Resonant two-photon ionization, ultraviolet hole-burning, and resonant ion-dip infrared (RIDIR) spectroscopy were used to assign and characterize the hydrogen-bonding topology of two conformers of the benzene-(water) 8 cluster. In both clusters, the eight water molecules form a hydrogen-bonded cube to which benzene is surface-attached. Comparison of the RIDIR spectra with density functional theory calculations is used to assign the two (water) 8 structures in benzene-(water) 8 as cubic octamers of D 2 d and S 4 symmetry, which differ in the configuration of the hydrogen bonds within the cube. OH stretch vibrational fundamentals near 3550 wave numbers provide unique spectral signatures for these “molecular ice cubes.”

Resonant ion-dip infrared spectroscopy of benzene-(water) 9 : Expanding the cube The techniques of resonant two-photon ionization ͑R2PI͒, UV-UV ͑ultraviolet͒ hole-burning, and resonant ion-dip infrared ͑RIDIR͒ spectroscopies have been employed along with density functional theory ͑DFT͒ calculations to assign and characterize the hydrogen-bonding topologies of two isomers each of the benzene-͑water) 8 and (benzene͒ 2 ͑water) 8 gas-phase clusters. The BW 8 isomers ͑Bϭbenzene, Wϭwater͒ have R2PI spectra which are nearly identical to one another, but shifted by about 5 cm Ϫ1 from one another. This difference is sufficient to enable interference-free RIDIR spectra to be recorded. As with smaller BW n clusters, the BW 8 clusters fragment following photoionization by loss of either one or two water molecules. The OH stretch IR spectra of the two BW 8 isomers bear a close resemblance to one another, but differ most noticeably in the double-donor OH stretch transitions near 3550 cm Ϫ1 . Comparison to DFT calculated minimum energy structures, vibrational frequencies, and infrared intensities leads to an assignment of the H-bonding topology of the BW 8 isomers as nominally cubic water octamers of S 4 and D 2d symmetry surface attached to benzene through a H-bond. A series of arguments based on the R2PI and hole-burning spectra leads to an assignment of additional features in the R2PI spectra to two isomers of B 2 W 8 . The OH stretch RIDIR spectra of these isomers show them to be the corresponding S 4 and D 2d analogs of B 2 W 8 in which the benzene molecules each form a H-bond with a different dangling OH group on the W 8 sub-cluster.

The primary reactions of the lowest energy triplet states of diacetylene (C4H2*) with 1,3-butadiene (C4H6) in a helium buffer are characterized with a molecular beam pump−probe technique. Triplet diacetylene is prepared in the early portions of a molecular expansion by laser excitation of the 2 061 0 band of the 1Δu ← X1Σ+ g transition in C4H2 at 231.5 nm, which rapidly interconverts to high vibrational levels of the lowest energy triplet surfaces. The subsequent reactions with C4H6 are allowed to proceed for 20 μs while the expansion traverses a short ceramic reaction tube or slit channel. Primary products are observed by quenching secondary processes as molecular collisions cease outside the tube. The major photochemical products C6H6 and C8H6 are detected in a linear time-of-flight mass spectrometer using both vacuum ultraviolet photoionization and resonant two-photon ionization (R2PI). R2PI spectra of the C6H6 and C8H6 products unambiguously identify them as benzene and phenylacetylene, respectively. Based on deuterium substitution experiments, a mechanism for these ring-forming reactions is proposed. The potential importance of these reactions for forming aromatics in sooting flames and planetary atmospheres is discussed.

