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Bonding in the ground state of C 2 is still a matter of controversy, as reasonable arguments may be made for a dicarbon bond order of 2 , 3 , or 4 . Here we report on photoelectron spectra of the C 2 − anion, measured at a range of wavelengths using a high-resolution photoelectron imaging spectrometer, which reveal both the ground X 1 Σ g + and first-excited a 3 Π u electronic states. These measurements yield electron angular anisotropies that identify the character of two orbitals: the diffuse detachment orbital of the anion and the highest occupied molecular orbital of the neutral. This work indicates that electron detachment occurs from predominantly s -like ( 3 σ g ) and p -like ( 1 π u ) orbitals, respectively, which is inconsistent with the predictions required for the high bond-order models of strongly s p -mixed orbitals. This result suggests that the dominant contribution to the dicarbon bonding involves a double-bonded configuration, with 2 π bonds and no accompanying σ bond. In spite of its apparent simplicity, the dicarbon molecule has a bonding structure which is matter of debate. Here the authors measure high-resolution spectra of the C 2 anion by photoelectron imaging, revealing a bonding configuration dominated by a double π bond, with no accompanying σ bond.

In this overview we discuss the vibrational spectrum of phosphaethyne, HCP, in its electronic ground state, as revealed by complementary experimental and theoretical examinations. The main focus is the evolution of specific spectral patterns from the bottom of the potential well up to excitation energies of approximately 25,000 cm(-1), where large-amplitude, isomerization-type motion from H-CP to CP-H is prominent. Distinct structural and dynamical changes, caused by an abrupt transformation from essentially HC bonding to mainly PH bonding, set in around 13,000 cm(-1). They reflect saddle-node bifurcations in the classical phase space--a phenomenon well known in the nonlinear dynamics literature--and result in characteristic patterns in the spectrum and the quantum-number dependence of the vibrational fine-structure constants. Two polar opposites are employed to elucidate the spectral patterns: the exact solution of the Schrödinger equation, using an accurate potential energy surface and an effective or resonance Hamiltonian (expressed in a harmonic oscillator basis set and block diagonalized into polyads), which is defined by parameters adjusted to fit either the measured or the calculated vibrational energies. The combination of both approaches--together with classical mechanics and semiclassical analyses--provides a detailed spectroscopic picture of the breaking of one bond and the formation of a new one.

Highly accurate and precise electronic structure calculations of heavy radioactive atoms and their molecules are important for several research areas, including chemical, nuclear, and particle physics. Ab initio quantum chemistry can elucidate structural details in these systems that emerge from the interplay of relativistic and electron correlation effects, but the large number of electrons complicates the calculations, and the scarcity of experiments prevents insightful theory-experiment comparisons. Here we report the spectroscopy of the 14 lowest excited electronic states in the radioactive molecule radium monofluoride (RaF), which is proposed as a sensitive probe for searches of new physics. The observed excitation energies are compared with state-of-the-art relativistic Fock-space coupled cluster calculations, which achieve an agreement of ≥99.64% (within  ~12 meV) with experiment for all states. Guided by theory, a firm assignment of the angular momentum and term symbol is made for 10 states and a tentative assignment for 4 states. The role of high-order electron correlation and quantum electrodynamics effects in the excitation energies is studied and found to be important for all states. Heavy-atom molecules can possess complicated electronic structures due to pronounced electron correlation and relativistic effects. Here, the authors describe electronic states of RaF in detail by combining accurate spectroscopy and theory approaches.

We review stimulated emission pumping as used to study molecular dynamics. The review presents unimolecular as well as scattering studies. Topics include intramolecular vibrational redistribution, unimolecular isomerization and dissociation, van der Waals clusters, rotational energy transfer, vibrational energy transfer, gas-surface interactions, atmospheric effects resulting from nonequilibrium vibrational excitation, and vibrational promotion of electron transfer.

Transition state theory is central to our understanding of chemical reaction dynamics. We demonstrate a method for extracting transition state energies and properties from a characteristic pattern found in frequency-domain spectra of isomerizing systems. This pattern—a dip in the spacings of certain barrier-proximal vibrational levels—can be understood using the concept of effective frequency, ωeff. The method is applied to the cis-trans conformational change in the S₁ state of C₂H₂ and the bond-breaking HCN-HNC isomerization. In both cases, the barrier heights derived from spectroscopic data agree extremely well with previous ab initio calculations. We also show that it is possible to distinguish between vibrational modes that are actively involved in the isomerization process and those that are passive bystanders.

A point-of-use waterborne radon-222 (222Rn) survey of a small Iowa town was performed to determine the cause of unnaturally high waterborne 222Rn concentrations in the municipality. The source of the elevated 222Rn concentrations was a newly discovered reservoir of waterborne 222Rn originating from distribution-system radium-226 (226Ra) adsorbed internal pipe scale deposits. Because the proposed national drinking water regulations for 222Rn require sampling at the origin of the distribution system rather than at the point of use, the proposed scheme for collection of water samples may not represent actual consumer waterborne 222Rn exposure in all cases.

We measured radon (222Rn) concentrations in Iowa and Minnesota and found that unusually high annual average radon concentrations occur outdoors in portions of central North America. In some areas, outdoor concentrations exceed the national average indoor radon concentration. The general spatial patterns of outdoor radon and indoor radon are similar to the spatial distribution of radon progeny in the soil. Outdoor radon exposure in this region can be a substantial fraction of an individual's total radon exposure and is highly variable across the population. Estimated lifetime effective dose equivalents for the women participants in a radon-related lung cancer study varied by a factor of two at the median dose, 8 mSv, and ranged up to 60 mSv (6 rem). Failure to include these doses can reduce the statistical power of epidemiologic studies that examine the lung cancer risk associated with residential radon exposure.

Water-plant operators may be exposed to high airborne radon-222 (²²²Rn) concentrations created when ²²²Rn gas transfers from water to air during the water treatment processes. To evaluate this hazard, we placed yearlong alpha-track radon detectors in 31 water plants. The geometric mean of the annual average airborne ²²²Rn concentrations was 3.4 pd L⁻¹ (126 Bq m⁻³), with a maximum of 133 pCi L⁻¹ (4921 Bq m⁻³). We assessed the short-term temporal variability of ²²²Rn by monitoring four water plants continuously for a 3- to 6-day period. Cumulative working level months were estimated for the time workers were in the water plants. Because airborne ²²²Rn concentration in water plants can reach levels considered unsafe for underground miners, it would be prudent to monitor airborne ²²²Rn concentrations in water plants which aerate water as part of their treatment process.