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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
NASA NTRS2008

Thermally Actuated Hydraulic Pumps

Thermally actuated hydraulic pumps have been proposed for diverse applications in which direct electrical or mechanical actuation is undesirable and the relative slowness of thermal actuation can be tolerated. The proposed pumps would not contain any sliding (wearing) parts in their compressors and, hence, could have long operational lifetimes. The basic principle of a pump according to the proposal is to utilize the thermal expansion and contraction of a wax or other phase-change material in contact with a hydraulic fluid in a rigid chamber. Heating the chamber and its contents from below to above the melting temperature of the phase-change material would cause the material to expand significantly, thus causing a substantial increase in hydraulic pressure and/or a substantial displacement of hydraulic fluid out of the chamber. Similarly, cooling the chamber and its contents from above to below the melting temperature of the phase-change material would cause the material to contract significantly, thus causing a substantial decrease in hydraulic pressure and/or a substantial displacement of hydraulic fluid into the chamber. The displacement of the hydraulic fluid could be used to drive a piston. The figure illustrates a simple example of a hydraulic jack driven by a thermally actuated hydraulic pump. The pump chamber would be a cylinder containing encapsulated wax pellets and containing radial fins to facilitate transfer of heat to and from the wax. The plastic encapsulation would serve as an oil/wax barrier and the remaining interior space could be filled with hydraulic oil. A filter would retain the encapsulated wax particles in the pump chamber while allowing the hydraulic oil to flow into and out of the chamber. In one important class of potential applications, thermally actuated hydraulic pumps, exploiting vertical ocean temperature gradients for heating and cooling as needed, would be used to vary hydraulic pressures to control buoyancy in undersea research vessels. Heretofore, electrically actuated hydraulic pumps have been used for this purpose. By eliminating the demand for electrical energy for pumping, the use of the thermally actuated hydraulic pumps could prolong the intervals between battery charges, thus making it possible to greatly increase the durations of undersea exploratory missions.

Jones, Jack↗
NASA NTRS2009

Alternative OTEC Scheme for a Submarine Robot

A proposed system for exploiting the ocean thermal gradient to generate power would be based on the thawing-expansion/ freezing-contraction behavior of a wax or perhaps another suitable phase-change material. The power generated by this system would be used to recharge the batteries in a battery-powered unmanned underwater vehicle [UUV (essentially, a small exploratory submarine robot)] of a type that has been deployed in large numbers in research pertaining to global warming. A UUV of this type travels between the ocean surface and various depths, measuring temperature and salinity. This proposed system would be an alternative to another proposed ocean thermal energy conversion (OTEC) system that would serve the same purpose but would utilize a thermodynamic cycle in which CO2 would be the working fluid. That system is described in Utilizing Ocean Thermal Energy in a Submarine Robot (NPO-43304), immediately following this brief. The main advantage of this proposed system over the one using CO2 is that it could derive a useful amount of energy from a significantly smaller temperature difference. At one phase of its operational cycle, the system now proposed would utilize the surface ocean temperature (which lies between 15 and 20 C over most of the Earth) to melt a wax (e.g., pentadecane) that has a melting/freezing temperature of about 10 C. At the opposite phase of its operational cycle, the system would utilize the lower ocean temperature at depth (e.g., between 4 and 7 C at a depth of 300 m) to freeze the wax. The melting or freezing causes the wax to expand or contract, respectively, by about 8 volume percent.

Jones, Jack↗
NASA NTRS2012

Formulation and Testing of Paraffin-Based Solid Fuels Containing Energetic Additives for Hybrid Rockets

