Laser-Induced Fluorescence and Dispersed Fluorescence Spectroscopy of Jet-Cooled Isopentoxy Radicals.

The B̃-X̃ laser-induced fluorescence (LIF) and dispersed fluorescence (DF) spectra of jet-cooled isopentoxy radicals have been obtained. The LIF spectrum of isopentoxy lacks strong transitions to the CO-stretch levels that are typical for alkoxy radicals. Instead, it contains two low-frequency vibrational progressions due to large-amplitude motions of the GG' and GG conformers involving torsion of the C1C2C3H dihedral angle. Other vibronic bands observed in the LIF spectrum are attributed to the TG conformer. Molecular carriers of the vibronic transitions in the LIF spectrum are identified by comparing the experimentally obtained spectrum and the simulated one. DF spectra of the GG and TG conformers are dominated by strong vibrational progressions of the CO-stretch mode when the origin or the CO-stretch band is pumped. When non-CO-stretch bands are pumped, the DF spectra are dominated by combination bands of the CO stretch and the pumped mode. Ã-X̃ separations of the GG and TG conformers were also determined from the DF spectra.

Room-Temperature Cavity Ring-Down Spectroscopy of Methylallyl Peroxy Radicals.

We report room-temperature cavity ring-down (CRD) spectra of the à ← X̃ electronic transition of 1-, 2-, and 3-methylallyl peroxy (MAOO•) radicals produced by 193 nm photolysis of methyl-substituted allyl chlorides in the presence of O2. Vibronic structure of experimentally observed spectra was simulated using calculated relative populations of MAOO• conformers, their electronic transition frequencies and oscillator strengths, as well as their vibrational frequencies and Franck-Condon factors of the à ← X̃ electronic transition. The reaction intermediate for the production of 1- and 3-MAOO• radicals, CH3CHCHCH2, is a resonance-stabilized free radical. CRD spectra of 1- and 3-MAOO• radicals obtained using different precursors suggest that allylic rearrangement between the two resonance structures (CH3CH=CHCH2• and CH3CH•CH=CH2) is significantly faster than oxygen addition. Branching ratio between terminal and nonterminal oxygen addition was predicted to be 52:48 on the basis of calculated spin densities, which agrees qualitatively with the experimental CRD spectra of 1- and 3-MAOO• radicals.

Revealing Long-Range Substituent Effects in the Laser-Induced Fluorescence and Dispersed Fluorescence Spectra of Jet-Cooled CHxF3-xCH2O (x = 1, 2, 3) Radicals.

The B̃-X̃ laser-induced fluorescence (LIF) and dispersed fluorescence (DF) spectra of the atmospherically important ß-monofluoro ethoxy (MFEO), ß,ß-difluoro ethoxy (DFEO), and ß,ß,ß-trifluoro ethoxy (TFEO) radicals were recorded with vibronic resolution under jet-cooled conditions. To simulate the spectra, Franck-Condon factors were obtained from quantum chemical computations carried out at the CAM-B3LYP/6-311++G(d,p) level of theory. The simulations reproduce well both the LIF and DF spectra. Both conformers (G and T) of MFEO and one (G) of the two conformers of DFEO contribute to the LIF spectrum. A comparison between the experimental and calculated spectra confirms the expected long-range field effects of the CHxF3-x group on electronic transition energies and bond strengths, especially in the excited electronic (B̃) state. Although TFEO has only one conformer, its LIF spectrum is highly congested, which is attributed to the interaction between CO stretch and the -CF3 internal rotation.

Laser-induced fluorescence and dispersed-fluorescence spectroscopy of the Ã2E-X̃2A1 transition of jet-cooled calcium methoxide (CaOCH3) radicals.

Laser-induced fluorescence (LIF) and dispersed fluorescence (DF) spectra of the Ã2E-X̃2A1 electronic transition of the calcium methoxide (CaOCH3) radical have been obtained under jet-cooled conditions. Complete active space self-consistent field and coupled-cluster calculations on the free radical were performed to aid the assignment of vibronic transitions observed in the LIF/DF spectra. In addition to dominant spectral features that are well reproduced by vibrational frequencies and Franck-Condon (FC) factors calculated ab initio, the FC matrix for the Ã2E-X̃2A1 electronic transition contains considerable off-diagonal elements that connect (i) the CaO-stretch (ν4) mode and non-CaO stretch modes and (ii) the asymmetric CaOC stretch (ν3) and the CaOC bending (ν8) modes. The Jahn-Teller and pseudo-Jahn-Teller interactions involving the Ã2E state as well as the spin-orbit interaction induce additional vibronic transitions that are not allowed under the Born-Oppenheimer approximation. Additionally, anharmonic vibrational terms in the ground state induce transitions that are forbidden in the harmonic-oscillator approximation. Spin-orbit splitting has been observed for several vibrational levels of the Ã2E state, and an essentially constant value was measured at all levels accessed in the LIF experiment. Implications of the present spectroscopic investigation to the proposed schemes of laser-cooling MOCH3 (M = alkaline earth metals) molecules and detection of time-reversal-symmetry-violating interactions are discussed.

