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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

(Invited) Understanding Multi-Component Transport and Reaction Phenomena in Bipolar Membranes Used for Electrosynthesis

Bipolar membranes (BPMs), which have long seen usage in electrodialysis reactors for the generation of acid and base, have recently demonstrated potential to become critical components in electrochemical synthesis devices. Because they can operate under large pH gradients, BPMs enable favorable environments for electrocatalysis at the individual electrodes. Critical to the implementation of BPMs in these devices is understanding the kinetics of water dissociation that occurs within the BPM junction as well as the co- and counter-ion crossover through the BPM, which both present significant obstacles to developing efficient and stable BPM-devices for electrosynthesis applications. Prior work has modeled ion transport in bipolar membranes in neutral salt solutions for electrodialysis. However, no model exists for the BPM under the harsh applied pH gradients that would be present in electrosynthesis, and there is significant need to explore the effects of the internal hydration on the lifetime and performance of BPMs in such environments. Additionally, a mechanistic understanding of water dissociation catalysis will be required to develop interfacial catalysts that enable the high current density operation required for scalable electrosynthesis of fuels. In this talk, we discuss modeling methodologies and physics inherent in BPMs and present our recent model of ion transport and water dissociation catalysis in BPMs across the pH scale. Specifically, we simulate multi-ion transport for a BPM with various electrolyte combinations on each side of the membrane, demonstrating the significance of co- and counter-ion crossover in BPMs operating under harsh pH gradients. We then investigate effects caused by hydration gradients that occur due to internal ion-exchange and examine potential methods for improving performance and mitigating crossover. Finally, we examine the impact of the interfacial water dissociation catalyst and perform sensitivity analysis on the key properties (catalyst point of zero charge and pKa) that dictate catalyst performance. These results provide information that is critical to developing a comprehensive understanding of multi-component phenomena in BPMs and to informing the design and implementation of BPMs in next-generation devices for the numerous electrosynthesis chemistries that benefit from operation under an applied pH gradient.

Bui, Justin C↗
DOE OSTI2023

Defect-specific strength factors and superposition model for predicting strengthening of ion irradiated Fe18Cr alloy

Here, a high-purity binary alloy Fe18Cr was subjected to heavy-ion irradiation in order to provide improved understanding of the irradiation effect on radiation hardening associated with dislocation loop and network formation, α’ precipitation. The specimens were irradiated with 8 MeV Fe ions (~2 μm ion range) to midrange doses of 0.37 and 3.7 dpa at 300, 350 and 450 °C using dose rates of ~10 –5 –10 –3 dpa/s. Nanoindentation testing was performed to extract the bulk equivalent hardness at low depth from these ion irradiated specimens. High-quality transmission electron microscopy (TEM) images were acquired by utilizing a flash electropolishing method on the Focused Ion Beam (FIB) prepared liftouts. An accurate calculation of the strength factor was provided based on detailed TEM characterization of the irradiated microstructures. A newly refined hardening superposition method was applied to combine the strengthening components from each microstructure. The good agreement between microstructure predicted strength and measured strength further demonstrated the fidelity to use hardening model to quantify the mechanical properties of ion irradiated materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Synergistic Coupling Effect of Electronic Conductivity and Interphase Compatibility on High-Voltage Na 3 V 2 (PO 4 ) 2 F 3 Cathodes

Na 3 V 2 (PO 4 ) 2 F 3 (NVPF) has been considered an up-and-coming cathode material candidate for sodium (Na) ion batteries in light of its high specific capacity and working voltage. However, an erratic cathode/electrolyte interface layer is inevitably formed, accompanied by continuous electrolyte decomposition on the NVPF surface, when the voltage exceeds 4.2 V vs Na + /Na. Herein, the interphase features of NVPF are obviously enhanced owing to the ameliorated electronic conductivity obtained by combining it with carbon nanotubes (CNT). The NVPF with 3 wt % CNT (NVPF@3% CNT) reduces the Na + diffusion kinetic energy barrier and electron transport resistance. Furthermore, the conducting network formed by CNT with sturdy structure strength can promptly accommodate the volumetric changes during sequential Na + extraction/insertion and thus effectively improve the long-term cyclic performance of NVPF/hard carbon full cells. The initial discharge capacity approaches 105 mA h g –1 at 0.5C, and it retains 94% capacity retention after 200 cycles at the temperature of –10 °C. The cathode/electrolyte interphase characterization results further demonstrate that the interphase layer on the NVPF@3% CNT cathode is thinner and more compact compared with pristine samples. Here, this research provides a competitive strategy to facilitate the interfacial compatibility between the NVPF and electrolytes and accelerate the commercialization of high-performance Na-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2023

