Evan B. Jochnowitz

Electronic spectroscopy of carbon chains.

Investigators have recorded the electronic spectra of assorted carbon-chain systems in the gas phase using a variety of methods, ranging from direct cavity ringdown absorption spectroscopy to photofragmentation techniques that utilize the cooling capabilities of an ion trap. We summarize the results from these studies and compare them with astronomical measurements of the diffuse interstellar band (DIB) absorptions. Although carbon chains comprising up to a handful of carbon atoms cannot be the carrier species, we explore which chains remain viable. In particular, the (1)Sigma(u)(+)-Chi(1)Sigma(g)(+) transitions of the odd-numbered carbon chains (n = 17,19,...) possess large oscillator strengths and lie in the 400-900-nm DIB range. The origin bands of larger bare carbon rings, such as C(18), have also been observed, with striking similarities to some DIB measurements at high resolution, although at other wavelengths. Finally, we consider recently obtained electronic spectra of metal-containing carbon chains.

A Revisited Picture of the Mechanism of Glycerol Dehydration

The dehydration mechanism of neutral glycerol in the gas phase was investigated by means of metadynamics simulations. Structures, vibrational frequencies, Gibbs free energy barriers, and rate constants at 800 K were computed for the different steps involved in the pyrolytic process. In this article, we provide a novel mechanism for the dehydration of neutral glycerol, proceeding via formation of glycidol with a barrier of 66.8 kcal/mol. The formation of glycidol is the rate limiting step of the overall decomposition process. Once formed, glycidol converts into 3-hydroxypropanal with a barrier of 49.5 kcal/mol. 3-Hydroxypropanal can decompose further into acrolein or into formaldehyde and vinyl-alcohol with barriers of 53.9 and 35.3 kcal/mol, respectively. These findings offer new insights to available experimental data based on glycerol pyrolysis studies performed with isotopic labeling and on the interpretation of the chemistry of glycerol and sugars in pyrolytic conditions.

Electronic absorption spectra of the protonated polyacetylenes HC2nH2+ (n=3,4) in the gas phase

A new approach has been developed for the purpose of measuring the electronic transitions to bound exited states for cations that have been collisionally relaxed to low vibrational and rotational temperatures. This has been used to obtain the first gas phase electronic spectra of the protonated polyacetylenes using a two-color ion-photodissociation approach. Specifically, the origin bands in the B (1)A(1)<-- X(1)A(1) transitions of HC(6)H(2) (+) and HC(8)H(2) (+) (C(2v) geometry) were observed at 26,403.3 and 21,399.8 cm(-1). Data on such cooled systems allow a direct comparison between laboratory and astrophysical measurements.

Electronic spectroscopy of carbon chains

Gas phase electronic spectra allow direct comparisons between laboratory data and the wealth of astrophysical measurements that have been tabulated. Over the past decade a number of assorted carbon chain systems have been spectroscopically investigated, yielding an understanding of the transitions and trends apparent among their homologous series. This rigorous program begins with trapping unstable carbon chain ions and radicals in neon matrices, where origin bands and vibrational data are obtained. From these results one can then seek out the gas phase transitions in higher resolution in order to more accurately determine assignments and spectroscopic constants. To this purpose, laser spectroscopic methods are employed, including pulsed and cw cavity ringdown, resonant enhanced multiphoton ionisation, and more recently, a two-photon two-colour excitation/fragmentation approach to investigate trapped ions. From a comparison involving the electronic spectra of a number of carbon chain systems measured in the laboratory with diffuse interstellar band (DIB) absorptions, one concludes that species involving only a handful of carbon atoms can not be the carriers. However, larger carbon chains and ring species still remain viable. In this review, we consider which systems require further investigation, including these longer species, metal-capped chains and other cationic radicals.

Gas phase electronic spectrum of T-shaped AlC2 radical

Gas phase electronic transitions for the C 2B2<--X 2A1 and D 2B1<--X 2A1 band systems of T-shaped AlC2 (C2v) radical have been measured in the 345-475 nm range. Vibrational analyses of both band systems are reported. Simulation of several rotationally resolved bands confirms previously obtained rotational parameters for the C 2B2 state. The radical is produced by ablating an aluminum rod in the presence of acetylene gas. The resulting supersonic molecular beam is probed using both mass-selective resonant two-color two-photon ionization and laser induced fluorescence. Ab initio calculations and vertical electronic excitation energies help the assignment. Vibrational frequencies for the X 2A1, C 2B2, and D 2B1 states have been determined. Rotational analysis of a number of bands yields spectroscopic constants for one vibronic state in the C 2B2 manifold and the origin band of the D 2B1<--X 2A1 system.