Resonant two-photon ionization spectroscopy was used to study jet-cooled Ni2 produced by pulsed laser ablation of a nickel target in the throat of a supersonic nozzle using argon as the carrier gas. Spectral regions previously investigated using helium as the carrier gas were reinvestigated, and the improved cooling achieved was found to suppress transitions arising from an Ω=4 state that had been thought to be the ground state. Seven new vibronic progressions were assigned, with spectroscopic constants determined for the excited states. The predissociation threshold in Ni2 was reinvestigated, and a revised value for the binding energy is given as D○0(Ni2)=2.042±0.002 eV. The ionization energy of Ni2 was found to be 7.430±0.025 eV, and from this result and the revised bond dissociation energy of the neutral, the binding energy of the cation was calculated to be D○0(Ni+2)=2.245±0.025 eV. Similarly, D○0(Ni−2)=1.812±0.014 eV is obtained using D○0(Ni2) and the electron affinities of Ni and Ni2. Twenty bands were rotationally resolved, all originating from a lower state of Ω″=0+g or 0−u which we argue is the true ground state, in agreement with ligand field and ab initio theoretical studies. The rotational analysis also yielded a ground state bond length of 2.1545±0.0004 Å for 58Ni2.

Fluorescence-dip infrared spectroscopy ͑FDIRS͒ is employed to record the infrared spectra of the isolated, jet-cooled tropolone molecule ͑TrOH͒ and its singly deuterated isotopomer TrOD in the O-H and C-H stretch regions. The ability of the method to monitor a single ground-state level enables the acquisition of spectra out of the lower and upper levels of the zero-point tunneling doublet free from interference from one another. The high power of the optical parametric oscillator used for infrared generation produces FDIR spectra with good signal-to-noise despite the weak intensity of the C-H and O-H stretch transitions in tropolone. The expectation that both spectra will exhibit two OH stretch transitions separated by the OH(vϭ1) tunneling splitting is only partially verified in the present study. The spectra of TrOH are compared with those from deuterated tropolone ͑TrOD͒ to assign transitions due to C-H and O-H, which are in close proximity in TrOH. The appearance of the spectra out of lower ͑a 1 symmetry͒ and upper ͑b 2 symmetry͒ tunneling levels are surprisingly similar. Two sharp transitions at 3134.9 cm Ϫ1 ͑out of the a 1 tunneling level͒ and 3133.9 cm Ϫ1 ͑out of the b 2 tunneling level͒ are separated by the ground-state tunneling splitting ͑0.99 cm Ϫ1 ͒, and thereby terminate in the same upper state tunneling level. Their similar intensities relative to the C-H stretch transitions indicate that the y-and z-polarized transitions are of comparable intensity, as predicted by ab initio calculations. The corresponding transitions to the other member of the upper state tunneling doublet are not clearly assigned by the present study, but the broad absorptions centered about 12 cm Ϫ1 below the assigned transitions are suggested as the most likely possibility for the missing transitions.

The first definitive experimental characterization of the unusual HBBH molecule is reported. It has been generated by several different methods and trapped in neon and argon matrices for a detailed electron spin resonance (ESR) investigation. A complete resolution of the IlB and 'H nuclear hyperfine structure into isotropic and dipolar components was possible. Ab initio CI calculations, conducted as part of this experimental study, yielded Aiso and Adip parameters in good agreement with the observed values. These ESR results offer the first confirmation that HBBH has a 3Xgelectronic ground state as predicted by earlier theoretical calculations. The HBBH molecule resembles acetylene with one electron removed from each of the x-type molecular orbitals. Molecules that contain boron-boron double bonds are extremely rare.

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The electron affinity of NO has been measured to be 0.026 eV by laser photodetachment experiments. This low electron affinity (just 2.5 kJ/mol or 210 cm-1) presents a computational challenge that requires careful attention to several aspects of the computational procedure required to predict the electron affinity of NO from first principles. We have used augmented correlation consistent basis sets with several coupled cluster methods to calculate the molecular energies, bond dissociation energies, bond lengths, vibrational frequencies, and potential energy curves for NO and NO-. The electron affinity of NO, EA0, using the CCSD(T) method and extrapolating to the complete basis set limit, is calculated to be 0.028 eV. The calculated bond dissociation energies, D0, for NO and NO- are 622 and 487 kJ/mol, respectively, compared with experimental values of 626.8 and 487.8 kJ/mol. From the calculated potential energy curves for NO and NO- the vibrational wavefunctions were determined. The calculated vibrational wavefunctions predict Franck-Condon factor ratios in good agreement with the values determined in the photodetachment experiment.