of the adducts, as well as provide a universal means for acquiring highly resolved vibrational action spectra of the embedded species by photoinduced mass loss. Moreover, the spectroscopic measurements can be obtained with readily available, broadly tunable pulsed infrared lasers because absorption of a single photon is sufficient to induce evaporation. We discuss the implementation of these methods with a new type of hybrid photofragmentation mass spectrometer involving two stages of mass selection with two laser excitation regions interfaced to the cryogenic ion source. We illustrate several capabilities of the cryogenic ion spectrometer by presenting recent applications to peptides, a biomimetic catalyst, a large antibiotic molecule (vancomycin), and reaction intermediates pertinent to the chemistry of the ionosphere. First, we demonstrate how site-specific isotopic substitution can be used to identify bands due to local functional groups in a protonated tripeptide designed to stereoselectively catalyze bromination of biaryl substrates. This procedure directly reveals the particular H-bond donor and acceptor groups that enforce the folded structure of the bare ion as well as provide contact points for noncovalent interaction with substrates. We then show how photochemical hole-burning involving only vibrational excitations can be used in a double-resonance mode to systematically disentangle overlapping spectra that arise when several conformers of a dipeptide are prepared in the ion source. Finally, we highlight our ability to systematically capture reaction intermediates and spectroscopically characterize their structures. Through this method, we can identify the pathway for water-network-mediated, proton-coupled transformation of nitrosonium, NO(+) to HONO, a key reaction controlling the cations present in the ionosphere. Through this work, we reveal the critical role played by water molecules occupying the second solvation shell around the ion, where they stabilize the emergent product ion in a fashion reminiscent of the s...

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Electronic spectra of C₄H₃Cl⁺ isomers

Cited by 2 publications

References 17 publications

Electronic spectroscopy of transient species in solid neon: the indene-motif polycyclic hydrocarbon cation family C9Hy+ (y = 7–9) and their neutrals

Electronic spectroscopy of transient species in solid neon: the indene-motif polycyclic hydrocarbon cation family C9Hy+ (y = 7–9) and their neutrals

Cryogenic Ion Chemistry and Spectroscopy

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