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At least 289 records · Page 16
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Crystalline Organic Compounds as Effective Nuclei in Contact Efflorescence of Ammonium Sulfate

Contact nucleation is believed to play a role in liquid-to-solid phase transitions in the atmosphere including ice nucleation and salt efflorescence. Here, for this work, contact efflorescence of optically levitated ammonium sulfate droplets by collisions with organic particles is probed using a long working-distance optical trap. Two highly viscous water-soluble organic compounds (d-(+)-raffinose and citric acid), and two insoluble highly surface-active organic compounds (stearic acid and cis-pinonic acid) were probed for their ability to induce efflorescence upon contact. While three of the organics showed minimal effectiveness as contact nuclei, cis-pinonic acid showed a remarkable ability to initiate contact efflorescence of ammonium sulfate, occurring near ammonium sulfate’s deliquescence relative humidity. Further analysis of cis-pinonic acid using bright-field microscopy in an electrodynamic balance provided evidence that the cis-pinonic acid particles are crystalline under the laboratory conditions. We suggest that the close lattice match between crystalline ammonium sulfate and crystalline cis-pinonic acid may account for the observed effectiveness in initiating contact efflorescence of ammonium sulfate. In contrast, tests of contact nucleation between cis-pinonic acid and sodium chloride, a pair with a poor lattice match, did not result in efflorescence. These findings suggest that crystalline organic compounds in the atmosphere could act as effective nuclei for contact efflorescence of atmospherically relevant salts, provided they share a compatible lattice structure.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Unravelling the Correlation of Electronic Structure and Carrier Dynamics in CuInS 2 Nanoparticles

Here, we report the direct correlation of photoinduced carrier dynamics and electronic structure of CuInS 2 (CIS) nanoparticles (NPs) using the combination of multiple spectroscopic techniques including steady-state X-ray absorption spectroscopy (XAS), optical transient absorption (OTA), and X-ray transient (XTA) absorption spectroscopy. XAS results show that CIS NPs contain a large amount of surface Cu atoms with << four-coordination, which is more severe in CIS NPs with shorter nucleation times, indicating the presence of more Cu defect states in CIS NPs with smaller size particles. Using the combination of OTA and XTA spectroscopy, we show that electrons are trapped at states with mainly In or S nature while holes are trapped in sites characteristic of Cu. While there is no direct correlation of ultrafast trapping dynamics with NP nucleation time, charge recombination is significantly inhibited in CIS NPs with larger particles. These results suggest the key roles that Cu defect sites play in carrier dynamics and imply the possibility to control the carrier dynamics by controlling the surface structure at the Cu site in CIS NPs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Stereospecific Ring-Opening Metathesis Polymerization (ROMP) of endo -Dicyclopentadiene by Molybdenum and Tungsten Catalysts

