Infrared Spectrum and Structure of the Adamantane Cation: Direct Evidence for Jahn–Teller Distortion

Patzer, A. B. C.; Schütz, Markus; Möller, Thomas; Dopfer, Otto

doi:10.1002/ange.201108937

Cited by 21 publications

(26 citation statements)

References 60 publications

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“…2d) and obscuring the T-t 2 Jahn-Teller fingerprint. The resulting anomalous Jahn-Teller lineshape identified here reconciles previous contrasting interpretations 37,38 . Most importantly, the Jahn-Teller signature of adamantane is strikingly similar to that calculated for bulk diamond using path-integral molecular dynamics 26 (black line in Fig.…”

Section: Resultssupporting

confidence: 76%

“…The HOMO of adamantane is triply degenerate and hence expected to undergo a Jahn-Teller splitting upon photoexcitation 36 . However, different experiments led to contrasting conclusions on the existence of a Jahn-Teller effect in adamantane 37,38 . Figure 2c shows how the threefolddegenerate HOMO of adamantane is split into a triplet by the C-C stretching vibrations of T 2 symmetry at 161.2 meV.…”

Section: Resultsmentioning

confidence: 99%

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Quantum nuclear dynamics in the photophysics of diamondoids

2013

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The unusual electronic properties of diamondoids, the nanoscale relatives of diamond, make them attractive for applications ranging from drug delivery to field emission displays. Identifying the fundamental origin of these properties has proven highly challenging, with even the most advanced quantum many-body calculations unable to reproduce measurements of a quantity as ubiquitous as the optical gap. Here, by combining first-principles calculations and Importance Sampling Monte Carlo methods, we show that the quantum dynamics of carbon nuclei is key to understanding the electronic and optical properties of diamondoids. Quantum nuclear effects dramatically modify the absorption lineshapes and renormalize the optical gaps. These findings allow us to formulate a complete theory of optical absorption in diamondoids, and establish the universal role of quantum nuclear dynamics in nanodiamond across the length scales.

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Section: Resultssupporting

confidence: 76%

Section: Resultsmentioning

confidence: 99%

Quantum nuclear dynamics in the photophysics of diamondoids

2013

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“…The anisotropy of the charge-induced dipole and charge-quadrupole interaction favors a linear over a T-shaped approach of the N 2 ligand toward a positive charge, q HNN = 1748. [8,[56][57][58][59][60][61][62][63][64] The NÀH donor bond elongates by 4 m upon formation of the hydrogen bond with N 2 . As a result, both NÀH stretching modes experience frequency redshifts of Dn s/a = À32/À23 cm À1 and an IR intensity enhancement of 76/85 %.…”

Section: Quantum Chemical Calculationsmentioning

confidence: 99%

Microsolvation of the 4‐Aminobenzonitrile Cation (ABN⁺) in a Nonpolar Solvent: IR Spectra of ABN⁺L_n (L=Ar and N₂, n≤4)

et al. 2012

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IR photodissociation (IRPD) spectra of mass-selected cluster ions of 4-aminobenzonitrile (ABN(+)) with up to four Ar and N2 ligands are recorded over the spectral range of the N-H stretching vibrations (ν(s/a)) of ABN(+) in its (2)B1 ground electronic state. ABN(+)-L(n) clusters are produced in an electron impact cluster ion source, which predominantly generates the most stable isomer of a given cluster ion. Vibrational frequency shifts of ν(s/a) provide information about the sequential microsolvation process of ABN(+) in a nonpolar solvent. In ABN(+)-(N2)n, the first two ligands fill a first subshell by forming hydrogen bonds to the acidic protons of the amino group, whereas further ligands bind more weakly to the aromatic ring (π bonds). Although the preferred cluster growth sequence in ABN(+)-Ar(n) is similar, several isomers are observed because the hydrogen bonds are only slightly stronger than the π bonds. Quantum chemical calculations at the M06-2X/aug-cc-pVTZ level confirm the cluster growth sequence derived from the IR spectra and provide further details of the intermolecular potential. The calculated binding energies of D0(H)=532 and 895 cm(-1) for hydrogen-bonded and D0(π)=512 and 530 cm(-1) for π-bonded Ar and N2 ligands are consistent with the observed photofragmentation branching ratios. Comparison between ABN(+)-L(n) and the corresponding clusters with the aniline cation demonstrates that the NH protons of the amino group become slightly more acidic upon H→CN substitution at the para position. Comparison between charged and neutral ABN((+))-L dimers indicates that ionization switches the preferred ion-ligand binding motif from π to hydrogen bonding.

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“…Interesting to note is that the small mixed clusters of adamantane cations, C10H16 + •He1,2,3 and C10H16 + •N2, have been generated and observed previously by others in studies of the infrared spectrum of the adamantane cation. 20 These cluster ions were generated in a pulsed supersonic plasma beam expansion of adamantane by electron ionization followed by three-body aggregation of either He or N2 with a rotational temperature of less than 50 K.…”

Section: Introductionmentioning

confidence: 99%

Magic Numbers for Packing Adamantane in Helium Droplets: Cluster Cations, Dications, and Trications

et al. 2017

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We report the first observation of cations, dications and trications of large clusters of adamantane. Cluster formation was initiated near 0 K in helium droplets and ionization was achieved with one or more collisions with energetic He species (He*, He + or He* -). The occurrence of Coulomb explosion appeared to discriminate against the formation of small multiply charged clusters. High resolution mass spectrometry revealed the presence of "magic number" m/z peaks that can be attributed to the packing of adamantane molecules into cluster structures of special stability involving preferred arrangements of these molecules. These abundance anomalies were seen to be independent of charge state. While some dehydrogenation of adamantane and its clusters was seen as well, no major transformations into adamantoids or microdiamonds were observed.

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Infrared Spectrum and Structure of the Adamantane Cation: Direct Evidence for Jahn–Teller Distortion

Cited by 21 publications

References 60 publications

Quantum nuclear dynamics in the photophysics of diamondoids

Quantum nuclear dynamics in the photophysics of diamondoids

Microsolvation of the 4‐Aminobenzonitrile Cation (ABN⁺) in a Nonpolar Solvent: IR Spectra of ABN⁺L_n (L=Ar and N₂, n≤4)

Magic Numbers for Packing Adamantane in Helium Droplets: Cluster Cations, Dications, and Trications

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Infrared Spectrum and Structure of the Adamantane Cation: Direct Evidence for Jahn–Teller Distortion

Cited by 21 publications

References 60 publications

Quantum nuclear dynamics in the photophysics of diamondoids

Quantum nuclear dynamics in the photophysics of diamondoids

Microsolvation of the 4‐Aminobenzonitrile Cation (ABN+) in a Nonpolar Solvent: IR Spectra of ABN+Ln (L=Ar and N2, n≤4)

Magic Numbers for Packing Adamantane in Helium Droplets: Cluster Cations, Dications, and Trications

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Microsolvation of the 4‐Aminobenzonitrile Cation (ABN⁺) in a Nonpolar Solvent: IR Spectra of ABN⁺L_n (L=Ar and N₂, n≤4)