Many approaches have been considered in an effort to improve the regression rate of solid fuels for hybrid rocket applications. One promising method is to use a fuel with a fast burning rate such as paraffin wax; however, additional performance increases to the fuel regression rate are necessary to make the fuel a viable candidate to replace current launch propulsion systems. The addition of energetic and/or nano-sized particles is one way to increase mass-burning rates of the solid fuels and increase the overall performance of the hybrid rocket motor.1,2 Several paraffin-based fuel grains with various energetic additives (e.g., lithium aluminum hydride (LiAlH4) have been cast in an attempt to improve regression rates. There are two major advantages to introducing LiAlH4 additive into the solid fuel matrix: 1) the increased characteristic velocity, 2) decreased dependency of Isp on oxidizer-to-fuel ratio. The testing and characterization of these solid-fuel grains have shown that continued work is necessary to eliminate unburned/unreacted fuel in downstream sections of the test apparatus.3 Changes to the fuel matrix include higher melting point wax and smaller energetic additive particles. The reduction in particle size through various methods can result in more homogeneous grain structure. The higher melting point wax can serve to reduce the melt-layer thickness, allowing the LiAlH4 particles to react closer to the burning surface, thus increasing the heat feedback rate and fuel regression rate. In addition to the formulation of LiAlH4 and paraffin wax solid-fuel grains, liquid additives of triethylaluminum and diisobutylaluminum hydride will be included in this study. Another promising fuel formulation consideration is to incorporate a small percentage of RDX as an additive to paraffin. A novel casting technique will be used by dissolving RDX in a solvent to crystallize the energetic additive. After dissolving the RDX in a solvent chosen for its compatibility with both paraffin and RDX, the mixture will be combined with the melted paraffin. With the melting point of the paraffin far below the decomposition temperature of the RDX, the solvent will be boiled off, leaving the crystallized RDX embedded in the paraffin. At low percentages of RDX additive and with crystallized RDX surrounded by paraffin, the fuel grains will remain inert, maintaining a key benefit of hybrids in the safety of the solid fuel.

Larson, Daniel B.↗
DOE OSTI2025

3D Printing of Highly Porous Polypropylene Separators for Lithium‐Ion Batteries Using Fused Deposition Modeling and Thermally Induced Phase Separation

Appearing as one of the key-components of lithium-ion batteries (LIBs), this work specifically focuses on the additive manufacturing (AM) of custom-shape separators, facilitated by the filament material extrusion process, also called fused deposition modeling (FDM). The development and optimization of composite thermoplastic filament feedstocks combining polypropylene and paraffin wax, followed by the 3D printing of the separator membranes is shown. A post-processing step, based on thermal induced phase separation (TIPS), is introduced to promote porosity formation through removal of the paraffin wax sacrificial phase within the 3D printed items. Separators with different polypropylene/paraffin wax ratios are developed and the impact on printability, mechanical strength, porosity, and electrochemical performances, is thoroughly discussed. X-ray micro-computed tomography is employed to assess the geometric fidelity and to detect printing defects in a complex 3D lattice structure. The performance of the 3D printed porous separators is also compared to a commercial separator. This pioneering research establishes a foundation for the creation of porous separators that can adapt to and conform into 3D printed battery architectures with novel form factors, and also creates opportunities for the use of FDM and TIPS for a wide range of applications that employ porous structures beyond the energy storage field.

3D printing↗
DOE OSTI2024

Molten-Phase Unsaturation Enhanced Pyrolytic Upcycling of Polyolefins

Fast pyrolysis is a robust deconstruction technology for chemically upcycling waste plastics without losing significant carbon to noncondensable gases. However, fast pyrolysis of polyolefins often produces hydrocarbons with broad molecular weight distributions, mainly waxes, which can also negatively affect the commercial reactor operation and downstream upgrading of the products. We discovered that combining molten-phase thermal treatment with subsequent fast pyrolysis offers a facile method to enhance polyolefin pyrolysis and catalytic upgrading. The molten-phase thermal treatment increased unsaturated C–C bonds in the treated polyolefins. During subsequent pyrolysis, the preheated polyolefins significantly reduced wax range hydrocarbons in the condensable products without an increase in gas formation. Here, the wax yields from pyrolysis of high-density polyethylene (HDPE) preheated to 295 °C and low-density polyethylene (LDPE) preheated to 275 °C were 20.5% and 26.5%, respectively, compared to 38.6% and 46% produced from pyrolyzing untreated polyolefins. When catalytically pyrolyzed using a zeolite catalyst, the preheated polyolefins promoted higher yields of olefins during ex-situ catalytic pyrolysis and higher yields of aromatic hydrocarbons during in-situ catalytic pyrolysis. During ex-situ catalytic pyrolysis, ethylene yields were 23.3% and 24.7% for the preheated HDPE and LDPE compared to 16.7% and 9.3% for untreated HDPE and LDPE, respectively.