The Linkage Between Electro-Chemical Mechanical Instabilities in Battery Materials

Battery chemistry must be diversified to achieve a sustainable energy landscape by effectively utilizing renewable energy sources. Alkali metal-ion, all-solid-state, metal–air batteries, and multivalent batteries offer unique cost, safety, raw material abundance, energy, and power density solutions. However, realizing these “beyond Li-ion batteries” must uncover their working principles and performance & property relationships. In this aspect, mitigating chemo-mechanical instabilities in the structure and surface of the electrodes plays a crucial role in their performance. Unfortunately, the coupling between electrochemical and mechanical interactions is often poorly understood due to a lack of operando characterization. Here, this review article explains the working principles of curvature measurement and digital image correlation for measuring stress and strain generations in battery materials. We provided specific examples of how these operando mechanical measurements shed light on instabilities in alkali metal ion electrodes, solid electrolytes, Li-O 2 batteries, and aqueous Zn-ion batteries. Operando mechanical measurements offer an effective way to map changes in the physical fingerprint of the battery materials, therefore providing crucial information to elucidate instabilities in battery materials.

25 ENERGY STORAGE↗
DOE OSTI2024

Ion diffusion retarded by diverging chemical susceptibility

Abstract For first-order phase transitions, the second derivatives of Gibbs free energy (specific heat and compressibility) diverge at the transition point, resulting in an effect known as super-elasticity along the pressure axis, or super-thermicity along the temperature axis. Here we report a chemical analogy of these singularity effects along the atomic doping axis, where the second derivative of Gibbs free energy (chemical susceptibility) diverges at the transition point, leading to an anomalously high energy barrier for dopant diffusion in co-existing phases, an effect we coin as super-susceptibility. The effect is realized in hydrogen diffusion in vanadium dioxide (VO 2 ) with a metal-insulator transition (MIT). We show that hydrogen faces three times higher energy barrier and over one order of magnitude lower diffusivity when it diffuses across a metal-insulator domain wall in VO 2 . The additional energy barrier is attributed to a volumetric energy penalty that the diffusers need to pay for the reduction of latent heat. The super-susceptibility and resultant retarded atomic diffusion are expected to exist universally in all phase transformations where the transformation temperature is coupled to chemical composition, and inspires new ways to engineer dopant diffusion in phase-coexisting material systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Tuning working potential of silicon-phosphorus anode via microstructure control for high-energy lithium-ion batteries

The primary research on anode materials of lithium-ion batteries have been focused on increasing the specific capacity, while the working potential that is also closely related to the practical energy density of batteries has been paid much less attention. In this paper, starting from micrometer-sized silicon and black phosphorus, we have reported a high-energy silicon-phosphorus/carbon anode (denoted as mSPC) via a high-energy ball milling process, which demonstrates an average discharge working potential of 0.3 volts versus lithium, together with a high reversible capacity of > 2000 mAh/g, high initial coulombic efficiency of 84%, excellent cycle stability, and superior rate capability up to 15 A/g. Furthermore, in situ focused-ion-beam scanning electron microscopy reveals that the volume change of the mSPC anode during repeated (de) lithiation is effectively alleviated. In contrast, starting from nanometer-sized silicon, the resulted anode (denoted as nSPC) not only presents a lower reversible capacity (~1200 mAh/g), but also exhibits a higher charge/discharge working potential, leading to reduced energy density. Our results indicate the importance of composition/structure control in tailoring the working potential and specific capacity of alloying-type anodes towards high-energy lithium-ion batteries.

25 ENERGY STORAGE↗
DOE OSTI2021

Silicon-silicon oxide-carbon composites for lithium battery electrodes and methods for forming the composites

Composite silicon based materials are described that are effective active materials for lithium ion batteries. The composite materials comprise processed, e.g., high energy mechanically milled, silicon suboxide and graphitic carbon in which at least a portion of the graphitic carbon is exfoliated into graphene sheets. The composite materials have a relatively large surface area, a high specific capacity against lithium, and good cycling with lithium metal oxide cathode materials. The composite materials can be effectively formed with a two step high energy mechanical milling process. In the first milling process, silicon suboxide can be milled to form processed silicon suboxide, which may or may not exhibit crystalline silicon x-ray diffraction. In the second milling step, the processed silicon suboxide is milled with graphitic carbon. Composite materials with a high specific capacity and good cycling can be obtained in particular with balancing of the processing conditions.