Here we report an examination of the ring-opening metathesis polymerization (ROMP) of endo -dicyclopentadiene (DCPD) by 10 well-defined molybdenum-based and 16 tungsten-based alkylidene initiators. Five tungsten-based MAP (monoaryloxide pyrrolide) initiators with the general formula W(X)(CHCMe 2 Ph)(Me 2 Pyr)(OAr) (X = arylimido, alkylimido, or oxo; Me 2 Pyr =2,5-dimethylpyrrolide; OAr = an aryloxide) were found to yield >98% cis , >98% syndiotactic poly(DCPD); they are W(N- t -Bu)(CHCMe 3 )(pyr)(OHMT) ( 2 , OHMT = O-2,6-(2,4,6-Me 3 C 6 H 2 ) 2 C 6 H 3 , pyr = pyrrolide), W(N-2,6- i -Pr 2 C 6 H 3 )(CHCMe 2 Ph)(pyr)(OHMT) ( 3 ), W(O)(CHCMe 2 Ph)(Me 2 Pyr)(OHMT)(PPh 2 Me) ( 7 , Me 2 Pyr =2,5-dimethylpyrrolide), W(O)(CHCMe 2 Ph)(Me 2 Pyr)(ODFT)(PPh 2 Me) ( 9 , ODFT = O-2,6-(C 6 F 5 ) 2 C 6 H 3 ), and W(O)(CHCMe 2 Ph)(Me 2 Pyr)(OTPP)(PMePh 2 ) ( 10 , OTPP = O-2,3,5,6-Ph 4 C 6 H). Two biphenolate alkylidene complexes, Mo(N-2,6-Me 2 C 6 H 3 )(CHCMe 2 Ph)(rac-biphen) ( 17 ) and W(N-2,6-Me 2 C 6 H 3 )(CHCMe 2 Ph)(rac-biphen) ( 22 , biphen =3,3'-( t -Bu) 2 -5,5'-6,6'-(CH 3 ) 4 -1,1'-biphenyl-2,2'-diolate), were found to yield >98% cis , >98% isotactic poly(DCPD). Cis , syndiotactic or cis , isotactic poly(DCPD)s (made with 50–1000 equiv of DCPD) are accessible within seconds to minutes in dichloromethane at room temperature. No isomerization or cross-linking reactions are determined, and addition of a chain transfer reagent (1-hexene) or the use of THF as a solvent does not decrease the stereospecificity of the polymerizations. Cis , syndiotactic and cis , isotactic poly(DCPD)s can be distinguished readily from each other by 13 C NMR spectroscopy. Hydrogenation of each stereoregular poly(DCPD) produces H-poly(DCPD)s that have melting points near 270 °C ( syndiotactic ) or 290 °C ( isotactic ) and high crystallinities ( w c = 0.83 for syndiotactic and w c = 0.74 for isotactic ).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Stereospecific Ring-Opening Metathesis Polymerization (ROMP) of Norbornene and Tetracyclododecene by Mo and W Initiators

Here we report the synthesis of >98% cis , isotactic and cis , syndiotactic polynorbornene (poly(NBE)) and poly( endo,anti -tetracyclododecene) (poly(TCD)). Cis , isotactic poly(NBE) and poly(TCD) were prepared employing Mo-based biphenolate imido alkylidene initiators, Mo(NR)(CHCMe 2 Ph)(Biphen) (Biphen = e.g., 3,3'-( t -Bu)2-5,5'-6,6'-(CH 3 )4-1,1'-biphenyl-2,2'-diolate), while cis , syndiotactic poly(NBE) and poly(TCD) were prepared employing W-based imido or oxo monoaryloxide pyrrolide (MAP) initiators, W(X)(CHR')(Pyrrolide)(OTer) (X = NR or O; OTer = a 2,6-terphenoxide). Addition of 1-hexene or coordinating solvents such as THF do not decrease the stereospecificity of the polymerization. Cis ,iso and cis ,syndio dyads can be distinguished through investigation of 1 H and 13 C NMR spectra of the two polymers in a mixture. The polymers were hydrogenated to give isotactic and syndiotactic H-poly(NBE) and H-poly(TCD).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Isolation of Inner-Sphere Aquo Complexes of Samarium(II)

The cis-anti-cis and cis-syn-cis isomers of [Sm(dicyclohexano-18-crown-6)(H 2 O) 2 ]I 2 exhibiting trans water molecules bound to the Sm 2+ ion have been isolated and characterized. Sm 2+ possesses an electrochemical potential sufficient for water reduction, and thus these complexes add to the recent body of evidence that the oxidation of Sm 2+ by water can operate by a mechanism that is not straightforward. These complexes are obtained by the direct addition of stoichiometric amounts of water to solutions of the respective Sm(dicyclohexano-18-crown-6)I 2 isomers under an inert atmosphere. The parent complex, Sm(dicyclohexano-18-crown-6)I 2 , lacking coordinating water molecules can be obtained through rigorous exclusion of water. It was determined that the bulky cyclohexano-substituents deter intramolecular interactions between [Sm(dicyclohexano-18-crown-6)(H 2 O) 2 ]I 2 complexes and slow the oxidization of the metal centers. The extent of the stability of these complexes to the presence of water has been further probed through cyclic voltammetry, where it was found that the redox potential of both isomers of [Sm(dicyclohexano-18-crown-6)(H 2 O) 2 ]I 2 maintains quasi-reversible behavior with a 50,000-fold excess of water to Sm 2+ in solution with the cis-syn-cis complex being quasi-reversible at even higher concentrations of water. Solution-phase spectroscopy of these complexes in acetonitrile shows a corresponding hypsochromic shift of the Sm 2+ 4f → 5d transition typically observed in the visible region from Sm 2+ complexes. Here, the crystalline compounds obtained in this study support solid-state spectroscopic trends observed from other Sm 2+ crown-ether complexes containing iodide counterions, wherein the proximity of the iodide ions to the metal center determines whether the complex can exhibit 4f → 4f photoluminescence.

