Temperature is a very important concept in ion spectroscopy and its control has seen tremendous advances in recent years. Cryogenic ion traps are now found in many experiments and serve as thermostats, reaction vessels, clustering sources and spectroscopic sample chambers. The control over internal degrees of freedom provides routes to forming ions that are relevant at cryogenic temperatures such as in the interstellar medium and to control and lock-in conformations. It also provides a condensing environment and allows weakly bound clusters to be formed, which in turn provides new routes to action spectroscopy. This session will discuss the most recent developments in cryogenic spectroscopy and the research it enables and how new theoretical methods allow the prediction of experimental spectra as a function of temperature. The main discussion topics will cover: the best cooling methods; how temperature can be used to form exotic clusters and weakly interacting systems; and the possibilities for probing conformational locking and metastable structures.

Ahmed, Musahid↗

DOE OSTI2019

Going large(r): General Discussion

With the introduction of new ion sources and advanced mass-spectrometric techniques coupled to spectroscopy, ever larger complexes are being probed. This increase in size is coupled with an increase in complexity requiring new methodologies (both experimental and theoretical) but also providing new opportunities. This session will primarily focus on the application of ion spectroscopy of non-covalent interactions in clusters and biological systems. These include solvent clusters, secondary and tertiary structure of proteins, and weakly-bound molecular clusters. Topics covered will include: structural probes for weak interactions; advances in action spectroscopy; and conformationally selective spectroscopy. A key discussion point will concern the marriage of mass-spectrometery with optical spectroscopy. The interpretation of experimental data obtained for these larger systems demands concomitant developments in theoretical methods, and the session will provide an opportunity for comparative discussions of new theoretical approaches in this field.

Ahmed, Musahid↗

DOE OSTI2016

Communication: Thermal unimolecular decomposition of syn-CH 3 CHOO: A kinetic study

The thermal decomposition of syn-ethanal-oxide (syn-CH 3 CHOO) through vinyl hydrogen peroxide (VHP) leading to hydroxyl radical is characterized using a modification of the HEAT thermochemical protocol. The isomerization step of syn-CH 3 CHOO to VHP via a 1,4 H-shift, which involves a moderate barrier of 72 kJ/mol, is found to be rate determining. A two-dimensional master equation approach, in combination with semi-classical transition state theory, is employed to calculate the time evolution of various species as well as to obtain phenomenological rate coefficients. This work suggests that, under boundary layer conditions in the atmosphere, thermal unimolecular decomposition is the most important sink of syn-CH 3 CHOO. Thus, the title reaction should be included into atmospheric modeling. Here, the fate of cold VHP, the intermediate stabilized by collisions with a third body, has also been investigated

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DOE OSTI2015

Reactive intermediates in {sup 4}He nanodroplets: Infrared laser Stark spectroscopy of dihydroxycarbene

Singlet dihydroxycarbene (HOC{sup ¨}OH) is produced via pyrolytic decomposition of oxalic acid, captured by helium nanodroplets, and probed with infrared laser Stark spectroscopy. Rovibrational bands in the OH stretch region are assigned to either trans,trans- or trans,cis-rotamers on the basis of symmetry type, nuclear spin statistical weights, and comparisons to electronic structure theory calculations. Stark spectroscopy provides the inertial components of the permanent electric dipole moments for these rotamers. The dipole components for trans, trans- and trans, cis-rotamers are (μ{sub a}, μ{sub b}) = (0.00, 0.68(6)) and (1.63(3), 1.50(5)), respectively. The infrared spectra lack evidence for the higher energy cis,cis-rotamer, which is consistent with a previously proposed pyrolytic decomposition mechanism of oxalic acid and computations of HOC{sup ¨}OH torsional interconversion and tautomerization barriers.

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DOE OSTI2013

The Performance of Density Functionals for Sulfate-Water Clusters

The performance of 24 density functionals, Hartree-Fock, and MP2 is assessed with respect to the energetics of 49 sulfate-water clusters with between three and six water molecules. Included among the density functionals are GGA, meta-GGA, hybrid GGA, hybrid meta-GGA, and double hybrid density functionals, as well as the LDA. Three types of dispersion corrections (VV10, XDM, and -D) are tested in conjunction with these functionals. The functionals are compared using the relative and binding energies of the sulfatewater clusters as the main criteria. It is discovered that a majority of current density functionals are unable to simultaneously capture the physics necessary to describe both the relative and binding energies of the anionic solvation clusters. The only density functionals that perform acceptably with respect to both measures are XYG3 and XYGJOS, primarily due to their balanced treatment of exchange and correlation. On the other hand, density functionals with exact exchange that lack nonlocal correlation tend to perform well only for the relative energies. However, there is evidence that hybrid density functionals that provide a more comprehensive treatment of local correlation through their dependence on the kinetic energy density and their ability to treat the inhomogeneities in the present system can partially resolve this issue. While dispersion correction functionals cannot replace the accuracy provided by MP2 correlation, it is shown that the proper combination of a hybrid GGA functional with a dispersion correction functional can lead to drastic improvements in the binding energies of the parent functional, while preserving its performance with respect to the relative energies.

Environmental Molecular Sciences Laboratory↗

DOE OSTI2012

Refined energetic ordering for sulphate–water ( n = 3–6) clusters using high-level electronic structure calculations

This work reports refinements of the energetic ordering of the known low-energy structures of sulfate-water clusters SO 4 2- (H2O)n (n = 3-6) using high-level electronic structure methods. Coupled cluster singles and doubles with perturbative triples (CCSD(T)) is used in combination with an estimate of basis set effects up to the complete basis set limit using second order Møller-Plesset theory. Harmonic zero point energy (ZPE), included at the B3LYP/6-311++G** level, was found to have a significant effect on the energetic ordering. Limitations of the ZPE calculations, both due to electronic structure errors, and use of the harmonic approximation, probably constitute the largest remaining errors. Due to the often small energy differences between cluster isomers, and the significant role of ZPE, deuteration can alter the relative energies of low-lying structures, and, when it is applied in conjunction with calculated harmonic ZPE’s, even alters the global minimum for n = 4.

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