Anguchamy, Yogesh Kumar↗
DOE OSTI2023

Methods for forming silicon-silicon oxide-carbon composites for lithium ion cell electrodes

Composite silicon based materials are described that are effective active materials for lithium ion batteries. The composite materials comprise processed, e.g., high energy mechanically milled, silicon suboxide and graphitic carbon in which at least a portion of the graphitic carbon is exfoliated into graphene sheets. The composite materials have a relatively large surface area, a high specific capacity against lithium, and good cycling with lithium metal oxide cathode materials. The composite materials can be effectively formed with a two-step high energy mechanical milling process. In the first milling process, silicon suboxide can be milled to form processed silicon suboxide, which may or may not exhibit crystalline silicon x-ray diffraction. In the second milling step, the processed silicon suboxide is milled with graphitic carbon. Composite materials with a high specific capacity and good cycling can be obtained in particular with balancing of the processing conditions.

Anguchamy, Yogesh Kumar↗
DOE OSTI2020

Molecular-Level Overhaul of y-Aminopropyl Aminosilicone/Triethylene Glycol Post-Combustion CO2-Capture Solvents

Capturing carbon dioxide (CO2) from post-combustion gas streams is an energy-intensive process that is required prior to either converting or sequestering CO2. There are a few commercial offerings of 1st and 2nd generation aqueous amine technologies, however the cost of capturing CO2 with these technologies remains high. To decrease costs of capture, researchers are designing efficient solvent systems with the goal of being drop-in replacements for 1st and 2nd generation infrastructure. One approach has seen the development of water-lean solvents that aim to increase efficiency by reducing the water content in solution. Water-lean solvents such as GE’s GAP/TEG are promising technologies, with potential to halve the parasitic load to a coal-fired power plant, only if the intrinsically high solution viscosities and hydrolysis of the siloxane moieties could be mitigated. We present here, an integrated multidisciplinary approach to overhaul the GAP/TEG solvent system at the molecular level to mitigate hydrolysis while also reducing viscosity. We present molecular-level insights into chemical speciation of CO2-containing ions, showing that co-solvents and diluents have a negligible effect on reducing viscosity and are not needed. This finding allowed for the design of singlecomponent siloxane-free diamine derivatives with site-specific incorporation of selective chemical moieties for direct placement and orientation of hydrogen bonding to reduce viscosity. Ultimately, we present new single-component diamine formulations less susceptible to hydrolysis that exhibit up to a 98% reduction in viscosity compared to the initial GAP/TEG formulation.

Cantu Cantu, David↗
DOE OSTI2021

Factors Influencing Preferential Anion Interactions during Solvation of Multivalent Cations in Ethereal Solvents

Most multivalent secondary batteries have employed electrolytes composed of cyclic ether solvents such as tetrahydrofuran or linear glycol ether solvents (glymes) such as 1,2-dimethoxyethane (G1). A robust understanding of multivalent cation solvation tendencies in these classes of solvents provides insight into corresponding structure–property relationships which, in turn, promotes the design and discovery of improved electrolytes. In this work, our goal is to systematically address how electrolyte constituent properties, namely, ether solvent structure and dication size, direct the solvation interactions of divalent electrolytes and their resultant properties. This study utilizes pulsed-field gradient (PFG) nuclear magnetic resonance (NMR) spectroscopy in conjunction with Raman spectroscopy and ionic conductivity measurements to elucidate the preferential interactions between multivalent cations, anions, and solvent molecules along with their correlated ion dynamics. These investigations incorporate two representative divalent cations (Ca 2+ and Zn 2+ ) as well as two ethereal solvent representatives from both the cyclic ether and glyme structural classes. The results reveal that anions coordinate more readily with divalent cations in cyclic ethers than in glymes. Furthermore, the coordination of the anions with Ca 2+ , i.e., contact-ion pair (CIP) formation is more pronounced than with Zn 2+ in a glyme solvent of limited chain length (G1), providing insight into cation size effects that are important for translating solvation behavior across various multivalent electrolytes. Importantly, we find that specific anion coordination is more strongly controlled by solvent structure than by salt concentration in the practical range of 0.1–0.5 M. However, simply reducing these inner-sphere inter-ionic interactions by changing solvent structure does not necessarily de-correlate ionic motion. Instead, concentration-dependent changes in molar ionic conductivity suggest that second-shell interactions, i.e., solvent separated ion pairs (SSIPs), are prevalent in these electrolytes and that the solution dielectric constant, which is increased by the presence of dipolar ion pairs, is critical for controlling these interactions. These findings thus provide a basis for understanding the physical chemistry of multivalent battery electrolytes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