Crystals↗
DOE OSTI2013

Effect of Isomeric Structures of Branched Cyclic Hydrocarbons on Densities and Equation of State Predictions at Elevated Temperatures and Pressures

The cis and trans conformation of a branched cyclic hydrocarbon affects the packing and, hence, the density, exhibited by that compound. Reported here are density data for branched cyclohexane (C6) compounds including methylcyclohexane, ethylcyclohexane (ethylcC6), cis-1,2-dimethylcyclohexane (cis-1,2), cis-1,4-dimethylcyclohexane (cis-1,4), and trans-1,4-dimethylcyclohexane (trans-1,4) determined at temperatures up to 525 K and pressures up to 275 MPa. Of the four branched C6 isomers, cis-1,2 exhibits the largest densities and the smallest densities are exhibited by trans-1,4. The densities are modeled with the Peng–Robinson (PR) equation of state (EoS), the high-temperature, high-pressure, volume-translated (HTHP VT) PREoS, and the perturbed chain, statistical associating fluid theory (PC-SAFT) EoS. Model calculations highlight the capability of these equations to account for the different densities observed for the four isomers investigated in this study. The HTHP VT-PREoS provides modest improvements over the PREoS, but neither cubic EoS is capable of accounting for the effect of isomer structural differences on the observed densities. The PC-SAFT EoS, with pure component parameters from the literature or from a group contribution method, provides improved density predictions relative to those obtained with the PREoS or HTHP VT-PREoS. However, the PC-SAFT EoS, with either set of parameters, also cannot fully account for the effect of the C6 isomer structure on the resultant density.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Tracking the reaction networks of acetaldehyde oxide and glyoxal oxide Criegee intermediates in the ozone-assisted oxidation reaction of crotonaldehyde

The reaction of unsaturated compounds with ozone (O 3 ) is recognized to lead to the formation of Criegee intermediates (CIs), which play a key role in controlling the atmospheric budget of hydroxyl radicals and secondary organic aerosols. The reaction network of two CIs with different functionality, i.e. acetaldehyde oxide (CH 3 CHOO) and glyoxal oxide (CHOCHOO) formed in the ozone-assisted oxidation reaction of crotanaldehyde (CA), is investigated over a temperature range between 390 K and 840 K in an atmospheric pressure jet-stirred reactor (JSR) at a residence time of 1.3 s, stoichiometry of 0.5 with a mixture of 1% crotonaldehyde, 10% O 2 , at an fixed ozone concentration of 1000 ppm and 89% Ar dilution. Molecular-beam mass spectrometry in conjunction with single photon tunable synchrotron vacuum-ultraviolet (VUV) radiation is used to identify elusive intermediates by means of experimental photoionization energy scans and ab initio threshold energy calculations for isomer identification. Addition of ozone (1000 ppm) is observed to trigger the oxidation of CA already at 390 K, which is below the temperature where the oxidation reaction of CA was observed in the absence of ozone. The observed CA + O 3 product, C 4 H 6 O 4 , is found to be linked to a ketohydroperoxide (2-hydroperoxy-3-oxobutanal) resulting from the isomerization of the primary ozonide. Products corresponding to the CIs uni- and bi-molecular reactions were observed and identified. A network of CI reactions is identified in the temperature region below 600 K, characterized by CIs bimolecular reactions with species like aldehydes, i.e., formaldehyde, acetaldehyde, and crotonaldehyde and alkenes, i.e., ethene and propene. The region below 600 K is also characterized by the formation of important amounts of typical low-temperature oxidation products, such as hydrogen peroxide (H 2 O 2 ), methyl hydroperoxide (CH 3 OOH), and ethyl hydroperoxide (C 2 H 5 OOH). Detection of additional oxygenated species such as alcohols, ketene, and aldehydes are indicative of multiple active oxidation routes. This study provides important information about the initial step involved in the CIs assisted oligomerization reactions in complex reactive environments where CIs with different functionalities are reacting simultaneously. It provides new mechanistic insights into ozone-assisted oxidation reactions of unsaturated aldehydes, which is critical for the development of improved atmospheric and combustion kinetics models.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Nonadiabatic ab initio molecular dynamics of photoisomerization in bridged azobenzene

