Fabio J. Mazzotti

IDENTIFICATION OF H2CCC AS A DIFFUSE INTERSTELLAR BAND CARRIER

We present strong evidence that the broad, diffuse interstellar bands (DIBs) at 4881 and 5450 A are caused by the B 1 B1 ← X 1 A1 transition of H2CCC (l-C3H2). The large widths of the bands are due to the short lifetime of the B 1 B1 electronic state. The bands are predicted from absorption measurements in a neon matrix and observed by cavity ring-down in the gas phase and show exact matches to the profiles and wavelengths of the two broad DIBs. The strength of the 5450 A DIB leads to a l-C3H2 column density of ∼5 × 10 14 cm −2 toward HD 183143 and ∼2 × 10 14 cm −2 to HD 206267. Despite similar values of E(B −V), the 4881 and 5450 A DIBs in HD 204827 are less than one-third their strength in HD 183143, while the column density of interstellar C3 is unusually high for HD 204827 but undetectable for HD 183143. This can be understood if C3 has been depleted by hydrogenation to species such as l-C3H2 toward HD 183143. There are also three rotationally resolved sets of triplets of l-C3H2 in the 6150–6330 A region. Simulations, based on the derived spectroscopic constants and convolved with the expected instrumental and interstellar line broadening, show credible coincidences with sharp, weak DIBs for the two observable sets of triplets. The region of the third set is too obscured by the α-band of telluric O2.

ASSIGNMENT OF 5069 A DIFFUSE INTERSTELLAR BAND TO HC4H+: DISAGREEMENT WITH LABORATORY ABSORPTION BAND

Krelowski et al. have reported a weak, diffuse interstellar band (DIB) at 5069 A which appears to match in both mid-wavelength and width the A 2Πu-X 2Πg gas-phase origin absorption band of HC4H+. Here, we present laboratory rotational profiles at low temperatures which are then compared with the 5069 A DIB using ~0.1 and 0.3 A line widths based on a realistic line-of-sight interstellar velocity dispersion. Neither the band shape nor the wavelength of the maximum absorption match, which makes the association of the 5069 A DIB with HC4H+ unlikely. The magnetic dipole transition X 2Πg Ω = 1/2→X 2Πg Ω = 3/2 within the ground electronic state which competes with collisional excitation is also considered. In addition, we present the laboratory gas-phase spectrum of the A 2Πu-X 2Πg transition of HC4H+ measured at 25 K in an ion trap and identify further absorption bands at shorter wavelengths for comparison with future DIB data.

Characterization of C4H in the A2Π and X2Σ+ states by double resonance four-wave mixing.

The B(2)Π-X(2)Σ(+) electronic spectrum of C(4)H has been studied by degenerate and double resonance four-wave mixing. The technique identifies vibrational levels in the X(2)Σ(+) ground state. Its sensitivity and unique characteristics permit detection of new levels. The A(2)Π state lying 222 cm(-1) above the X(2)Σ ground state is also observed, confirming the analysis from anion photoelectron spectroscopy but with improved accuracy. Vibrational level determination in the A(2)Π electronic manifold up to 700 cm(-1) above v = 0 is made. A Renner-Teller analysis is carried out for the two lowest bending modes v(6) and v(7) in the A(2)Π state by diagonalization of the effective Hamiltonian matrix. The Renner-Teller parameters ∈(6), ∈(7), and ∈(67), the vibrations ω(6) and ω(7) and the spin-orbit coupling constant A(so) are determined.

Electronic spectra of radicals in a supersonic slit-jet discharge by degenerate and two-color four-wave mixing

Four-wave mixing techniques have been used for the measurement of electronic transitions of cold transient species generated in a supersonic slit-jet discharge expansion. The origin band of the d(3)Pi(g)-a(3)Pi(u) system of C(2) and A(2)Pi(3/2)-X[combining tilde](2)Pi(3/2) electronic transition of HC(4)S were recorded. A signal-to-noise ratio of 10(4) in the spectra was achieved, resulting in detection limits of 10(10) cm(-3) for these two molecules. Application of selective two-color resonant four-wave mixing is used for the spectral assignment utilizing the double-resonance nature of the method. The combination of these techniques with a slit source proves to be a sensitive approach for the detection of transient molecules in a molecular beam discharge.

