Arghya Chakraborty

The Electronic Spectrum of the Fulvenallenyl Radical

The fulvenallenyl radical was produced in 6 K neon matrices after mass-selective deposition of C7H5(-) and C7H5(+) generated from organic precursors in a hot cathode ion source. Absorption bands commencing at λ=401.3 nm were detected as a result of photodetachment of electrons from the deposited C7H5(-) and also by neutralization of C7H5(+) in the matrix. The absorption system is assigned to the 1 (2)B1 ←X (2)B1 transition of the fulvenallenyl radical on the basis of electronic excitation energies calculated with the MS-CASPT2 method. The vibrational excitation bands detected in the spectrum concur with the structure of the fulvenallenyl radical. Employing DFT calculations, it is found that the fulvenallenyl anion and its radical are the global minima on the potential energy surface among plausible structures of C7H5.

Electronic transitions of C₅H₃⁺ and C₅H₃: neon matrix and CASPT2 studies.

Two absorption systems of C5H3(+) starting at 350 and 345 nm were detected following mass-selective deposition of m/e = 63 ions in a 6 K neon matrix. These are assigned to the 1 (1)A1 ← X (1)A1 electronic transition of 1,2,3,4-pentatetraenylium H2CCCCCH(+) (isomer B(+)) and 1 (1)B2 ← X (1)A1 of penta-1,4-diyne-3-ylium HCCCHCCH(+) (C(+)). The absorptions of neutral C5H3 isomers with onsets at 434.5, 398.3, 369.0, and 267.3 nm are also detected. The first two systems are assigned to the 1 (2)B1 ← X (2)B1 and 1 (2)A2 ← X (2)B1 transitions of isomer B and C, respectively, and the latter two to ethynylcyclopropenyl (A) and 3-vinylidenecycloprop-1-enyl (D) radicals. The structural assignments are based on the adiabatic excitation energies calculated with the MS-CASPT2 method. A vibrational analysis of the electronic spectra, based on the calculated harmonic frequencies, supports this.

Electronic Absorption Spectra of H2C6O+ Isomers : Produced by Ion-Molecule Reactions

Three absorption systems with origins at 354, 497, and 528 nm were detected after mass-selected deposition of H2C6O(+) in a 6 K neon matrix. The ions were formed by the reaction of C2O with HC4H(+) in a mixture of C3O2 and diacetylene in a hot cathode source, or by dissociative ionization of tetrabromocyclohexadienone. The 497 and 354 nm systems are assigned to the 1(2)A″ ← X(2)A″ and 2(2)A″ ← X(2)A″ electronic transitions of B(+), (2-ethynylcycloallyl)methanone cation, and the 528 nm absorption to the 1(2)A2 ← X(2)B1 transition of F(+), 2-ethynylbut-3-yn-1-enone-1-ylide, on the basis of calculated excitation energies with CASPT2.

OPTICAL ABSORPTIONS OF OXYGENATED CARBON CHAIN CATIONS IN THE GAS PHASE

The gas-phase electronic spectra of linear OC4O+ and a planar C6H2O+ isomer were obtained at a rotational temperature of ≈10 K. Absorption measurements in a 6 K neon matrix were followed by gas-phase observations in a cryogenic radiofrequency ion trap. The origin bands of the

Electronic absorption spectrum of HC7O

1{}^{2}{{\rm{\Pi }}}_{u}\;\leftarrow \;X{}^{2}{{\rm{\Pi }}}_{g}

Electronic transitions of C5H+ and C5H: neon matrix and CASPT2 studies

transition of OC4O+ and the

Electronic Spectroscopy of a C7H4+ Isomer in a Neon Matrix: Methyltriacetylene Cation

1{}^{2}

Spectroscopic characterization of C7H3(+) and C7H3˙: electronic absorption and fluorescence in 6 K neon matrices.

A

Electronic Characterization of Reaction Intermediates: The Fluorenylium, Phenalenylium, and Benz[f]indenylium Cations and Their Radicals

{}_{2}\;\leftarrow X{}^{2}

Electronic Spectra of Protonated Fluoranthene in a Neon Matrix and Gas Phase at 10 K.

B1 of HCCC(CO)CCH+ lie at 417.31 ± 0.01 nm and 523.49 ± 0.01 nm, respectively. These constitute the first electronic spectra of oxygenated carbon chain cations studied under conditions that are relevant to the diffuse interstellar bands (DIBs), as both have a visible transition. The recent analysis of the 579.5 nm DIB indicates that small carriers, five to seven heavy atoms, continue to be possible candidates (Huang & Oka 2015). Astronomical implications are discussed regarding this kind of oxygenated molecules.