The photoisomerization mechanisms of bridged azobenzene are investigated by means of surface hopping dynamics simulations based on the Zhu-Nakamura theory. In the geometry optimizations and potential energy surface calculations, four minimum-energy conical intersections between the ground state and the lowest excited state are found to play important roles in the trans-cis and cis-trans isomerization processes. The trans-cis photoisomerization proceeds through two minimum-energy conical intersections. Ultrafast pedal motion of the N atoms and twisting of phenyl rings around their N-C bonds allows the molecule to move to a minimum-energy conical intersection, after which surface hopping from S{sub 1} to S{sub 0} occurs. In the S{sub 0} state, further rotation occurs around the N=N bond and two N-C bonds until the azo moiety and phenyl rings complete their isomerization. Finally, the cis form is achieved by subsequent adjustment of the ethylene bridge. In the cis-trans photodynamics, there is one rotational pathway, in the middle of which two CIs are responsible for the surface hopping to the S{sub 0} state. After the nonadiabatic transition, the molecule reaches the trans form through a barrierless pathway and the two phenyl rings and the additional bridge complete their reorientation almost at the same time.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Reduced dimension rovibrational variational calculations of the S{sub 1} state of C{sub 2}H{sub 2}. II. The S{sub 1} rovibrational manifold and the effects of isomerization

Reduced dimension variational calculations have been performed for the rovibrational level structure of the S{sub 1} state of acetylene. The state exhibits an unusually complicated level structure, for various reasons. First, the potential energy surface has two accessible conformers, trans and cis. The cis conformer lies about 2700 cm{sup −1} above the trans, and the barrier to cis-trans isomerization lies about 5000 cm{sup −1} above the trans minimum. The trans vibrations ν{sub 4} (torsion) and ν{sub 6} (asym. bend) interact very strongly by Darling-Dennison and Coriolis resonances, such that their combination levels and overtones form polyads with unexpected structures. Both conformers exhibit very large x{sub 36} cross-anharmonicity since the pathway to isomerization is a combination of ν{sub 6} and ν{sub 3} (sym. bend). Near the isomerization barrier, the vibrational levels show an even-odd K-staggering of their rotational levels as a result of quantum mechanical tunneling through the barrier. The present calculations address all of these complications, and reproduce the observed K-structures of the bending and C–C stretching levels with good qualitative accuracy. It is expected that they will assist with the assignment of the irregular patterns near the isomerization barrier.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2014

Ordered defect compounds in CuInSe{sub 2} for photovoltaic solar cell application

Due to the complete compensation, defect complex (2V{sub Cu}+In{sub Cu}), namely two Cu vacancies and In located at Cu site, is stable in CuInSe{sub 2} (CIS). It is known that the series of ordered defect compounds (ODC) are constracted by ordering the defect complex. Based on the total energy calcalation by using the Korringa-Kohn-Rostoker coherent potential approxiamtion (KKR-CPA) method, we discuss phase separation of the CIS with the defect complexes into ODC and CIS. Since the band alignment between ODC and CIS is calculated to be type 2, effective electron-hole separation at the interface between ODC and CIS can be expected. This causes the enhancement of conversion efficiency of CIS-based solar cell materials.

