Direct Exfoliation of Nanoribbons from Bulk van der Waals Crystals.

Confinement of monolayers into quasi-1D atomically thin nanoribbons could lead to novel quantum phenomena beyond those achieved in their bulk and monolayer counterparts. However, current experimental availability of nanoribbon species beyond graphene is limited to bottom-up synthesis or lithographic patterning. In this study, a versatile and direct approach is introduced to exfoliate bulk van der Waals crystals as nanoribbons.

Hidden phonon highways promote photoinduced interlayer energy transfer in twisted transition metal dichalcogenide heterostructures.

Vertically stacked van der Waals (vdW) heterostructures exhibit unique electronic, optical, and thermal properties that can be manipulated by twist-angle engineering. However, the weak phononic coupling at a bilayer interface imposes a fundamental thermal bottleneck for future two-dimensional devices. Using ultrafast electron diffraction, we directly investigated photoinduced nonequilibrium phonon dynamics in MoS/WS at 4° twist angle and WSe/MoSe heterobilayers with twist angles of 7°, 16°, and 25°.

Demystifying the Diffuse Vibrational Spectrum of Aqueous Protons Through Cold Cluster Spectroscopy.

The ease with which the pH is routinely determined for aqueous solutions masks the fact that the cationic product of Arrhenius acid dissolution, the hydrated proton, or H(aq), is a remarkably complex species. Here, we review how results obtained over the past 30 years in the study of H⋅(HO) cluster ions isolated in the gas phase shed light on the chemical nature of H(aq). This effort has also revealed molecular-level aspects of the Grotthuss relay mechanism for positive-charge translocation in water.

Ionic Liquid Clusters Generated from Electrospray Thrusters: Cold Ion Spectroscopic Signatures of Size-Dependent Acid-Base Interactions.

We determine the intramolecular distortions at play in the 2-hydroxyethylhydrazinium nitrate (HEHN) ionic liquid (IL) propellant, which presents the interesting case that the HEH cation has multiple sites (i.e., hydroxy, primary amine, and secondary ammonium groups) available for H-bonding with the nitrate anion.

Chain Length Dependence of Hydrogen Bond Linkages between Cationic Constituents in Hydroxy-Functionalized Ionic Liquids: Tracking Bulk Behavior to the Molecular Level with Cold Cluster Ion Spectroscopy.

Hydroxy functionalization of cations in ionic liquids (ILs) can lead to formation of contacts between their OH groups [so-called (c-c) interactions]. One class of these linkages involves cooperatively enhanced hydrogen bonds to anionic partners that are sufficiently strong to overcome the repulsion between two positively charged centers. Herein, we clarify how the propensity for the formation of (c-c) contacts depends on the alkyl chain length between two cationic rings and their OH groups by analyzing the temperature-dependent IR spectra of bulk ILs as well as the vibrational predissociation spectra of ∼35 K complexes comprised of two cations and one anion.

Spectroscopic Assessment of Intra- and Intermolecular Hydrogen Bonding in Ether-Functionalized Imidazolium Ionic Liquids.

Functionalization of the imidazolium (Im) cationic component of ionic liquids (ILs) with ether chains affords the possibility of tuning their properties through manipulation of the resulting interion and intramolecular interactions. Herein, we quantify these interactions at the molecular level through analysis of the vibrational spectra displayed by size-selected and cryogenically cooled ions. These spectra are obtained using the "tagging" approach carried out with photofragmentation tandem mass spectrometry.

Cooperatively enhanced hydrogen bonds in ionic liquids: closing the loop with molecular mimics of hydroxy-functionalized cations.

We address the cooperative hydrogen bonding interactions in play between the ionic constituents of ionic liquids (ILs) with particular attention to those involving the attractive interactions between two cations in the system 1-(2-hydroxyethyl)pyridinium tetrafluoroborate [HEPy][BF4]. This is accomplished by comparing the temperature-dependent linear infrared spectra of [HEPy][BF4] with that of the molecular mimic of its cation, 2-phenylethanol (PhenEthOH). We then explored the structural motifs of these H-bonded configurations at the molecular level by analyzing the cryogenic ion vibrational predissociation spectroscopy of cold (∼35 K) gas phase cluster ions with quantum chemical methods.

Introductory lecture: advances in ion spectroscopy: from astrophysics to biology.

This introduction provides a historical context for the development of ion spectroscopy over the past half century by following the evolution of experimental methods to the present state-of-the-art. Rather than attempt a comprehensive review, we focus on how early work on small ions, carried out with fluorescence, direct absorption, and photoelectron spectroscopy, evolved into powerful technologies that can now address complex chemical problems ranging from catalysis to biophysics. One of these developments is the incorporation of cooling and temperature control to enable the general application of "messenger tagging" vibrational spectroscopy, first carried out using ionized supersonic jets and then with buffer gas cooling in radiofrequency ion traps.

Spectroscopic Evidence for an Attractive Cation-Cation Interaction in Hydroxy-Functionalized Ionic Liquids: A Hydrogen-Bonded Chain-like Trimer.

We address the formation of hydrogen bonded domains among the cationic constituents of the ionic liquid (IL) 1-(3-hydroxypropyl)pyridinium tetrafluoroborate [HPPy][BF ] by means of cryogenic ion vibrational predissociation spectroscopy of cold (ca. 35 K) gas-phase cluster ions and quantum chemistry. Specifically, analysis of the OH stretching bands reveals a chain-like OH⋅⋅⋅OH⋅⋅⋅OH⋅⋅⋅BF binding motif involving the three cations in the cationic quinary cluster ion (HPPy ) (BF ) .

Structural Motifs in Cold Ternary Ion Complexes of Hydroxyl-Functionalized Ionic Liquids: Isolating the Role of Cation-Cation Interactions.

We address the competition between intermolecular forces underlying the recent observation that ionic liquids (ILs) with a hydroxyl-functionalized cation can form domains with attractive interactions between the nominally repulsive positively charged constituents. Here we show that this behavior is present even in the isolated ternary (HEMIm)NTf complex (HEMIm = 1-(2-hydroxyethyl)-3-methylimidazolium) cooled to about 35 K in a photodissociation mass spectrometer. Of the three isomers isolated by double resonance techniques, one is identified to exhibit direct contact between the cations.