Selective detection of radicals and ions in a slit-jet discharge by degenerate and two-color four-wave mixing.

Degenerate four-wave mixing (DFWM) was used to record the spectra of charged and neutral carbon-containing radicals generated in a pulsed discharge source within a supersonic slit-jet expansion. Detection limits of approximately 10(9) molecules cm(-3) are achieved. The DFWM method allows a selective molecular detection by varying the discharge timings. Increased spectral selectivity is obtained by applying the two-color, doubly resonant four-wave mixing variant. This shows the potential of the techniques for sensitive and selective spectral analysis of radicals in discharges. The methods are successfully used for the detection of C(4)H, HC(2)S, and HC(4)H(+) with signal-to-noise in the range of 10(2)-10(4).

Electronic absorption spectrum of triacetylene cation for astronomical considerations.

The A(2)Πg ← X(2)Πu electronic transition (4800-6000 Å) of triacetylene cation was measured in an ion trap, where the vibrational and rotational degrees of freedom were equilibrated to 25 K. The rotational profile of the origin band is predicted by a collisional-radiative rate model under conditions expected in diffuse interstellar clouds. Variation in the density of the surrounding gas, rotational temperature, and velocity dispersion are taken into account.

Electronic spectra of C6H+ and C6H3+ in the gas phase.

Measurement of the 3Π-3Π transition of C6H+ in the gas phase near 19486 cm−1 is reported. The experiment was carried out with a supersonic slit-jet expansion discharge using cavity ringdown absorption spectroscopy. Partly resolved P lines and observation of band heads permitted a rotational contour fit. Spectroscopic constants in the ground and excited-state were determined. The density of ions being sampled is merely 2×108 cm−3. Broadening of the spectral lines indicates the excited-state lifetime to be ≈100 ps. The electronic transition of HC6H2+ at 26402 cm−1 assumed to be 1A1-X1A1 in C2v symmetry could not be rotationally resolved.

Electronic spectra of C4H3Cl+ isomers

Two experimental methods were applied to identify the structure and electronic transitions of C4H3Cl+ isomers. The first is a direct absorption technique where mass-selected ions are embedded in 6 K neon matrices using a mass-selected ion beam and absorption spectra of different C4H3Cl+ isomers were thus observed. The second is a gas phase method on ions which have been collisional cooled with cryogenic helium inside of a 22-pole ion trap. The c-type (1)2 A′ ← X 2 A″ electronic transition of a C4H3Cl+ isomer could then be measured by a one-colour, two-photon technique at 20 and 50 K in the gas phase. The two sets of data, complemented by calculated excitation energies, allowed the assignment of particular isomers. Rotational structure in the gas phase spectra was resolved for C4H3 35Cl+ and C4H3 37Cl+ isomers of cis-1-chlorobutenynylium. The analysis leads to the spectroscopic constants: T 00 = 19 184.680(5), , , , , and (all in cm−1).

Three-level depletion by cavity ringdown absorption spectroscopy: proof of concept

Theoretical quantitative considerations as well as experimental data are presented based on absorption population depletion coupled with cavity ringdown spectroscopy. The absorbing number densities inside the cavity are determined by numerical integration of the coupled rate equations. The number of photons involved in absorption, cavity losses due to mirror reflectivity and stimulated emission are taken into account. The principle is to monitor a first transition by cavity ringdown spectroscopy while a second transition, with a state in common, is resonantly excited by the decaying radiation of different frequency also trapped inside the optical cavity. A numerical example is given for atomic lines of neon and the measurements carried out in a supersonic slit-jet expansion discharge demonstrate the feasibility of the technique. The technique is also proven to work with two resonant transitions of C2. Translational velocity of the jet modifying the rate equations is included in the model.

Electronic spectra of astrophysically interesting cations

The electronic spectra of polyacetylene cations were recorded at 20K in the laboratory in an ion trap instrument. These can then be compared with diffuse interstellar band (DIB) absorptions. Examination of recently published data shows that the attribution of a weak DIB at ∼506.9 nm to diacetylene cation is not justified. Study of the higher excited electronic states of polyacetylene cations shows that their widths can still be sufficiently narrow for consideration as DIB carriers.