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The C3 molecule is an important species with implications in combustion and astrochemistry, and much of the interest in this molecule is related to its interactions with other species found in these environments. We have utilized helium droplet beam techniques along with a recently developed carbon cluster evaporation source to assemble C3–(H2O)n and C3–(D2O)n complexes with n = 1–2 and to record their rovibrational spectra. We observe only a single isomer of the n = 1 complex, in agreement with theoretical predictions as well as data from earlier matrix isolation studies. The spectra of the n = 1 complex are consistent with the ab initio structure, which involves a nearly linear arrangement of CCC–HO atoms in the complex. The C3–H2O spectrum we obtain exhibits slight differences from the analogous C3–D2O spectrum, which we assign to a difference in linewidth between the two spectra. We have also examined the n = 2 species and obtained a structure that appears to be distinct from those observed in matrix isolation studies and, to our knowledge, has not been previously observed. [ABSTRACT FROM AUTHOR]

The catalytic reduction of CO2 to produce hydrocarbon fuels is a topic that has gained significant attention. Development of efficient catalysts is a key enabler to such approaches, and metal-based catalysts have shown promise towards this goal. The development of a fundamental understanding of the interactions between CO2 molecules and metal atoms is expected to offer insight into the chemistry that occurs at the active site of such catalysts. In the current study, we utilize helium droplet methods to assemble complexes composed of a CO2 molecule and a Mg or Al atom. High-resolution infrared (IR) spectroscopy and optically selected mass spectrometry are used to probe the structure and binding of the complexes, and the experimental observations are compared with theoretical results determined from ab initio calculations. In both the Mg-CO2 and Al-CO2 systems, two IR bands are obtained: one assigned to a linear isomer and the other assigned to a T-shaped isomer. In the case of the Mg-CO2 complexes, the vibrational frequencies and rotational constants associated with the two isomers are in good agreement with theoretical values. In the case of the Al-CO2 complexes, the vibrational frequencies agree with theoretical predictions; however, the bands from both structural isomers exhibit significant homogeneous broadening sufficient to completely obscure the rotational structure of the bands. The broadening is consistent with an upper state lifetime of 2.7 ps for the linear isomer and 1.8 ps for the T-shaped isomer. The short lifetime is tentatively attributed to a prompt photo-induced chemical reaction between the CO2 molecule and the Al atom comprising the complex. [ABSTRACT FROM AUTHOR]

The ionization and charge transfer processes, which occur when a doped helium droplet undergoes electron impact, are studied for droplets doped with van der Waals complexes with various structures and electrostatic moments. The mass spectra of the two isomers of hydrogen cyanide complexed with either cyanoacetylene or acetylene in helium droplets were obtained using optically selected mass spectrometry, and show that the structure of the complex has a large effect on the fragmentation pattern. The resulting fragmentation pattern is consistent with an ionization process in which charge steering strongly influences the site of initial ionization. The observed dissociation products may also be subject to caging by the helium matrix. [ABSTRACT FROM AUTHOR]

Rotationally resolved infrared spectra are reported for the binary complexes of HCN and LiF, LiCl, NaF, and NaCl, formed in helium nanodroplets. Stark spectroscopy is used to determine the dipole moments for these complexes. Ab initio calculations are also reported for these complexes, revealing the existence of several different isomers of these binary systems. In the frequency region examined in this experimental study we only observe one of these, corresponding to the salt binding to the nitrogen end of the HCN molecule. The experimental rotational constants, dipole moments, and vibrational frequency shifts are all compared with the results from ab initio calculations for this isomer. [ABSTRACT FROM AUTHOR]

A technique that combines infrared laser spectroscopy and helium nanodroplet mass spectrometry, which we refer to as optically selected mass spectrometry, is used to study the efficiency of ion cooling in helium. Electron-impact ionization is used to form He+ ions within the droplets, which go on to transfer their charge to the HCN dopant molecules. Depending upon the droplet size, the newly formed ion either fragments or is cooled by the helium before fragmentation can occur. Comparisons with gas-phase fragmentation data suggest that the cooling provided by the helium is highly nonthermal. An “explosive” model is proposed for the cooling process, given that the initially hot ion is embedded in such a cold solvent. [ABSTRACT FROM AUTHOR]

The process of electron impact ionization of a helium atom in a helium nanodroplet is studied for the cases of hydrogen cyanide, acetylene, and cyanoacetylene in helium by using a new experimental method called optically selected mass spectroscopy. This method is used to study the charge migration in helium and reveals that the probability of charge transfer to a solvated molecule does not approach unity for small droplets and depends on the identity of the solvated molecule.

A study is conducted to examine the effects of liquid helium cooling on the fragmentation of ions formed by electron impact mass ionization. It is estimated that as much as 90% of the energy released by the charge transfer process is dissipated to the helium on the time scale of fragmentation.

