How Vibrational Notations Can Spoil Infrared Spectroscopy: A Case Study on Isolated Methanol.

Unraveling methanol's infrared spectrum has challenged spectroscopists for a century, with numerous loose ends still to be explored. We engage in this exploration based on experiments of isolating single methanol molecules in solid argon and neon matrices. We report infrared spectra of methanol in its natural isotopic composition and with partial and full deuteration.

Solving the Puzzle of the Carbonic Acid Vibrational Spectrum - an Anharmonic Story.

Against the general belief that carbonic acid is too unstable for synthesis, it was possible to synthesize the solid as well as gas-phase carbonic acid. It was suggested that solid carbonic acid might exist in Earth's upper troposphere and in the harsh environments of other solar bodies, where it undergoes a cycle of synthesis, decomposition, and dimerization. To provide spectroscopic data for probing the existence of extraterrestrial carbonic acid, matrix-isolation infrared (MI-IR) spectroscopy has shown to be essential.

Kinetic isotope effects on hydrogen/deuterium disordering and ordering in ice crystals: A Raman and dielectric study of ice VI, XV, and XIX.

Ice XIX and ice XV are both partly hydrogen-ordered counterparts to disordered ice VI. The ice XIX → XV transition represents the only order-to-order transition in ice physics. Using Raman and dielectric spectroscopies, we investigate the ambient-pressure kinetics of the two individual steps in this transition in real time (of hours), that is, ice XIX → transient ice VI (the latter called VI‡) and ice VI‡ → ice XV.

The impact of alcohol and ammonium fluoride on pressure-induced amorphization of cubic structure I clathrate hydrates.

We have investigated pressure-induced amorphization (PIA) of an alcohol clathrate hydrate (CH) of cubic structure type I (sI) in the presence of NH4F utilizing dilatometry and x-ray powder diffraction. PIA occurs at 0.98 GPa at 77 K, which is at a much lower pressure than for other CHs of the same structure type.

Configurational entropy of ice XIX and its isotope effect.

Ice XIX is a partly hydrogen-ordered polymorph related to disordered ice VI, similar to ice XV. We here investigate the order-order-disorder sequence ice XIX→ice XV→ice VI based on calorimetry at ambient pressure both for DO and HO-ice XIX. From these data we extract configurational entropy differences between ice XIX, ice XV and ice VI.

Tuning the low-temperature phase behavior of aqueous ionic liquids.

Water's anomalous behavior is often explained using a two-liquid model, where two types of water, high-density liquid (HDL) and low-density liquid (LDL), can be separated a liquid-liquid phase transition (LLPT) at low temperature. Mixtures of water and the ionic liquid hydrazinium trifluoroacetate were suggested to also show an LLPT but with the advantage that there is no rapid ice crystallization hampering its observation. It remains controversial whether these solutions exhibit an LLPT or are instead associated with complex phase separation phenomena.

Thermodynamically Stable Intermediate in the Course of Hydrogen Ordering from Ice V to Ice XIII.

Even though many partially ordered ices are known, it remains elusive to understand and categorize them. In this study, we study the ordering from ice V to XIII using calorimetry at ambient pressure and discover that the transition takes place via an intermediate that is thermodynamically stable at 113-120 K. Our isothermal ordering approach allows us to highlight the distinction of this intermediate from ice V and XIII, where there are clear differences both in terms of enthalpy and ordering kinetics.

A laboratory-based multifunctional near ambient pressure X-ray photoelectron spectroscopy system for electrochemical, catalytic, and cryogenic studies.

A versatile multifunctional laboratory-based near ambient pressure x-ray photoelectron spectroscopy (XPS) instrument is presented. The entire device is highly customized regarding geometry, exchangeable manipulators and sample stages for liquid- and solid-state electrochemistry, cryochemistry, and heterogeneous catalysis. It therefore delivers novel and unique access to a variety of experimental approaches toward a broad choice of functional materials and their specific surface processes.

Investigating freezing-induced acidity changes in citrate buffers.

Citrate buffers are commonly utilized in the field of biomolecule stabilization. We investigate their applicability in the frozen state within a range of initial pHs (2.5 to 8.

Enthalpy Change from Pure Cubic Ice I to Hexagonal Ice I.

The preparation of pure cubic ice without hexagonal stacking faults has been realized only recently by del Rosso et al. ( 2020, 19, 663-668) and Komatsu et al. ( 2020, 11, 464).

Neutron scattering study of polyamorphic THF·17(HO) - toward a generalized picture of amorphous states and structures derived from clathrate hydrates.

From crystalline tetrahydrofuran clathrate hydrate, THF-CH (THF·17HO, cubic structure II), three distinct polyamorphs can be derived. First, THF-CH undergoes pressure-induced amorphization when pressurized to 1.3 GPa in the temperature range 77-140 K to a form which, in analogy to pure ice, may be called high-density amorphous (HDA).

Nucleation and growth of crystalline ices from amorphous ices.

