Measurement of the spectral signature of small carbon clusters at near and far infrared wavelengths

A significant percentage of the carbon inventory of the circumstellar and interstellar media may be in the form of large refractory molecules (or small grains) referred to as carbon clusters. At the small end, uneven numbers of carbon atoms seem to be preferred, whereas above 12 atoms, clusters containing an even number of carbon atoms appear to be preferred in laboratory chemistry. In the lab, the cluster C-60 appears to be a particularly stable form and has been nicknamed Bucky Balls because of its resemblance to a soccer ball and to geodesic domes designed by Buckminster Fuller. In order to investigate the prevalence of these clusters, and their relationship to the polycyclic aromatic hydrocarbons (PAHs) that have become the newest focus of IR astronomy, it is necessary to determine the spectroscopic characteristics of these clusters at near and far infrared wavelengths. Described here is the construction of a near to far IR laser magnetic resonance spectrometer that has been built at the University of California Berkeley in order to detect and characterize these spectra. The equipment produces carbon clusters by laser evaporation of a graphitic target. The clusters are then cooled in a supersonic expansion beam in order to simulate conditions in the interstellar medium (ISM). The expansion beam feeds into the spectrometer chamber and permits concentrations of clusters sufficiently high as to permit ultra-high resolution spectroscopy at near and far IR wavelengths. The first successful demonstration of this apparatus occurred last year when the laboratory studies permitted the observational detection of C-5 in the stellar outflow surrounding IRC+10216 in the near-IR. Current efforts focus on reducing the temperature of the supersonic expansion beam that transport the C clusters evaporated from a graphite target into the spectrometer down to temperatures as low as 1 K

The C9 cluster: Structure and infrared frequencies

The high resolution infrared spectrum of the C9 cluster has been measured in direct absorption by infrared diode laser spectroscopy of a pulsed supersonic carbon cluster jet. Fifty-one rovibrational transitions have been assigned to the nu6 (sigmau ) antisymmetric stretch fundamental of the 1Sigma + 9 linear ground state of C9. The measured rotational constant [429.30(50) MHz] is in good agreement with ab initio calculations and indicates an effective bond length of 1.278 68(75) Å, consistent with cumulenic bonding in this cluster. Several perturbations are observed in the upper state, and the upper- and lower-state centrifugal distortion constants are observed to be anomolously large, evidencing a high degree of Coriolis mixing of the normal modes

The structure of the C4 cluster radical

The first infrared spectrum of gas phase, jet-cooled C4 has been measured by high resolution diode laser absorption spectroscopy. Twelve rovibrational transitions are assigned to the nu3(sigmau) antisymmetric stretch of linear 3Sigma - g C4. No evidence is observed for the bent structure of triplet C4 recently observed in a matrix study by Cheung and Graham [J. Chem. Phys. 91, 6664 (1989)]. Indeed, the measured band origin (1548.9368(21) cm^–1) and effective ground state C–C bond length [1.304 31(21)A] are consistent with several ab initio predictions of a rigid, linear, cumulenic structure for this cluster radical

Direct measurement of the fine-structure interval and g_J factors of singly ionized atomic carbon by laser magnetic resonance

We present the results of laser magnetic resonance measurements performed on the ground ^2P state of singly ionized atomic carbon (C_II). The 2^P_(3/2) ← ^2P_(1/2) fine-structure intervals of both ^(12)C^+ and ^(13)C^+ have been determined with a precision of approximately 1 ppm, and the g_J factors to approximately one part in 10^4. Specifically, we find that g_(J=(1/2)) = 0.66576(11) and g_(J=(3/2)) = 1.33412(11), while for ^(12)C^+ ΔE_0(^2P_(3/2) ← ^2P_(1/2))= 1900536.9(1.3) MHz, with ΔE_0(^2P_(3/2) ← ^2P_(1/2)) = 1900545.8(2.1) and ΔE(^2P(3/2) ← ^2P_(1/2), F = 2 ← 1) = 1900466.1(2.3) MHz in ^(13)C^+. The highly precise values of the ^(12)C_II and ^(13)C_II fine-structure intervals verify the already secure far-infrared astronomical identification of C^+ and should allow the interstellar (^(12)C / ^(13)C) ratio to be unambiguously determined in a number of environments

Experimental determination of dipole moments for molecular ions: Improved measurements for ArH^+