Helium droplet beam methods are a versatile technique that can be used to assemble a wide variety of atomic and molecular clusters. In recent years, methods have been developed to utilize helium droplets as nano-calorimeters to measure the binding energies of weakly bound complexes assembled within the droplet. In the current investigation we extend the helium droplet calorimetry approach to the study of a very strongly bound system: carbon clusters which are bound by several eV per atom. We utilize laser heating of bulk carbon samples to dope the helium droplets with evaporated carbon species. Depending on the laser target, the vaporization plume is found to consist primarily of C3 alone or C2 and C3. These species are sequentially captured by the droplet and assembled into larger carbon clusters in a stepwise manner. The assembled Cn clusters are detected via mass spec-trometry of the doped droplets and the droplet sizes required to detect the various carbon clusters observed are used to estimate the reaction energies of the associated assembly pathways. The helium droplet data qualitatively reflect the trends in assembly energetics, but at first glance appear to yield energies that differ dramatically from theoretical values. Statistical modeling of the helium droplet calorimetry experiment reconciles the differences quantitatively. Our modeling also generates a calibration curve that relates the assembly/reaction energy and threshold mean droplet size over a range of energies from van der Waals interactions to chemical bonding, enabling helium droplet calorimetry methods to be applied quantitatively to a large number of systems. [ABSTRACT FROM AUTHOR]

Helium droplet beam methods are a versatile technique that can be used to assemble a wide variety of atomic and molecular clusters. In recent years, methods have been developed to utilize helium droplets as nano-calorimeters to measure the binding energies of weakly bound complexes assembled within the droplet. In the current investigation we extend the helium droplet calorimetry approach to the study of a very strongly bound system: carbon clusters which are bound by several eV per atom. We utilize laser heating of bulk carbon samples to dope the helium droplets with evaporated carbon species. Depending on the laser target, the vaporization plume is found to consist primarily of C3 alone or C2 and C3. These species are sequentially captured by the droplet and assembled into larger carbon clusters in a stepwise manner. The assembled Cn clusters are detected via mass spec-trometry of the doped droplets and the droplet sizes required to detect the various carbon clusters observed are used to estimate the reaction energies of the associated assembly pathways. The helium droplet data qualitatively reflect the trends in assembly energetics, but at first glance appear to yield energies that differ dramatically from theoretical values. Statistical modeling of the helium droplet calorimetry experiment reconciles the differences quantitatively. Our modeling also generates a calibration curve that relates the assembly/reaction energy and threshold mean droplet size over a range of energies from van der Waals interactions to chemical bonding, enabling helium droplet calorimetry methods to be applied quantitatively to a large number of systems. [ABSTRACT FROM AUTHOR]

The C3 molecule is an important species known to participate in key chemical reactions in combustion and astrochemistry. Its occurrence in environments of interest, its intramolecular physics, and its intermolecular reactivity have been areas of extensive and ongoing study. Much of the interest in C3 is related to investigating its interactions with other species relevant to combustion processes or astrochemistry. Helium droplet methods offer a promising route to assemble and study a wide variety of novel complexes, clusters, and adducts made from C3. Here we report the results of our recent efforts to dope cold helium droplets with C3 molecules and record the rotationally-resolved infrared spectrum of the embedded C3. The spectrum consists of P(2), R(0), and R(2) lines well-described by a linear rotor Hamiltonian with ν0 = 2039.09(2) cm-1, B = 0.204(5) cm-1, and T = 0.37 K. The B rotational constant of the C3 molecule is found to be reduced from its gas-phase value by a factor of 2.1 due to rotational following by the helium solvent. [ABSTRACT FROM AUTHOR]

The C 3 molecule is an important species with implications in combustion and astrochemistry, and much of the interest in this molecule is related to its interactions with other species found in these environments. We have utilized helium droplet beam techniques along with a recently developed carbon cluster evaporation source to assemble C 3 -(H 2 O) n and C 3 -(D 2 O) n complexes with n = 1-2 and to record their rovibrational spectra. We observe only a single isomer of the n = 1 complex, in agreement with theoretical predictions as well as data from earlier matrix isolation studies. The spectra of the n = 1 complex are consistent with the ab initio structure, which involves a nearly linear arrangement of CCC-HO atoms in the complex. The C 3 -H 2 O spectrum we obtain exhibits slight differences from the analogous C 3 -D 2 O spectrum, which we assign to a difference in linewidth between the two spectra. We have also examined the n = 2 species and obtained a structure that appears to be distinct from those observed in matrix isolation studies and, to our knowledge, has not been previously observed.

Competing Interests: AUTHOR DISCLOSURES The authors report no actual or potential conflicts of interest with regard to this article.