School of Chemistry - Research Publications

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Subject: Physical Chemistry not elsewhere classified; Expanding Knowledge in the Chemical Sciences × Author: Sanelli, Julian × Start date: 2012 ×

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    Electronic spectra of gas-phase polycyclic aromatic nitrogen heterocycle cations: isoquinoline+ and quinoline+.
    DRYZA, VIKTORAS ; SANELLI, JULIAN ; Robertson, E ; BIESKE, EVAN ( 2012)
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    Electronic absorptions of the benzylium cation
    Dryza, V ; Chalyavi, N ; Sanelli, JA ; Bieske, EJ (AMER INST PHYSICS, 2012-11-28)
    The electronic transitions of the benzylium cation (Bz(+)) are investigated over the 250-550 nm range by monitoring the photodissociation of mass-selected C(7)H(7)(+)-Ar(n) (n = 1, 2) complexes in a tandem mass spectrometer. The Bz(+)-Ar spectrum displays two distinct band systems, the S(1)←S(0) band system extending from 370 to 530 nm with an origin at 19,067 ± 15 cm(-1), and a much stronger S(3)←S(0) band system extending from 270 to 320 nm with an origin at 32,035 ± 15 cm(-1). Whereas the S(1)←S(0) absorption exhibits well resolved vibrational progressions, the S(3)←S(0) absorption is broad and relatively structureless. Vibronic structure of the S(1)←S(0) system, which is interpreted with the aid of time-dependent density functional theory and Franck-Condon simulations, reflects the activity of four totally symmetric ring deformation modes (ν(5), ν(6), ν(9), ν(13)). We find no evidence for the ultraviolet absorption of the tropylium cation, which according to the neon matrix spectrum should occur over the 260 - 275 nm range [A. Nagy, J. Fulara, I. Garkusha, and J. Maier, Angew. Chem., Int. Ed. 50, 3022 (2011)].
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    Electronic Spectra of Gas-Phase Polycyclic Aromatic Nitrogen Heterocycle Cations: Isoquinoline(+) and Quinoline(+)
    Dryza, V ; Sanelli, JA ; Robertson, EG ; Bieske, EJ (AMER CHEMICAL SOC, 2012-05-03)
    Electronic spectra of the gas-phase isoquinoline(+)-Ar and quinoline(+)-Ar complexes are recorded using photodissociation spectroscopy by monitoring the Ar loss channel. The D(3)←D(0) and D(4)←D(0) band origins for isoquinoline(+)-Ar are observed at 15245 ± 15 cm(-1) and 21960 ± 15 cm(-1), respectively, whereas for quinoline(+)-Ar they appear at 16050 ± 15 cm(-1) and 21955 ± 15 cm(-1), respectively. Strong vibronic progressions for the D(3)←D(0) band systems of both isoquinoline(+)-Ar and quinoline(+)-Ar are modeled and assigned in terms of ring deformation and carbon-carbon stretch vibrational modes using time-dependent density functional theory calculations in conjunction with Franck-Condon simulations. The properties of the isoquinoline(+) and quinoline(+) molecules are compared with those of the isoelectronic naphthalene(+) molecule. The existence of strong progressions in the visible spectra of isoquinoline(+)-Ar and quinoline(+)-Ar suggests that the corresponding isoquinoline(+) and quinoline(+) molecular cations are unlikely to be responsible for diffuse interstellar bands.