Anisole is a multifunctional molecule that can form intermolecular complexes via its aromatic π-electron system as well as its methoxy group. We have studied the complexation of anisole with methanol. This serves as a prototype system to... more
Anisole is a multifunctional molecule that can form intermolecular complexes via its aromatic π-electron system as well as its methoxy group. We have studied the complexation of anisole with methanol. This serves as a prototype system to explore the competition between O-HO, O-Hπ, C-HO and C-Hπ hydrogen bonding. The anisolemethanol molecular complexes were formed in superfluid helium droplets and were detected using high-resolution laser-infrared spectroscopy, in the frequency range between 2630 and 2730 cm-1 covering the O-D stretches of methanol-d4 (CD3OD). Several bands assigned to (anisole)m(methanol)n complexes (where m = 1, and 2 and n = 1) were observed. The experimental results are complemented by the ab initio electronic structure calculations at the MP2/6-311++G(d,p) and B3LYP-D3/aug-cc-pVTZ levels of theory. Based on a comparison of the observed spectra with the ab initio theoretical spectra, we suggest that for the anisolemethanol complex, structures bound via O-HO and O-Hπ hydrogen bonding are almost equally preferred.
Electrostatic interactions are central to the structure and function of nucleic acids, including their folding, condensation, and interaction with proteins and other charged molecules. These interactions are profoundly affected by...
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A combined THz and simulation study on MgSO4 find no contact ion pairs in highly concentrated solutions.
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We have exploited glycine as zwitterionic model system to experimentally probe the cation specific interaction of protein surface charges in dilute (≤ 0.25 mol/lit) aqueous solutions of four biologically relevant...
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We have studied ion pairing of ytterbium halide solutions. THz spectra (30-400 cm) of aqueous YbCl and YbBr solutions reveal fundamental differences in the hydration structures of YbCl and YbBr at high salt concentrations: While for YbBr... more
We have studied ion pairing of ytterbium halide solutions. THz spectra (30-400 cm) of aqueous YbCl and YbBr solutions reveal fundamental differences in the hydration structures of YbCl and YbBr at high salt concentrations: While for YbBr no indications for a changing local hydration environment of the ions were experimentally observed within the measured concentration range, the spectra of YbCl pointed towards formation of weak contact ion pairs. The proposed anion specificity for ion pairing was confirmed by supplementary Raman measurements.
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Spectroscopy in the THz frequency regime is a sensitive tool to probe solvation-induced effects in aqueous solutions. Yet, a systematic understanding of spectral lineshapes as a result of distinct solvation contributions remains terra... more
Spectroscopy in the THz frequency regime is a sensitive tool to probe solvation-induced effects in aqueous solutions. Yet, a systematic understanding of spectral lineshapes as a result of distinct solvation contributions remains terra incognita. We demonstrate that modularization of amino acids in terms of functional groups allows us to compute their distinct contributions to the total THz response. Introducing the molecular cross-correlation analysis method provides unique access to these site-specific contributions. Equivalent groups in different amino acids lead to look-alike spectral contributions, whereas side chains cause characteristic but additive complexities. Specifically, hydrophilic solvation of the zwitterionic groups in valine and glycine leads to similar THz responses which are fully decoupled from the side chain. The THz response due to H-bonding within the large hydrophobic solvation shell of valine turns out to be nearly indistinguishable from that in bulk water in...
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While the real-space structure of solvation shells has been explored for decades, a dynamical perspective that directly relies on changes in the H-bond network became accessible more recently mainly via far-infrared (THz) spectroscopies.... more
While the real-space structure of solvation shells has been explored for decades, a dynamical perspective that directly relies on changes in the H-bond network became accessible more recently mainly via far-infrared (THz) spectroscopies. A remaining key question is how many hydration shells are affected by ion-induced network perturbations. We disclose that theoretical THz difference spectra of aqueous salt solutions can be deciphered in terms of only a handful of dipolar auto- and cross-correlations, including the second solvation shell. This emphasizes the importance of cross-correlations being often neglected in multicomponent models. Analogously, experimental THz responses of simple ions can be deciphered in a similar way. Dramatic intensity cancellations due to large positive and negative contributions are found to effectively shift intensity maxima. Thus, THz spectroscopy provides an unprecedented view on the details of hydration dynamics, which can be understood by a combination of experiment and theory.