14 SOLAR ENERGY↗
DOE OSTI2019

Riddles of the structure and vibrational dynamics of HO 3 resolved near the ab initio limit

The hydridotrioxygen (HO 3 ) radical has been explored in many previous theoretical and experimental studies over several decades, originally because of its possible relevance to the tropospheric HO x cycle but more recently because of its fascinating chemical bonding, geometric structure, and vibrational dynamics. We have executed new, comprehensive research on this vexing molecule via focal point analyses (FPA) to approach the ab initio limit of optimized geometric structures, relative energies, complete quartic force fields, and the entire reaction path for cis-trans isomerization. High-order coupled cluster theory was applied through the CCSDT(Q) and even CCSDTQ(P) levels, and CBS extrapolations were performed using cc-pVXZ (X = 2–6) basis sets. The cis isomer proves to be higher than trans by 0.52 kcal mol -1 , but this energetic ordering is achieved only after the CCSDT(Q) milestone is reached; the barrier for cis → trans isomerization is a minute 0.27 kcal mol -1 . The FPA central re(O–O) bond length of trans-HO3 is astonishingly long (1.670 Å), consistent with the semiexperimental re distance we extracted from microwave rotational constants of 10 isotopologues using FPA vibration-rotation interaction constants (α i ). The D 0 (HO–O 2 ) dissociation energy converges to a mere 2.80 ± 0.25 kcal mol -1 . Contrary to expectation for such a weakly bound system, vibrational perturbation theory performs remarkably well with the FPA anharmonic force fields, even for the torsional fundamental near 130 cm -1 . Exact numerical procedures are applied to the potential energy function for the torsional reaction path to obtain energy levels, tunneling rates, and radiative lifetimes. The cis → trans isomerization occurs via tunneling with an inherent half-life of 1.4 × 10 -11 s and 8.6 × 10 -10 s for HO 3 and DO 3 , respectively, thus resolving the mystery of why the cis species has not been observed in previous experiments executed in dissipative environments that allow collisional cooling of the trans-HO 3 product. However, the pure ground eigenstate of the cis species in a vacuum is predicted to have a spontaneous radiative lifetime of about 1 h and 5 days for HO 3 and DO 3 , respectively.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Photocyclic behavior of rhodopsin induced by an atypical isomerization mechanism

Vertebrate rhodopsin (Rh) contains 11- cis -retinal as a chromophore to convert light energy into visual signals. On absorption of light, 11- cis -retinal is isomerized to all- trans -retinal, constituting a one-way reaction that activates transducin (G t ) followed by chromophore release. Here we report that bovine Rh, regenerated instead with a six-carbon-ring retinal chromophore featuring a C 11 =C 12 double bond locked in its cis conformation (Rh6mr), employs an atypical isomerization mechanism by converting 11- cis to an 11,13- dicis configuration for prolonged G t activation. We report time-dependent UV-vis spectroscopy, HPLC, and molecular mechanics analyses revealed an atypical thermal reisomerization of the 11,13- dicis to the 11- cis configuration on a slow timescale, which enables Rh6mr to function in a photocyclic manner similar to that of microbial Rhs. With this photocyclic behavior, Rh6mr repeatedly recruits and activates G t in response to light stimuli, making it an excellent candidate for optogenetic tools based on retinal analog-bound vertebrate Rhs. Overall, we report these comprehensive structure–function studies unveil a unique photocyclic mechanism of Rh activation by an 11- cis –to–11,13- dicis isomerization.

