Proton transfer and isotope-induced reaction in aniline cluster ions

Lengyel, Jozef; Poterya, Viktoriya; Fárnı́k, Michal

doi:10.1002/jms.3572

Cited by 3 publications

(5 citation statements)

References 36 publications

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“…1(d) exhibits aniline cluster ions (PhNH 2 ) n + , and clusters larger than n Z 10 are observed. We have shown in our recent detailed mass spectrometric study 24 that under the present conditions pure aniline clusters (PhNH 2 ) N were generated.…”

Section: Large Aniline Clustersmentioning

confidence: 67%

“…The CLUB experiments will be briefly outlined below, further details of the apparatus can be found in our recent publications. 24,28,32,33 A specially designed temperature controlled nozzle setup with a built in reservoir for solid and liquid samples inside the vacuum chamber was used to generate various aniline species from single molecules to large aniline (PhNH 2 ) N clusters and mixed clusters of aniline complexed with water (PhNH 2 ) N Á (H 2 O) M . To generate the beam composed mostly of aniline monomers the He carrier gas under 1 bar stagnation pressure passed through the reservoir with aniline at room temperature.…”

Section: Methodsmentioning

confidence: 99%

“…The aniline cluster mass spectrometry has been investigated in detail by our recent study where also a more detailed description of our RTOFMS can be found. 24…”

Section: Methodsmentioning

confidence: 99%

“…More about the generation of different aniline clusters in supersonic expansions under various conditions can be found in our recent publication. 24 Water can act as an effective quencher in photochemical reactions and is an important biological solvent. Therefore we investigate also aniline in water clusters from small mixed PhNH 2 Á(H 2 O) N , N r 10, species to PhNH 2 molecules deposited on large (H 2 O) N , % N = 430 (ice nanoparticles).…”

Section: Introductionmentioning

confidence: 99%

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Photodissociation of aniline N–H bonds in clusters of different nature

Poterya

Nachtigallová

Lengyel

et al. 2015

Phys. Chem. Chem. Phys.

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We investigated the solvent effects on the N-H bond photodisociation dynamics of aniline (PhNH2) in clusters using velocity map imaging (VMI). The VMI experiment was accompanied by a time-of-flight mass spectrometry after electron ionization to reveal the cluster nature. The H-fragment images were recorded at 243 nm in various expansion regimes corresponding to different species: isolated molecules; small (PhNH2)N, N ≤ 3, clusters; larger (PhNH2)N, N ≥ 10; small mixed PhNH2·(H2O)N, N ≤ 10, clusters; and individual PhNH2 molecules deposited on large (H2O)N, N̄ = 430. The H-fragment kinetic energy distributions exhibit fast fragments around 0.8 eV (A) assigned previously to a direct dissociation along a repulsive πσ* state potential, and slow statistical fragments peaking near 0.2 eV (B). In the aniline clusters the contribution of fast fragments (A) decreases relatively to (B) with increasing cluster size. A similar effect is observed when aniline is solvated with water molecules. The experimental data are interpreted with ab initio calculations. Cluster structures were calculated with both N-H bonds of an aniline molecule participating in hydrogen bonding, as well as the ones with free N-H bonds. The latter ones yield preferentially the fast fragments as the isolated molecule. For N-H engaged in hydrogen bonding a barrier increased along the N-H coordinate on the dissociative πσ* state potential surface, and also the energy of πσ*/S0 conical intersection increased. Thus the fast dissociation channel was closed stabilizing the molecule in clusters. The population could be funnelled through other conical intersections into the hot ground state which decayed statistically, yielding the slow H-fragments.

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Section: Large Aniline Clustersmentioning

confidence: 67%

Section: Methodsmentioning

confidence: 99%

“…The aniline cluster mass spectrometry has been investigated in detail by our recent study where also a more detailed description of our RTOFMS can be found. 24…”

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Photodissociation of aniline N–H bonds in clusters of different nature

Poterya

Nachtigallová

Lengyel

et al. 2015

Phys. Chem. Chem. Phys.

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“…This study was performed on CLuster Beam (CLUB) apparatus, which is a complex experiment dedicated to photochemistry, ,, mass spectrometry, − and pickup , studies of clusters in molecular beams. Detailed descriptions of the apparatus are given in the mentioned publications.…”

Section: Methodsmentioning

confidence: 99%

Biomolecule Analogues 2-Hydroxypyridine and 2-Pyridone Base Pairing on Ice Nanoparticles

et al. 2016

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Ice nanoparticles (H2O)N, N ≈ 450 generated in a molecular beam experiment pick up individual gas phase molecules of 2-hydroxypyridine and 2-pyridone (HP) evaporated in a pickup cell at temperatures between 298 and 343 K. The mass spectra of the doped nanoparticles show evidence for generation of clusters of adsorbed molecules (HP)n up to n = 8. The clusters are ionized either by 70 eV electrons or by two photons at 315 nm (3.94 eV). The two ionization methods yield different spectra, and their comparison provides an insight into the neutral cluster composition, ionization and intracluster ion-molecule reactions, and cluster fragmentation. Quite a few molecules were reported not to coagulate on ice nanoparticles previously. The (HP)n cluster generation on ice nanoparticles represents the first evidence for coagulating of molecules and cluster formation on free ice nanoparticles. For comparison, we investigate the coagulation of HP molecules picked up on large clusters ArN, N ≈ 205, and also (HP)n clusters generated in supersonic expansions with Ar buffer gas. This comparison points to a propensity for the (HP)2 dimer generation on ice nanoparticles. This shows the feasibility of base pairing for model of biological molecules on free ice nanoparticles. This result is important for hypotheses of the biomolecule synthesis on ice grains in the space. We support our findings by theoretical calculations that show, among others, the HP dimer structures on water clusters.

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