اشترك بالحزمة الذهبية واحصل على وصول غير محدود شمرا أكاديميا
تسجيل مستخدم جديدIdentification of the fragment of the 1-methylpyrene cation by mid-IR spectroscopy
87
0
0.0
(
0
)
تأليف
Pavol Jusko
اسأل ChatGPT حول البحث
ﻻ يوجد ملخص باللغة العربية
The fragment of the 1-methylpyrene cation, C17H11+, is expected to exist in two isomeric forms, 1-pyrenemethylium PyrCH2+ and the tropylium containing species PyrC7+ . We measured the infrared (IR) action spectrum of cold C17H11+ tagged with Ne using a cryogenic ion trap instrument coupled to the FELIX laser. Comparison of the experimental data with density functional theory calculations allows us to identify the PyrCH2+ isomer in our experiments. The IR Multi-Photon Dissociation spectrum was also recorded following the C2H2 loss channel. Its analysis suggests combined effects of anharmonicity and isomerisation while heating the trapped ions, as shown by molecular dynamics simulations.
قيم البحث
اقرأ أيضاً
We present the gas-phase infrared spectra of the phenyl cation, phenylium, in its perprotio C$_6$H$_5^+$ and perdeutero C$_6$D$_5^+$ forms, in the 260-1925 cm$^{-1}$ (5.2-38 $mu$m) spectral range, and investigate the observed photofragmentation. The
spectral and fragmentation data were obtained using Infrared Multiple Photon Dissociation (IRMPD) spectroscopy within a Fourier Transform Ion Cyclotron Resonance Mass Spectrometer (FTICR MS) located inside the cavity of the free electron laser FELICE (Free Electron Laser for Intra-Cavity Experiments). The $^1$A$_1$ singlet nature of the phenylium ion is ascertained by comparison of the observed IR spectrum with DFT calculations, using both harmonic and anharmonic frequency calculations. To investigate the observed loss of predominantly [2C,nH] (n=2-4) fragments, we explored the potential energy surface (PES) to unravel possible isomerization and fragmentation reaction pathways. The lowest energy pathways toward fragmentation include direct H elimination, and a combination of facile ring-opening mechanisms ($leq2.4$ eV), followed by elimination of H or CCH$_2$. Energetically, all H-loss channels found are more easily accessible than CCH$_2$-loss. Calculations of the vibrational density of states for the various intermediates show that at high internal energies, ring opening is the thermodynamically the most advantageous, eliminating direct H-loss as a competing process. The observed loss of primarily [2C,2H] can be explained through entropy calculations that show favored loss of [2C,2H] at higher internal energies.
Many models that seek to explain the origin of the unresolved X-ray background predict that Compton-thick Active Galactic Nuclei (AGNs) are ubiquitious at high redshift. However, few distant Compton-thick AGNs have been reliably identified to date. H
ere we present Spitzer-IRS spectroscopy and 3.6-70um photometry of a z=2.2 optically identified AGN (HDF-oMD49) that is formally undetected in the 2Ms Chandra Deep Field-North (CDF-N) survey. The Spitzer-IRS spectrum and spectral energy distribution of this object is AGN dominated, and a comparison of the energetics at X-ray wavelengths to those derived from mid-infrared (mid-IR) and optical spectroscopy shows that the AGN is intrinsically luminous (L_X~3x10^44 erg/s) but heavily absorbed by Compton-thick material (N_H>>10^24 cm^{-2}); i.e., this object is a Compton-thick quasar. Adopting the same approach that we applied to HDF-oMD49, we found a further six objects at z~2-2.5 in the literature that are also X-ray weak/undetected but have evidence for AGN activity from optical and/or mid-IR spectroscopy, and show that all of these sources are also Compton-thick quasars with L_X>10^44 erg/s. On the basis of the definition of Daddi etal. (2007), these Compton-thick quasars would be classified as mid-IR excess galaxies, and our study provides the first spectroscopic confirmation of Compton-thick AGN activity in a subsample of these z~2 mid-IR bright galaxies. Using the four objects that lie in the CDF-N field, we estimate the space-density of Compton-thick quasars [Phi~(0.7-2.5)x10^-5 Mpc^-3 for L_X>10^44 erg/s objects at z~2-2.5] and show that Compton-thick accretion is as ubiquitious as unobscured accretion in the distant Universe.