Aromatic compounds↗
NASA NTRS1985

Near infrared leaf reflectance modeling

Near infrared leaf reflectance modeling using Fresnel's equation (Kumar and Silva, 1973) and Snell's Law successfully approximated the spectral curve for a 0.25-mm turgid oak leaf lying on a Halon background. Calculations were made for ten interfaces, air-wax, wax-cellulose, cellulose-water, cellulose-air, air-water, and their inverses. A water path of 0.5 mm yielded acceptable results, and it was found that assignment of more weight to those interfaces involving air versus water or cellulose, and less to those involving wax, decreased the standard deviation of the error for all wavelengths. Data suggest that the air-cell interface is not the only important contributor to the overall reflectance of a leaf. Results also argue against the assertion that the near infrared plateau is a function of cell structure within the leaf.

Parrish, J. B.↗
NASA NTRS2006

Novel Thermal Powered Technology for UUV Persistent Surveillance

Buoyancy Generation: Various technology attempts include melting a wax, which pushes directly against a piston (U.S. Patent 5,291,847) or against a bladder (Webb Research), using ammonia or Freon 21 (U.S. Patent 5,303,552), and using solar heat to expand an oil (www.space.com, April, 10, 2002). All these heat-activated buoyancy control designs have thus far proved impractical and have ultimately failed during repeated cycling in ocean testing. JPL has demonstrated fully reversible 10 C encapsulated wax phase change, which can be used to change buoyancy without electrical hydraulic pumps. This technique has greatly improved heat transfer and much better reversibility than previous designs. Power Generation: Ocean Thermal Energy Conversion (OTEC) systems have been designed that transfer deep, cold sea water to the surface to generate electricity using turbine cycles with ammonia or water as the working fluid. JPL has designed several UUV systems: 1) Using a propeller water turbine to generate power on a gliding submersible; 2) Employing a compact CO2 turbine cycle powered by moving through thermoclines; and 3) Using melted wax to directly produce power through a piston-geared generator.

submersible↗
NASA NTRS2009

Development, Testing, and Failure Mechanisms of a Replicative Ice Phase Change Material Heat Exchanger

Phase change materials (PCM) may be useful for thermal control systems that involve cyclical heat loads or cyclical thermal environments such as Low Earth Orbit (LEO) and Low Lunar Orbit (LLO). Thermal energy can be stored in the PCM during peak heat loads or in adverse thermal environments. The stored thermal energy can then be released later during minimum heat loads or in more favorable thermal environments. One advantage that PCM s have over evaporators in this scenario is that they do not use a consumable. Wax PCM units have been baselined for the Orion thermal control system and also provide risk mitigation for the Altair Lander. However, the use of water as a PCM has the potential for significant mass reduction since the latent heat of formation of water is approximately 70% greater than that of wax. One of the potential drawbacks of using ice as a PCM is its potential to rupture its container as water expands upon freezing. In order to develop a space qualified ice PCM heat exchanger, failure mechanisms must first be understood. Therefore, a methodical experimental investigation has been undertaken to demonstrate and document specific failure mechanisms due to ice expansion in the PCM. An ice PCM heat exchanger that replicates the thermal energy storage capacity of an existing wax PCM unit was fabricated and tested. Additionally, methods for controlling void location in order to reduce the risk of damage due to ice expansion are investigated. This paper presents the results to date of this investigation.