We here review mostly experimental and some computational work devoted to nucleation in amorphous ices. In fact, there are only a handful of studies in which nucleation and growth in amorphous ices are investigated as two separate processes. In most studies, crystallization temperatures T or crystallization rates R are accessed for the combined process.

Glass Polymorphism in Hyperquenched Aqueous LiCl Solutions.

We investigate the glass polymorphism of dilute LiCl-HO in the composition range of 0-5.8 mol % LiCl. The solutions are vitrified at ambient pressure (requires hyperquenching with ∼10 K s) and transformed to their high-density state using a special high-pressure annealing protocol.

Raman Marker Bands for Secondary Structure Changes of Frozen Therapeutic Monoclonal Antibody Formulations During Thawing.

In this work we use Raman spectroscopy for protein characterization in the frozen state. We investigate the behavior of frozen therapeutic monoclonal antibody IgG1 formulation upon thawing by Raman spectroscopy. Secondary and tertiary structure of the protein in three different mab formulations in the frozen state are followed through observation of marker bands for α-helix, β-sheet and random coil.

Infrared Spectroscopy on Equilibrated High-Density Amorphous Ice.

High-density (HDA) and low-density amorphous ices (LDA) are believed to be counterparts of the high- and low-density liquid phases of water, respectively. In order to better understand how the vibrational modes change during the transition between the two solid states, we present infrared spectroscopy measurements, following the change of the decoupled OD-stretch () (∼2460 cm) and OH-combinational mode ( + , + 2) (∼5000 cm). We observe a redshift from HDA to LDA, accompanied with a drastic decrease of the bandwidth.

Pressure-annealed high-density amorphous ice made from vitrified water droplets: A systematic calorimetry study on water's second glass transition.

In previous work, water's second glass transition was investigated based on an amorphous sample made from crystalline ice [Amann-Winkel et al., Proc. Natl.

Increase of Radiative Forcing through Midinfrared Absorption by Stable CO Dimers?

We performed matrix-isolation infrared (MI-IR) spectroscopy of carbon dioxide monomers, CO, and dimers, (CO), trapped in neon and in air. On the basis of vibration configuration interaction (VCI) calculations accounting for mode coupling and anharmonicity, we identify additional infrared-active bands in the MI-IR spectra due to the (CO) dimer. These bands are satellite bands next to the established CO monomer bands, which appear in the infrared window of Earth's atmosphere at around 4 and 15 μm.

Raman spectroscopy study of the slow order-order transformation of deuterium atoms: Ice XIX decay and ice XV formation.

The nature of the hydrogen substructure of a deuterated and deuterium chloride (DCI)-doped ice VI sample after cooling at 1.8 GPa has been a topic of recent interest-especially because the novel ice polymorph ice XIX was discovered in the course of such studies. We here investigate deuterated samples containing 5% HO using Raman spectroscopy to probe for transitions associated with rearrangement of D-atoms in ice XIX.

Oxygen NMR of high-density and low-density amorphous ice.

Using oxygen-17 as a nuclear probe, spin relaxometry was applied to study the high-density and low-density states of amorphous ice, covering temperatures below and somewhat above their glass transitions. These findings are put in perspective with results from deuteron nuclear magnetic resonance and with calculations based on dielectrically detected correlation times. This comparison reveals the presence of a wide distribution of correlation times.

The impact of temperature and unwanted impurities on slow compression of ice.

For slowly compressed hexagonal ice pressure-induced amorphisation to high-density amorphous ice (HDA) takes place below and at 130 K, but polymorphic transformation to ice IX takes place at 140-170 K. Stable ice II only forms above 170 K. Ice IX impurities trigger ice IX growth even at 120 K.

Advances in the study of supercooled water.

In this review, we report recent progress in the field of supercooled water. Due to its uniqueness, water presents numerous anomalies with respect to most simple liquids, showing polyamorphism both in the liquid and in the glassy state. We first describe the thermodynamic scenarios hypothesized for the supercooled region and in particular among them the liquid-liquid critical point scenario that has so far received more experimental evidence.

Calorimetric Investigation of Hydrogen-Atom Sublattice Transitions in the Ice VI/XV/XIX Trio.

Ice XIX represents the latest discovery of ice polymorphs and exists in the medium pressure range near 1-2 GPa. Ice XIX is a partially hydrogen-ordered phase, by contrast to its disordered mother phase ice VI, which shares the same oxygen-atom network with ice XIX. Ice XIX differs in terms of the ordering of the hydrogen-atom sublattice, and hence the space group, from its hydrogen-ordered sibling ice XV, which also features the same type of oxygen network.

Experimental evidence for glass polymorphism in vitrified water droplets.

The nature of amorphous ices has been debated for more than 35 years. In essence, the question is whether they are related to ice polymorphs or to liquids. The fact that amorphous ices are traditionally prepared from crystalline ice via pressure-induced amorphization has made a clear distinction tricky.