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THz spectroscopy was used to probe changes that occur in the dynamics of the hydrogen bond network upon solvation of alcohol chains. The THz spectra can be decomposed into the spectrum of bulk water, tetrahedral hydration water, and more... more
THz spectroscopy was used to probe changes that occur in the dynamics of the hydrogen bond network upon solvation of alcohol chains. The THz spectra can be decomposed into the spectrum of bulk water, tetrahedral hydration water, and more disordered (or interstitial) hydration water. The tetrahedrally ordered hydration water exhibits a band at 195 cm-1 and is localized around the hydrophobic moiety of the alcohol. The interstitial component yields a band at 164 cm-1 which is associated with hydration water in the first hydration shell. These temperature-dependent changes in the low-frequency spectrum of solvated alcohol chains can be correlated with changes of heat capacity, entropy, and free energy upon solvation. Surprisingly, not the tetrahedrally ordered component but the interstitial hydration water is found to be mainly responsible for the temperature-dependent change in ΔCp and ΔG. The solute-specific offset in free energy is attributed to void formation and scales linearly with the chain length.
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The infrared spectrum of allyl:water clusters embedded in helium nanodroplets was recorded. Allyl radicals were produced by flash vacuum pyrolysis and trapped in helium droplets. Deuterated water was added to the doped droplets, and the... more
The infrared spectrum of allyl:water clusters embedded in helium nanodroplets was recorded. Allyl radicals were produced by flash vacuum pyrolysis and trapped in helium droplets. Deuterated water was added to the doped droplets, and the infrared spectrum of the radical water aggregates was recorded in the frequency range 2570-2820 cm-1. Several absorption bands are observed and assigned to 1:1 and 1:2 allyl:D2O clusters, based on pressure dependent measurements and accompanying quantum chemical calculations. The analysis of the 1:1 cluster spectrum revealed a tunneling splitting as well as a combination band. For the 1:2 cluster, we observe a water dimer-like motif that is bound by one π-hydrogen bond to the allyl radical.
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The valency of aqueous solutes plays a large role in determining the extent of ion-water dynamics, which can greatly influence the chemical and physical properties of solutions. In these experiments, broadband Fourier transform terahertz... more
The valency of aqueous solutes plays a large role in determining the extent of ion-water dynamics, which can greatly influence the chemical and physical properties of solutions. In these experiments, broadband Fourier transform terahertz spectroscopy is used to probe perturbations to the low-frequency dynamics of water molecules by three different multivalent hexacyanoferrate salts. K3Fe(CN)6, K4Fe(CN)6 and Na4Fe(CN)6 were investigated as a function of concentration up to their solubility limits using spectral subtractions and fitting with damped harmonic lineshapes. Regions with subtle nonlinearities in amplitude with respect to solute concentration provide insight into ion-pairing events. The extent of nonlinearity suggests that ion pairs are major constituents in solution for all concentrations measured and is consistent with ion-pairing observed at millimolar concentrations by potentiometric and spectroscopic measurements. A lower estimate for the number of water molecules that ...
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Cyclopentadienyl radicals were produced by vacuum flash pyrolysis and trapped in superfluid helium nanodroplets. The infrared spectrum of the embedded radicals was recorded in the range 3020-3120 cm(-1). Three bands observed at 3056.3,... more
Cyclopentadienyl radicals were produced by vacuum flash pyrolysis and trapped in superfluid helium nanodroplets. The infrared spectrum of the embedded radicals was recorded in the range 3020-3120 cm(-1). Three bands observed at 3056.3, 3086.9, and 3117.3 cm(-1) were assigned to the transitions from the ground state to the three levels of the quadratically Jahn-Teller distorted (i.e., second order Jahn-Teller active) CH stretch vibration with E1' symmetry. Accompanying ab initio calculations showed a vibrationally averaged symmetric equilibrium structure in agreement with the observed vibronic transitions. Our results confirm a symmetric configuration of the cyclopentadienyl (cp) radical that is dynamically Jahn-Teller distorted. Density functional theory calculations and infrared data further suggest that barrier-less reactions of two cp radicals occur within the droplets.
