Infrared spectra and structures of diamantyl and triamantyl carbocations

Pirali, Olivier; Galué, Héctor Alvaro; Dahl, Jeremy E. P.; Carlson, Robert M. K.

doi:10.1016/j.ijms.2010.05.018

Cited by 10 publications

(10 citation statements)

References 35 publications

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“…Since these modes are IR inactive, experimental frequencies for these modes have been obtained by Raman spectroscopy of adamantane in condensed-phase samples. 14,16 When strong Coriolis interaction occurs, the perturbing mode may become weakly active, but we did not detect any absorption in the region of ν 12 or ν 19 . Since no large perturbations were detected in the branches of ν 30 , it was treated as an isolated band in the analysis.…”

Section: Resultscontrasting

confidence: 60%

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Rotationally resolved infrared spectroscopy of adamantane

Pirali

Boudon

Oomens

et al. 2012

The Journal of Chemical Physics

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Rotationally resolved infrared spectroscopy of adamantanePirali, O.; Boudon, V.; Oomens, J.; Vervloet, M. General rightsIt is not permitted to download or to forward/distribute the text or part of it without the consent of the author(s) and/or copyright holder(s), other than for strictly personal, individual use, unless the work is under an open content license (like Creative Commons). Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. We present the first rotationally resolved spectra of adamantane (C 10 H 16 ) applying gas-phase Fourier transform infrared (IR) absorption spectroscopy. High-resolution IR spectra are recorded in the 33-4500 cm −1 range using as source of IR radiation both synchrotron radiation (at the AILES beamline of the SOLEIL synchrotron) as well as a classical globar. Adamantane is a spherical top molecule with tetrahedral symmetry (T d point group) and has no permanent dipole moment in its vibronic ground state. Of the 72 fundamental vibrational modes in adamantane, only 11 are IR active. Here we present rotationally resolved spectra for seven of them: ν 30 , ν 28 , ν 27 , ν 26 , ν 25 , ν 24 , and ν 23 . The typical rotational structure of spherical tops is observed and analyzed using the STDS software developed in the Dijon group, which provides the first accurate energy levels and rotational constants for seven fundamental modes. Rotational levels with quantum numbers as high as J = 107 have been identified and included in the fit leading to a typical standard deviation of about 10 −3 cm −1 .

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Section: Resultscontrasting

confidence: 60%

“…Vibrational spectra are available for adamantane, [14][15][16] various larger diamondoid molecules 17 including some of their positively charged ions 18,19 and diamond nanoparticles. 4,20 Adamantane displays strong Raman activity and Raman spectra of adamantane 16 as well as of several larger diamondoid molecules 21,22 have been reported.…”

Section: Introductionmentioning

confidence: 99%

Rotationally resolved infrared spectroscopy of adamantane

Pirali

Boudon

Oomens

et al. 2012

The Journal of Chemical Physics

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“…[14] Sparked by the astrophysical relevance, a large number of experimental and computational studies have been devoted to understanding the spectroscopic properties of neutral and ionized diamondoids in the gas phase. [22][23][24] Electronic spectra and ionization energies have also been characterized by DFT together with infrared spectra of neutral and cationic diamondoids up to C 38 H 42 . [18][19] Laserand synchrotron-induced vibrationally resolved photoluminescence spectra of diamondoids isolated in the gas phase have also been reported.…”

Section: Introductionmentioning

confidence: 99%

Spectroscopic Characterization of the Product Ions Formed by Electron Ionization of Adamantane

Bouwman

Horst

2018

ChemPhysChem

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A structural characterization of the products formed in the dissociative electron ionization of adamantane (C 10 H 16 ) is presented. Molecular structures of product ions are suggested based on multiple‐photon dissociation spectroscopy using the Free Electron Laser for Infrared eXperiments (FELIX) in combination with quantum‐chemical calculations. Product ions are individually isolated in an ion trap tandem mass spectrometer and their action IR spectra are recorded. Atomic hydrogen loss from adamantane yields the 1‐adamantyl isomer. The IR spectrum of the C 8 H 11 + product ion is best reproduced by computed spectra of 2‐ and 4‐protonated meta ‐xylene and ortho ‐ and para‐ protonated ethylbenzenes. The spectrum of the product ion at m/z 93 suggests that it is composed of a mixture of ortho ‐protonated toluene, para ‐protonated toluene and 1,2‐dihydrotropylium, while the spectrum of the m/z 79 ion is consistent with the benzenium ion. This study thus suggests that adamantane is efficiently converted into aromatic species and astrophysical implications for the interstellar medium are highlighted.

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“…Indeed, such behavior was observed for the three smallest diamondoids. By comparing the IR absorption bands of positively charged, gas phase adamantane (Polfer et al 2004), diamantane, and triamantane (Pirali et al 2010) with theoretical spectra of dehydrogenated diamondoid cations, it was shown that these molecules easily lose a hydrogen atom upon ionization to form stable closedshell species. The loss preferentially happens on a tertiary carbon (CH group) rather than on a secondary carbon (CH 2 group).…”

Section: Introductionmentioning

confidence: 99%

Electronic Spectroscopy of Fuv-Irradiated Diamondoids: A Combined Experimental and Theoretical Study

Steglich¹,

Huisken²,

Dahl³

et al. 2011

ApJ

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Irradiation with high energy photons (10.2 − 11.8 eV) was applied to small diamondoids isolated in solid rare gas matrices at low temperature. The photoproducts were traced via UV absorption spectroscopy. We found that upon ionization the smallest of these species lose a peripheral H atom to form a stable closed-shell cation. This process is also likely to occur under astrophysical conditions for gas phase diamondoids and it opens the possibility to detect diamond-like molecules using their rotational spectrum since the dehydrogenated cations possess strong permanent dipole moments. The lowest-energy electronic features of these species in the UV were found to be rather broad, shifting to longer wavelengths with increasing molecular size. Calculations using time-dependent density functional theory support our experimental findings and extend the absorption curves further into the vacuum ultraviolet. The complete σ − σ * spectrum displays surprisingly strong similarities to meteoritic nanodiamonds containing 50 times more C atoms.

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Infrared spectra and structures of diamantyl and triamantyl carbocations

Cited by 10 publications

References 35 publications

Rotationally resolved infrared spectroscopy of adamantane

Rotationally resolved infrared spectroscopy of adamantane

Spectroscopic Characterization of the Product Ions Formed by Electron Ionization of Adamantane

Electronic Spectroscopy of Fuv-Irradiated Diamondoids: A Combined Experimental and Theoretical Study

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