Dispersed Fluorescence Spectroscopy of Jet-Cooled Isobutoxy and 2-Methyl-1-butoxy Radicals.

We report dispersed fluorescence (DF) spectra of the isobutoxy and 2-methyl-1-butoxy radicals produced by photolysis of corresponding nitrites in supersonic jet expansion. Different vibrational structures have been observed in the DF spectra when different vibronic bands in the laser-induced fluorescence (LIF) spectra of each radical were pumped, which suggests that those vibronic bands be assigned to different conformers. Spectra simulated using calculated vibrational frequencies and Franck-Condon factors well reproduce the experimentally observed ones and support the assignment of the vibronic bands in the LIF spectra to the two lowest-energy conformers of each radical. DF spectra obtained by pumping the B̃ ← X̃ origin bands of the LIF spectra are dominated by CO stretch progressions because of the large difference in CO bond length between the ground (X̃) and the second excited (B̃) electronic states. Furthermore, with non-CO stretch bands pumped, the DF spectra are dominated by progressions of combination bands of the CO stretch and the pumped modes as a result of Duschinsky mixing. Ã-X̃ separation of both conformers of the isobutoxy radical has also been determined in the experiment.

Dispersed Fluorescence Spectroscopy of Jet-Cooled 2-, 3-, and 4-Methylcyclohexoxy Radicals.

Vibrational structures of the nearly degenerate X̃ and à states of the 2-, 3-, and 4-methylcyclohexoxy (MCHO) radicals were studied by jet-cooled dispersed fluorescence (DF) spectroscopy. The observed transitions were assigned on the basis of vibrational frequencies and Franck-Condon factors predicted by quantum chemical calculations. Intensities of vibronic transitions in the DF spectra are dependent on the laser-induced fluorescence (LIF) bands pumped in the experiment, which can be explained by the difference in geometry and symmetry between the lower X̃/à states and the highly excited B̃ state. All three studied isomers of MCHO have close-lying X̃ and à states although their energy separations are affected by the position of the methyl group. It is suggested by quantum chemical calculations that the lowest-energy conformers of all three isomers have the half-filled orbital oriented perpendicular to the OCH plane, which is consistent with the observed relative intensities of the B̃ → X̃ and B̃ → à origin bands. When the origin and the CO-stretch bands of the B̃ ← X̃ LIF excitation spectra were pumped, the DF spectra were dominated by CO-stretch progressions. When non-CO-stretch vibrational levels of the B̃ state were pumped, progressions of CO-stretch modes combined with the pumped vibrational mode were observed. Excited-state vibrational population relaxation from the CO stretch level to the vibrational ground level and from combination levels of the CO stretch mode and other vibrational modes to the non-CO stretch modes was observed. Analysis of the DF spectra confirms the previous conclusion that all strong LIF bands observed under jet-cooled conditions belong to a single conformer of each positional isomer (Lin et al. RSC Adv. 2012, 2, 583-589).

Direct Observation of Tetrahydrofuranyl and Tetrahydropyranyl Peroxy Radicals via Cavity Ring-Down Spectroscopy.

Room-temperature cavity ring-down (CRD) spectra of the à ← X̃ electronic transition of tetrahydrofuranyl peroxy (THFOO•) and tetrahydropyranyl peroxy (THPOO•) radicals were recorded. The peroxy radicals were produced by Cl-initiated oxidation of tetrahydrofuran and tetrahydropyran. Quantum chemical calculations of the lowest-energy conformers of all regioisomers of these two peroxy radicals have been carried out to aid the spectral simulation. Conformational identification and vibrational assignment were achieved by comparing the experimentally obtained spectra to the simulated ones. The absence of α-THPOO• absorption peaks in the CRD spectrum is attributed to ring opening due to its weak Cα'O bond.