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The IR spectrum of benzyl radical:water clusters was recorded. Benzyl radicals were produced by vacuum flash pyrolysis and trapped in superfluid helium nanodroplets. The infrared spectrum of benzyl radical water aggregates in the range... more
The IR spectrum of benzyl radical:water clusters was recorded. Benzyl radicals were produced by vacuum flash pyrolysis and trapped in superfluid helium nanodroplets. The infrared spectrum of benzyl radical water aggregates in the range 2585-2820 cm(-1) was recorded by subsequent addition of deuterated water. A total of seven peaks are observed at 2766, 2750, 2656, 2638, 2633, 2598, and 2593 cm(-1). Based on pressure dependent measurements and comparison to accompanying ab initio calculations, five of these bands are assigned to distinct O-D stretch vibrations of benzyl:water clusters with one and two water molecules. In line with previous experiments on benzene:water clusters, we observe the formation of a water dimer-like motif that is attached to one face of the benzyl radical.
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Abstract. A compact modular acousto-optical spectrometer (AOS) has been built for airborne astronomical observations. It has a bandwidth of 992 MHz and a resolution of 1.7 MHz. It is easy to transport and to adjust and provides it own... more
Abstract. A compact modular acousto-optical spectrometer (AOS) has been built for airborne astronomical observations. It has a bandwidth of 992 MHz and a resolution of 1.7 MHz. It is easy to transport and to adjust and provides it own data acquisition and handling system. The AOS was successfully flown on board the Kuiper Airborne Observatory in September 1988 and performed just as well as in the laboratory.
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Recently, we were able to show that aqueous solutions of alkali and earth-alkali halides show strong resonances in the THz range that may be attributed to movements of individual ions in their surrounding water cage. Here, we extend this... more
Recently, we were able to show that aqueous solutions of alkali and earth-alkali halides show strong resonances in the THz range that may be attributed to movements of individual ions in their surrounding water cage. Here, we extend this study to bromides and chlorides of selected lanthanides and transition metals. The effects of these strong ions on the water network as well as the detectability of contact ion complexes will be discussed.
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The Institute of Space Sensor Technology of the German Aerospace Center (DLR) is developing a heterodyne array receiver for the frequency range 2 to 6 THz for the Stratospheric Observatory for Infrared Astronomy (SOFIA). Key science... more
The Institute of Space Sensor Technology of the German Aerospace Center (DLR) is developing a heterodyne array receiver for the frequency range 2 to 6 THz for the Stratospheric Observatory for Infrared Astronomy (SOFIA). Key science issues in that frequency range are the observation of lines of atoms [e.g. (OI)], ions [e.g. (CII), (NII)], and molecules (e.g. OH, HD, CO) with high spectral resolution to study the dynamics and evolution of galactic and extragalactic objects. Long term goal is the development of an integrated array heterodyne receiver with superconducting hot electron bolometric (HEB) mixers and p-type Ge or Si lasers as local oscillators. The first generation receiver will be composed of HEB mixers in a 2 pixel 2 polarization array which will be pumped by a gas laser local oscillator. Improved Schottky diode mixers are the backup solution for the HEBs. The state of the art of HEB mixer and p-type Ge laser technology are described as well as possible improvements in th...
The Institute of Space Sensor Technology of the German Aerospace Center (DLR) is developing a heterodyne array receiver for the frequency range 2 to 6 THz for the Stratospheric Observatory for Infrared Astronomy (SOFIA). Key science... more
The Institute of Space Sensor Technology of the German Aerospace Center (DLR) is developing a heterodyne array receiver for the frequency range 2 to 6 THz for the Stratospheric Observatory for Infrared Astronomy (SOFIA). Key science issues in that frequency range are the observation of lines of atoms [e.g. (OI)], ions [e.g. (CII), (NII)], and molecules (e.g. OH, HD, CO) with high spectral resolution to study the dynamics and evolution of galactic and extragalactic objects. Long term goal is the development of an integrated array heterodyne receiver with superconducting hot electron bolometric (HEB) mixers and p-type Ge or Si lasers as local oscillators. The first generation receiver will be composed of HEB mixers in a 2 pixel 2 polarization array which will be pumped by a gas laser local oscillator. Improved Schottky diode mixers are the backup solution for the HEBs. The state of the art of HEB mixer and p-type Ge laser technology are described as well as possible improvements in th...