We report on a form of gas-phase anion action spectroscopy based on infrared multiple photon electron detachment and subsequent capture of the free electrons by a neutral electron scavenger in a Fourier Transform Ion Cyclotron Resonance (FTICR) mass
spectrometer. This method allows one to obtain background-free spectra of strongly bound anions, for which no dissociation channels are observed. The first gas-phase spectra of acetate and propionate are presented using SF6 as electron scavenger and a free electron laser as source of intense and tunable infrared radiation. To validate the method, we compare infrared spectra obtained through multiple photon electron detachment/attachment and multiple photon dissociation for the benzoate anion. In addition, different electron acceptors are used, comparing both associative and dissociative electron capture. The relative energies of dissociation (by CO2 loss) and electron detachment are investigated for all three anions by DFT and CCSD(T) methods. DFT calculations are also employed to predict vibrational frequencies, which provide a good fit to the infrared spectra observed. The frequencies of the symmetric and antisymmetric carboxylate stretching modes for the aliphatic carboxylates are compared to those previously observed in condensed-phase IR spectra and to those reported for gas-phase benzoate, showing a strong influence of the solution environment and a slight substituent effect on the antisymmetric stretch.
We present 5-38um mid-infrared spectra at a spectral resolution of R~65-130 of a large sample of 22 starburst nuclei taken with the Infrared Spectrograph IRS on board the Spitzer Space Telescope. The spectra show a vast range in starburst SEDs. The s
ilicate absorption ranges from essentially no absorption to heavily obscured systems with an optical depth of tau(9.8um)~5. The spectral slopes can be used to discriminate between starburst and AGN powered sources. The monochromatic continuum fluxes at 15um and 30um enable a remarkably accurate estimate of the total infrared luminosity of the starburst. We find that the PAH equivalent width is independent of the total starburst luminosity L_IR as both continuum and PAH feature scale proportionally. However, the luminosity of the 6.2um feature scales with L_IR and can be used to approximate the total infrared luminosity of the starburst. Although our starburst sample covers about a factor of ten difference in the [NeIII]/[NeII] ratio, we found no systematic correlation between the radiation field hardness and the PAH equivalent width or the 7.7um/11.3um PAH ratio. These results are based on spatially integrated diagnostics over an entire starburst region, and local variations may be ``averaged out. It is presumably due to this effect that unresolved starburst nuclei with significantly different global properties appear spectrally as rather similar members of one class of objects.
We performed an analysis of the mid-infared properties of the 12micron Seyfert sample, a complete unbiased 12micron flux limited sample of local Seyfert galaxies selected from the IRAS Faint Source Catalog, based on low resolution spectra obtained wi
th the Infrared Spectrograph (IRS) on-board Spitzer Space Telescope. A detailed presentation of this analysis is dicussed in Wu et al. (2009). We find that on average, the 15-30micron slope of the continuum is -0.85+/-0.61 for Seyfert 1s and -1.53+/-0.84 for Seyfert 2s, and there is substantial scatter in each type. Moreover, nearly 32% of Seyfert 1s, and 9% of Seyfert 2s, display a peak in the mid-infrared spectrum at 20micron, which is attributed to an additional hot dust component. The Polycyclic Aromatic Hydrocarbon (PAH) equivalent width decreases with increasing dust temperature, as indicated by the global infrared color of the host galaxies. However, no statistical difference in PAH equivalent width is detected between the two Seyfert types, 1 and 2, of the same bolometric luminosity. Finally, we propose a new method to estimate the AGN contribution to the integrated 12micron galaxy emission, by subtracting the star formation component in the Seyfert galaxies, making use of the tight correlation between PAH 11.2micron luminosity and 12micron luminosity for star forming galaxies.
سجل دخول لتتمكن من نشر تعليقات
التعليقات
جاري جلب التعليقات
سجل دخول لتتمكن من متابعة معايير البحث التي قمت باختيارها