An improved value for the dipole moment of ArH^+ has been obtained from new measurements of the rotational g factors of ArH^+ and ArD^+ made with tunable far‐IR laser spectroscopy. Systematic errors present in earlier measurements have been eliminated. The new result (μ=3.0±0.6 D) is slightly higher than the ab initio value of Rosmus (2.2 D) at the 2σ limits of precision

Dynamics of Micropollutant Adsorption to Polystyrene Surfaces Probed by Angle-Resolved Second Harmonic Scattering

Angle-resolved second harmonic scattering is used to probe the adsorption dynamics of aqueous cationic and anionic dye molecules onto polystyrene surfaces. The adsorptions of malachite green to negatively charged polystyrene and naphthol yellow S to positively charged polystyrene are both highly favorable, with Î"GAds values of -10.9 ± 0.2 and -10.27 ± 0.09 kcal/mol, respectively. A competitive displacement methodology was employed to obtain values for the adsorption free energies of various smaller neutral organic molecules, including the important micropollutant ascorbic acid, caffeine, and pentoxifylline. For charged adsorbers, electrostatic interactions appear to significantly contribute to adsorption behavior. However, electrostatic repulsion does not necessarily deter the adsorption of molecules with large uncharged moieties (e.g., surfactants). In these cases, the mechanism of adsorption is dominated by van der Waals interactions, with the surface charge playing a relatively minor role

Cavity ringdown laser absorption spectroscopy and time-of-flight mass spectroscopy of jet-cooled silver silicides

The cavity ringdown technique has been employed for the first spectroscopic characterization of the AgSi molecule, which is generated in a pulsed laser vaporization plasma reactor. A total of 20 rovibronic bands between 365 and 385 nm have been measured and analyzed to yield molecular properties for the X, B, and C 2Sigma states of AgSi. A time-of-flight mass spectrometer simultaneously monitors species produced in the molecular beam and has provided the first direct evidence for the existence of polyatomic silver silicides. Comparison of the AgSi data to our recent results for the CuSi diatom reveals very similar chemical bonding in the two coinage metal silicides, apparently dominated by covalent interactions

Carbon in The Universe: PAHs and Clusters

Following the initial demonstration of this new technique (Science 265 1686 (1994)) and its application to a series of neutral PAHs which have been proposed as condidates for the UIRs (Nature 380, 227 (1996)), we have concentrated on two major aspects of this project. 1. Developing a detailed model for infrared emission spectra of a collection of highly excited PAH molecules, in which experimental bandshapes and temperature-dependent redshifts are used in conjunction with ab initio vibrational frequencies and intensities to simulate the UIR bands. This shows that a collection of nine different cations (as large as ovalene) reproduce the UIR features better than do a collection of the corresponding neutrals, but a detailed match with the UIRs is not obtained. 2. Construction of SPIRES apparatus for the study of PAH ion emission spectra. The design of this experiment is shown and described. Unfortunately a disasterous accident occurred just as we were preparing to start the testing of the ion apparatus. A vacuum implosion occurred, destroying the liquid He cooled monochromator. It has taken us nearly one full year to reconstruct this, and we arc only now in the final testing of the new system. We expect to try the ion experiments by the end of summer

New Insights into the Charge-Transfer-to-Solvent Spectrum of Aqueous Iodide: Surface versus Bulk.

Liquid phase charge-transfer-to-solvent (CTTS) transitions are important, as they serve as photochemical routes to solvated electrons. In this work, broadband deep-ultraviolet electronic sum frequency generation (DUV-ESFG) and two-photon absorption (2PA) spectroscopic techniques were used to assign and compare the nature of the aqueous iodide CTTS excitations at the air/water interface and in bulk solution. In the one-photon absorption (1PA) spectrum, excitation to the 6s Rydberg-like orbital (5p → 6s) gives rise to a pair of spin-orbit split iodine states, 2P3/2 and 2P1/2. In the 2PA spectra, the lower-energy 2P3/2 peak is absent and the observed 2PA peak, which is ∼0.14 eV blue-shifted relative to the upper 2P1/2 CTTS peak seen in 1PA, arises from 5p → 6p electronic promotion. The band observed in the ESFG spectrum is attributed to mixing of excited states involving 5p → 6p and 5p → 6s promotions caused by both vibronic coupling and the external electric field generated by asymmetric interfacial solvation