The Migdal effect in semiconductors for dark matter with masses below ~ 100 MeV

Dark matter scattering off a nucleus has a small probability of inducing an observable ionization through the inelastic excitation of an electron, called the Migdal effect. We use an effective field theory to extend the computation of the Migdal effect in semiconductors to regions of small momentum transfer to the nucleus, where the final state of the nucleus is no longer well described by a plane wave. Our analytical result can be fully quantified by the measurable dynamic structure factor of the semiconductor, which accounts for the vibrational degrees of freedom (phonons) in a crystal. We show that, due to the sum rules obeyed by the structure factor, the inclusive Migdal rate and the shape of the electron recoil spectrum is well captured by approximating the nuclei in the crystal as free ions; however, the exclusive differential rate with respect to energy depositions to the crystal depends on the phonon dynamics encoded in the dynamic structure function of the specific material. Our results now allow the Migdal effect in semiconductors to be evaluated even for the lightest dark matter candidates (m χ ≳ 1 MeV) that can kinematically excite electrons.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗
DOE OSTI2024

Unraveling the conundrum of electronic leakage in protonic ceramic cells: Operation-specific insights and rational design strategies

Electronic conduction through proton-conducting electrolytes significantly impairs the efficiency of protonic ceramic cells (PCCs). Here, in this study, we explore the electron and ion mixed transport properties of four common protonic ceramics, BaZr 0.8 Y 0.2 O 3-δ (BZY82), BaZr 0.7 Ce 0.2 Y 0.1 O 3-δ (BZCY721), BaZr 04 Ce 0.4 Y 0.1 Yb 0.1 O 3-δ (BZCYYb4411), and BaZr 0.1 Ce 0.7 Y 0.1 Yb 0.1 O 3-δ (BZCYYb1711). It marks the first instance of investigating these properties under operation-specific scenarios: fuel side of electrolysis cell, air side of electrolysis cell, fuel side of fuel cell, and air side of the fuel cell. BZCYYb1711 exhibits the highest ionic conductivity, but two to three times higher electronic leakage when exposed to oxygen-containing environments than the others. BZY82 exhibits approximately two times higher electronic leakage in a hydrogen-containing environment. BZCY721 demonstrates excellent ion transport numbers (~0.95) across these four operating conditions. BZCYYb4411 behaves quite similarly to BZCY721. The most challenging operating environment for all candidates is the air side of fuel cell mode. This mode leads to a high initial electronic leakage, followed by a significant increase with polarization. The probable cause for this behavior is a H 2 -free, polarization-induced reduction that leads to the formation of V$^•_O$. The electron small polaron associated with V$^•_O$ is released by the electrical field due to the Poole-Frenkel effect. ZnO and NiO sintering aids are found to be detrimental to the ionic conductivity of the electrolytes. In particular, NiO substantially lowers the ion transport number. The correlation of the operation-specific electronic leakage to full cells is discussed. It is suggested that a rational PCC design should synergistically couple BZCYYb1711 at fuel side with BZCY4411 at air side to deliver a well-balanced performance and faradaic efficiency simultaneously, and the high temperature sintering process with a NiO fuel electrode should be shortened or replaced by ultra-fast sintering techniques or using a fuel electrode scaffold-infiltration fabrication strategy.

42 ENGINEERING↗
DOE OSTI2021

Measuring Electronic Structure of Multiply Charged Anions to Understand their Chemistry: A Case Study on Gaseous Polyhedral closo-Borate Dianions

