An automatic variable laser power attenuator for continuous-wave quantum cascade lasers in cryogenic ion vibrational predissociation spectroscopy.

Cryogenic ion vibrational predissociation (CIVP) spectroscopy is an established and valuable technique for molecular elucidation in the gas phase. CIVP relies on tunable lasers, wherein among typical laser schemes, the application of mid-infrared continuous-wave quantum cascade laser (cw-QCL) is the most robust and elegant solution, as we have recently demonstrated. However, potential challenges arise from an inhomogeneous character across laser power tuning curves.

Probing Electronic Effects in Tridentate Copper(I) Complexes by CIVP Spectroscopy.

Ligand electronic effects play an important role in catalysis, where small changes to ligand structure can bring about large changes in catalytic activity. Therefore, accurate experimental quantification of ligand electronic properties plays a crucial role in understanding and tuning chemical reactivity. In this work, we used cryogenic ion vibrational predissociation (CIVP) spectroscopy to experimentally quantify electronic effects in terpyridine ligands, as simple model systems, by measuring CIVP spectra of their copper complexes tagged by N molecules.

Increasing Complexity in a Conformer Space Step-by-Step: Weighing London Dispersion against Cation-π Interactions.

We report an evaluation of the importance of London dispersion in moderately large (up to 36 heavy atoms) organic molecules by means of a molecular torsion balance whose conformations "weigh" one interaction against another in the absence of solvents. The experimental study, with gas-phase cryogenic ion vibrational predissociation (CIVP) spectroscopy, solid-state Fourier transfer infrared (FT-IR), and single-crystal X-ray crystallography, is accompanied by density functional theory calculations, including an extensive search and analysis of accessible conformations. We begin with the unsubstituted molecular torsion balance, and then step up the complexity systematically by adding alkyl groups incrementally as dispersion energy donors (DEDs) to achieve a degree of chemical complexity comparable to what is typically found in transition states for many regio- and stereoselective reactions in organic and organometallic chemistry.

Application of continuous wave quantum cascade laser in combination with CIVP spectroscopy for investigation of large organic and organometallic ions.

Rapidly developing mid-infrared quantum cascade laser (QCL) technology gives easy access to broadly tunable mid-IR laser radiation at a modest cost. Despite several applications of QCL in the industry, its usage for spectroscopic investigation of synthetically relevant organic compounds has been limited. Here, we report the application of an external cavity, continuous wave, mid-IR QCL to cryogenic ion vibrational predissociation spectroscopy to analyze a set of large organic molecules, organometallic complexes, and isotopically labeled compounds.

Bond Dissociation Energies in the Gas Phase for Large Molecular Ions by Threshold Collision-Induced Dissociation Experiments: Stretching the Limits.

Accurate bond dissociation energies for large molecules are difficult to obtain by either experimental or computational methods. The former methods are hampered by a range of physical and practical limitations in gas-phase measurement techniques, while the latter require incorporation of multiple approximations whose impact on accuracy may not always be clear. When internal benchmarks are not available, one hopes that experiment and theory can mutually support each other.

Perturbation of Pyridinium CIVP Spectra by N and H Tags: An Experimental and BOMD Study.

In cryogenic ion vibrational predissociation (CIVP) spectroscopy, the influence of the tag on the spectrum is an important consideration. Whereas for small ions several studies have shown that the tag effects can be significant, these effects are less understood for large ions or for large numbers of tags. Nevertheless, it is commonly assumed that if the investigated molecular ion is large enough, the perturbations arising from the tag are small and can therefore be neglected in the interpretation.

Cryogenic ion vibrational predissociation (CIVP) spectroscopy of a gas-phase molecular torsion balance to probe London dispersion forces in large molecules.

We report a gas-phase molecular torsion balance that uses a conformational equilibrium to "weigh" London dispersion against a competing cation-π interaction, for which the readout is the shift in an N-H stretching frequency measured by cryogenic ion vibrational predissociation (CIVP) spectroscopy of electrosprayed pyridinium cations in a Fourier-transform ion cyclotron resonance trap. While frequency calculations with DFT, within the harmonic approximation, assist in the interpretation of the spectra, the observed complex spectrum most likely comes from a Fermi resonance of the N-H stretch with otherwise "dark" overtones of in-plane C-H wagging modes, as argued on the basis of comparison of the spectrum to those for a range of related cations with systematically varied substitution. An equilibrium in favor of the asymmetric conformer would suggest that the dispersion-corrected DFT calculations tested in this work appear to overestimate significantly the stability of the compact conformations favored by London dispersion in the gas phase, which would then pertain to the use of dispersion energy donors in the design of stereoselective reactions.