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

Electronic Absorption Spectroscopy and Photochemistry of Criegee Intermediates

Interest in Criegee intermediates (CIs), often termed carbonyl oxides, and their role in tropospheric chemistry has grown massively since the demonstration of laboratory-based routes to their formation and characterization in the gas phase. This article reviews current knowledge regarding the electronic spectroscopy of atmospherically relevant CIs like CH 2 OO, CH 3 CHOO, (CH 3 ) 2 COO and larger CIs like methyl vinyl ketone oxide and methacrolein oxide that are formed in the ozonolysis of isoprene, and of selected conjugated carbene-derived CIs of interest in the synthetic chemistry community. Of the aforementioned atmospherically relevant CIs, all except CH 2 OO and (CH 3 ) 2 COO exist in different conformers which, under tropospheric conditions, can display strikingly different thermal loss rates via unimolecular and bimolecular processes. Calculated photolysis rates based on their absorption properties suggest that solar photolysis will rarely be a significant contributor to the total loss rate for any CI under tropospheric conditions. Nonetheless, there is ever-growing interest in the absorption cross sections and primary photochemistry of CIs following excitation to the strongly absorbing 1 ππ* state, and how this varies with CI, with conformer and with excitation wavelength. Furthermore, the later part of this review surveys the photochemical data reported to date, including a range of studies that demonstrate prompt photo-induced fission of the terminal O–O bond, and speculates about possible alternate decay processes that could occur following non-adiabatic coupling to, and dissociation from, highly internally excited levels of the electronic ground state of a CI.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Optimization of closed ion source for a high-sensitivity residual gas analyzer

A closed ion source (CIS) has been optimized by investigating the effect of electron entrance slit size and the effect of mesh in the slit. A stainless steel mesh was placed on the electron entrance slits for a uniform potential distribution inside the CIS anode. Sensitivity of the closed ion sources having four different slit sizes with and without the mesh was compared using mass spectra of SF{sub 6} gas (97% He gas base) introduced into the CIS anode through a needle valve. For each CIS, isolation of anode potential with a mesh in the slit exhibited a significant sensitivity enhancement, but ion current measured directly behind each CIS showed negligible mesh effect. In order to elucidate the mesh effect, electron trajectories were simulated inside the anode. The computer simulation shows that, with mesh in the slit, more electrons are focused to a central region of the anode. This suggests ions generated in the CIS with mesh should have higher probability of passing through the quadrupole mass filter.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

Pro5 is not essential for the formation of ‘Ni-hook’ in nickel superoxide dismutase

The N-terminus of nickel-dependent superoxide dismutase (NiSOD) forms a structural motif known as the "Ni-hook," where the peptide wraps around the metal to bring cysteine-2 and cysteine-6 into spatial proximity, allowing these residues to coordinate in a cis-geometry. A highly conserved proline-5 residue in the Ni-hook adopts a cis-conformation that is widely considered important for its formation. Herein, we investigate this role by point mutation of Pro5 to alanine. The results obtained show that the variant exhibits wild-type-like redox catalysis and features a Ni(III) center very similar to that found in enzyme. Structural analysis using x-ray absorption spectroscopy of the nickel sites in as-isolated P5A-NiSOD reveals changes in the variant and are consistent with a six-coordinate Ni site with (N/O) 4 S 2 coordination. These changes are attributed to changes in the Ni(II) site structure. Nickel-binding studies using isothermal titration calorimetry reveal two binding events with K d = 25(20) nM, and 250(60) nM. These events are attributed to i) Ni(II) binding to a preformed Ni-hook containing cis-Pro5 and ii) the combination of trans- to cis- isomerization upon Ni(II) binding, respectively. Finally, the higher-affinity binding event is absent in P5A-NiSOD, an observation attributed to the low abundance of the cis-Ala5 isomer in the apo-protein.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

The à 1 A u state of acetylene: ungerade vibrational levels in the region 45,800–46,550 cm -1

The ungerade vibrational levels of the à 1 A u (S 1 -trans) state of C 2 H 2 lying in the region 45,800-46,550 cm -1 have been assigned from IR-UV double resonance spectra. The aim has been to classify the complete manifold of S 1 -trans levels in this region, so as to facilitate the assignment of the bands of S 1 -cis C 2 H 2 . The rotational structure is complicated because of the overlapping of vibrational polyads with different Coriolis and Darling–Dennison parameters, but assignments have been possible with the help of predictions based on the properties of polyads at lower energy. An important result is that the analysis of the (1 1 4 1 , 1 1 6 1 ) polyad determines the anharmonicity constants x14 and x16, which will be needed to proceed to higher energies. Some regions of impressive complexity occur. Among these is the band given by the 3 3 6 1 , K=1 state at 45,945 cm -1 , where a three-level interaction within the S 1 state is confused by triplet perturbations. Several probable S 1 -cis states have been observed, including cis-6 2 , K=1; this vibrational level appears to show a K-staggering, of the type that arises when quantum mechanical tunnelling through the barrier to cis-trans isomerization is possible. The total number of identified cis vibrational states is now 6 out of an expected 10 up to the energies discussed in this paper.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Ligand‐Directed Actinide Oxo‐Bond Manipulation in Actinyl Thiacalix[4]arene Complexes