Research on multiply charged anions (MCAs) in the gas phase has been intensively performed during the last decades, mainly to understand fundamental molecular physics phenomena, e.g., intramolecular Coulomb repulsion and existence of the repulsive Coulomb barrier. However, the relevance of these investigations with respect to understanding MCAs’ chemistry appears often vague. Here, we discuss how insights on the electronic structure obtained from negative ion photoelectron spectroscopy (NIPES) combined with theoretical calculations and collision induced dissociation can provide fundamental understanding on the intrinsic chemical reactivity of MCAs and their fragments. This is exemplified on our studies on polyhedral closo-borate dianions [BnXn]2- (n = 6, 10, 11, 12; X = H, F-I, CN) and their fragment ions. For example, the rational design of closo-borate dianions with specific electronic properties is described, which leads to generating highly reactive fragments. Depending on the dianionic precursor, these fragments are either tuned to bind noble gases effectively or to activate small molecules like CO and N2. The intrinsic electronic properties of closo-borate dianions are further compared to their electrochemistry in solutions, revealing solvent effects on the redox potentials. Neutral host molecules such as cyclodextrins are found to bind strongly to [BnXn]2-, and gas phase NIPES provides insights on the intrinsic host-guest interactions. Finally, outlooks including the direct NIPES of molecular fragment ions which cannot be generated in the condensed phase and their utilization in preparative mass spectrometry are discussed. J.W is grateful to the Volkswagen foundation for a Freigeist Fellowship. X. B. W acknowledges support from the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, the Division of Chemical Sciences, Geosciences and Biosciences. We are grateful to our colleagues who support our work on gas phase ion chemistry for many years. In particular we acknowledge the members of our groups, the Asmis group (Leipzig), Laskin Group (West Lafayette), the Jenne group (Wuppertal), the Finze group (Würzburg), the Grabowsky group (Bern), and the Sun group (Shanghai). We are grateful to Edoardo Apra for the many theoretical investigations on closo-borate anions. JW acknowledges support of Harald Knorke and Markus Rohdenburg with the preparation of graphical material, and XBW thanks Qinqin Yuan for the help in organizing references.

Warneke, Jonas↗
DOE OSTI2021

Poly(vinyl alcohol) Hydrogels with Broad-Range Tunable Mechanical Properties via the Hofmeister Effect

Hydrogels, exhibiting wide applications in soft robotics, tissue engineering, implantable electronics, etc., often require sophisticately tailoring of the hydrogel mechanical properties to meet specific demands. For examples, soft robotics necessitates tough hydrogels; stem cell culturing demands various tissue-matching modulus; and neuron probes desire dynamically tunable modulus. Herein, a strategy to broadly alter the mechanical properties of hydrogels reversibly via tuning the aggregation states of the polymer chains by ions based on the Hofmeister effect is reported. An ultratough poly(vinyl alcohol) (PVA) hydrogel as an exemplary material (toughness 150 ± 20 MJ m -3 ), which surpasses synthetic polymers like poly(dimethylsiloxane), synthetic rubber, and natural spider silk is fabricated. With various ions, the hydrogel's various mechanical properties are continuously and reversibly in situ modulated over a large window: tensile strength from 50 ± 9 kPa to 15 ± 1 MPa, toughness from 0.0167 ± 0.003 to 150 ± 20 MJ m -3 , elongation from 300 ± 100% to 2100 ± 300%, and modulus from 24 ± 2 to 2500 ± 140 kPa. Importantly, the ions serve as gelation triggers and property modulators only, not necessarily required to remain in the gel, maintaining the high biocompatibility of PVA without excess ions. Overall, this strategy, enabling high mechanical performance and broad dynamic tunability, presents a universal platform for broad applications from biomedicine to wearable electronics.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Design of multi neutron-to-gamma converter array for measuring time resolved ion temperature of inertial confinement fusion implosions

The ion temperature varying during inertial confinement fusion implosions changes the amount of Doppler broadening of the fusion products, creating subtle changes in the fusion neutron pulse as it moves away from the implosion. A diagnostic design to try to measure these subtle effects is introduced—leveraging the fast time resolution of gas Cherenkov detectors along with a multi-puck array that converts a small amount of the neutron pulse into gamma-rays, one can measure multiple snapshots of the neutron pulse at intermediate distances. Further, precise measurements of the propagating neutron pulse, specifically the variation in the peak location and the skew, could be used to infer time-evolved ion temperature evolved during peak compression.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2025

Advances and perspectives of hard carbon anode modulated by defect/hetero elemental engineering for sodium ion batteries

Sodium-ion batteries (SIBs) serve as a promising complement to lithium-ion batteries for large-scale energy storage, leveraging the abundance of sodium resources and notable safety advantages. The key advancement in SIB industrialization hinges on identifying a cost-effective and high-performance anode material, similar to the graphite anode in lithium-ion batteries. Hard carbon emerges as prime anode materials for SIBs, boasting high specific capacity, low sodium storage potential, and wide availability. However, practical applications of hard carbon encounters challenges such as low initial Coulombic efficiency (ICE), inadequate long-term cycling stability, and poor rate performance. Recent research has focused on the optimization of hard carbon electrodes through functional design. In this comprehensive review, we have meticulously examined the progress in enhancing sodium storage performance through microstructural modulation within hard carbon, encompassing four pivotal aspects: heteroatom doping, incorporation of oxygen functional groups, surface coating, and intrinsic defect engineering. Progress in implementing these strategies is scrutinized, while the merits and challenges of each defect engineering approach are discussed. In conclusion, this review also looks into forthcoming opportunities and challenges in the practical application process of hard carbon electrodes in SIBs.

25 ENERGY STORAGE↗
DOE OSTI2020

Progress in modelling fast-ion D-alpha spectra and neutral particle analyzer fluxes using FIDASIM

FIDASIM is a code that models signals produced by charge-exchange reactions between neutrals and ions (both fast and thermal) in magnetically confined plasmas. With the ion distribution function as input, the code predicts the efflux to a neutral particle analyzer diagnostic and the photon radiance of Balmer-alpha light to a fast-ion D α diagnostic, in addition to many other related quantities. A new, parallelized version of the Monte Carlo code FIDASIM has been developed in Fortran90 that is substantially faster than the original interactive data language version. Modified algorithms include more accurate treatments of the time dependent collisional-radiative equations that describe neutral energy levels, of the cloud of ‘halo’ neutrals that surround the injected neutral beam, and of finite Larmor radius effects. Enhanced physics capabilities include modelling ‘passive’ signals from cold edge neutrals, the ability to treat general three-dimensional magnetic confinement configurations, and calculations of diagnostic-specific weight functions that enable tomographic reconstructions of the fast-ion distribution function. Neutral beam attenuation, beam emission, and fast-ion birth profiles are also modelled. Finally, the new algorithms have been successfully validated against experimental data and new features have been tested through benchmarks between two independently developed versions of the code.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2023

Molecular Cage Reports on Its Contents: Spectroscopic Signatures of Cryo-Cooled K + - and Ba 2+ -Benzocryptand Complexes

UV photofragment spectroscopy and IR–UV double resonance methods are used to determine the structure and spectroscopic responses of a three-dimensional [2.2.2]-benzocryptand cage to the incorporation of a single K + or Ba 2+ imbedded inside it (labeled as K + -BzCrypt, Ba 2+ -BzCrypt). We studied the isolated ion-cryptand complex under cryo-cooled conditions, brought into the gas phase by nano-electrospray ionization. Incorporation of a phenyl ring in place of the central ethyl group in one of the three N-CH 2 -CH 2 -O-CH 2 -CH 2 -O-CH 2 -CH 2 -N chains provides a UV chromophore whose S 0 –S 1 transition we probe. K + -BzCrypt and Ba 2+ -BzCrypt have their S 0 –S 1 origin transitions at 35,925 and 36,446 cm –1 , respectively, blue-shifted by 174 and 695 cm –1 from that of 1,2-dimethoxybenzene. These origins are used to excite a single conformation of each complex selectively and record their IR spectra using IR–UV dip spectroscopy. The alkyl CH stretch region (2800–3000 cm –1 ) is surprisingly sensitive to the presence and nature of the encapsulated ion. We carried out an exhaustive conformational search of cage conformations for K + -BzCrypt and Ba 2+ -BzCrypt, identifying two conformations (A and B) that lie below all others in energy. Here, we extend our local mode anharmonic model of the CH stretch region to these strongly bound ion-cage complexes to predict conformation-specific alkyl CH stretch spectra, obtaining quantitative agreement with experiment for conformer A, the gas-phase global minimum. The large electrostatic effect of the charge on the O- and N-lone pairs affects the local mode frequencies of the CH 2 groups adjacent to these atoms. The localized CH 2 scissors modes are pushed up in frequency by the adjacent O/N-atoms so that their overtones have little effect on the alkyl CH stretch region. However, the localized CH 2 wags are nearly degenerate and strongly coupled to one another, producing an array of delocalized wag normal modes, whose highest frequency members reach up above 1400 cm –1 . As such, their overtones mix significantly with the CH stretch modes, most notably involving the CH 2 symmetric stretch fundamentals of the central ethyl groups in the all-alkyl chains and the CH stretches adjacent to the N-atoms and antiperiplanar to the nitrogen lone pair.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