Abstract Understanding the chemistry of the inert actinide oxo bond in actinyl ions AnO 2 2+ is important for controlling actinide behavior in the environment, during separations, and in nuclear waste (An=U, Np, Pu). The thioether calixarene TC4A (4‐ tert ‐butyltetrathiacalix[4]arene) binds equatorially to the actinyl cation forming a conical pocket that differentiates the two trans‐ oxo groups. The ‘ate’ complexes, [A] 2 [UO 2 (TC4A)] (A=[Li(DME) 2 ], HNEt 3 ) and [HNEt 3 ] 2 [AnO 2 (TC4A)] (An=U, Np, Pu), enable selective oxo chemistry. Silylation of the U VI oxo groups by bis(trimethylsilyl)pyrazine occurs first at only the unencapsulated exo oxo and only one silylation is needed to enable migration of the endo oxo out of the cone, whereupon a second silylation affords the stable U IV cis‐ bis(siloxide) [A] 2 [U(OSiMe 3 ) 2 (TC4A)]. Calculations confirm that only one silylation event is needed to initiate oxo rearrangement, and that the putative cis dioxo isomer of [UO 2 (TC4A)] 2− would be stable if it could be accessed synthetically, at only 23 kcal.mol −1 in energy above the classical trans dioxo. Calculations for the transuranic cis [AnO 2 (TC4A)] 2− (An=Np, Pu) are at higher energies, 30–35 kcal.mol −1 , retaining the U complexes as the more obvious target for a cis ‐dioxo actinyl ion. The aryloxide (OAr) groups of the macrocycle are essential in stabilizing this as‐yet unseen uranyl geometry as further bonding in the TC4A U‐O Ar groups stabilizes the U=O ‘yl’ bonds, explaining the stability of the putative cis [UO 2 (TC4A)] 2− in this ligand framework.

Pyrch, Mikaela M. [College of Chemistry University↗
DOE OSTI2025

Ligand‐Directed Actinide Oxo‐Bond Manipulation in Actinyl Thiacalix[4]arene Complexes

Understanding the chemistry of the inert actinide oxo bond in actinyl ions AnO2 2+ is important for controlling actinide behavior in the environment, during separations, and in nuclear waste (An=U, Np, Pu). The thioether calixarene TC4A (4-tert-butyltetrathiacalix[4]arene) binds equatorially to the actinyl cation forming a conical pocket that differentiates the two trans-oxo groups. The 'ate' complexes, [A]2[UO2(TC4A)] (A=[Li(DME)2], HNEt3) and [HNEt3]2[AnO2(TC4A)] (An=U, Np, Pu), enable selective oxo chemistry. Silylation of the UVI oxo groups by bis(trimethylsilyl)pyrazine occurs first at only the unencapsulated exo oxo and only one silylation is needed to enable migration of the endo oxo out of the cone, whereupon a second silylation affords the stable UIV cis-bis(siloxide) [A]2[U(OSiMe3)2(TC4A)]. Calculations confirm that only one silylation event is needed to initiate oxo rearrangement, and that the putative cis dioxo isomer of [UO2(TC4A)]2- would be stable if it could be accessed synthetically, at only 23 kcal.mol-1 in energy above the classical trans dioxo. Calculations for the transuranic cis[AnO2(TC4A)]2- (An=Np, Pu) are at higher energies, 30-35 kcal.mol-1, retaining the U complexes as the more obvious target for a cis-dioxo actinyl ion. The aryloxide (OAr) groups of the macrocycle are essential in stabilizing this as-yet unseen uranyl geometry as further bonding in the TC4A U-OAr groups stabilizes the U=O 'yl' bonds, explaining the stability of the putative cis[UO2(TC4A)]2- in this ligand framework.

Pyrch, Mikaela M↗