Leimkuehler, Thomas O.↗
NASA NTRS2010

Development, Testing, and Failure Mechanisms of a Replicative Ice Phase Change Material Heat Exchanger

Phase change materials (PCM) may be useful for thermal control systems that involve cyclical heat loads or cyclical thermal environments such as Low Earth Orbit (LEO) and Low Lunar Orbit (LLO). Thermal energy can be stored in the PCM during peak heat loads or in adverse thermal environments. The stored thermal energy can then be released later during minimum heat loads or in more favorable thermal environments. One advantage that PCM's have over evaporators in this scenario is that they do not use a consumable. Wax PCM units have been baselined for the Orion thermal control system and also provide risk mitigation for the Altair Lander. However, the use of water as a PCM has the potential for significant mass reduction since the latent heat of formation of water is approximately 70% greater than that of wax. One of the potential drawbacks of using ice as a PCM is its potential to rupture its container as water expands upon freezing. In order to develop a space qualified ice PCM heat exchanger, failure mechanisms must first be understood. Therefore, a methodical experimental investigation has been undertaken to demonstrate and document specific failure mechanisms due to ice expansion in the PCM. An ice PCM heat exchanger that replicates the thermal energy storage capacity of an existing wax PCM unit was fabricated and tested. Additionally, methods for controlling void location in order to reduce the risk of damage due to ice expansion are investigated. This paper presents the results to date of this investigation. Nomenclature

Leimkuehler, Thomas O.↗
NASA NTRS2005

Making a Metal-Lined Composite-Overwrapped Pressure Vessel

process has been devised for the fabrication of a pressure vessel that comprises a composite-material (matrix/fiber) shell with a metal liner on its inner surface. The use of the composite material makes it possible for the tank to be strong enough to withstand the anticipated operating pressure and yet weigh less than does an equivalent all-metal tank. The metal liner is used as a barrier against permeation: In the absence of such a barrier, the pressurized gas in the tank could leak by diffusing through the composite-material shell. The figure depicts workpieces at four key stages in the process, which consists of the following steps: 1. A mandrel that defines the size and shape of the pressure vessel is made by either molding or machining a piece of tooling wax. 2. Silver paint is applied to the surface of the mandrel to make it electrically conductive. 3. The ends of the mandrel are fitted with metal bosses. 4. The mandrel is put into a plating bath, wherein the metal liner is electrodeposited. Depending on the applications, the liner metal could be copper, nickel, gold, or an alloy. Typical liner thicknesses range from 1 to 10 mils (0.025 to 0.25 mm). 5. The wax is melted from within, leaving the thin metal liner. 6. A hollow shaft that includes holes and fittings through which the liner can be pressurized is sealed to both ends of the liner. The liner is pressurized to stiffen (and hence stabilize) it for the next step. 7. The pressurized liner is placed in a filament-winding machine, which is then operated to cover the liner with multiple layers of an uncured graphite-fiber/epoxy-matrix or other suitable composite material. 8. The composite-overwrapped liner is cured in an oven. 9. The pressure is relieved and the shaft is removed. The tank is then ready for use. The process as described above accommodates variations: a) The mandrel could be made of a wax that melts at a higher temperature and not removed until the tank is cured in the oven. b) The tank need not be cylindrical or axisymmetric, as long as the filament-winding machine can accommodate the chosen shape. c) Shallow grooves could be formed on the surface of the mandrel to give the liner a bellows-like character for reinforcement and/or to accommodate expansion and contraction.

DeLay, Tom↗
NASA NTRS2016

Water Phase Change Heat Exchanger System Level Analysis for Low Lunar Orbit

In low Lunar orbit (LLO) the thermal environment is cyclic - extremely cold in the eclipse and as warm as room temperature near the subsolar point. Phase change material heat exchangers (PCHXs) are the best option for long term missions in these environments. The Orion spacecraft will use a n-pentadecane wax PCHX for its envisioned mission to LLO. Using water as a PCM material is attractive because its higher heat of fusion and greater density result in a lighter, more compact PCHX. To assess the use of a water PCHX for a human spacecraft in a circular LLO, a system level analysis was performed for the Orion spacecraft. Three cases were evaluated: 1) A one-to-one replacement of the wax PCHX on the internal thermal control loop with a water PCHX (including the appropriate control modifications), 2) reducing the radiator return setpoint temperature below Orion's value to enhance PCHX freezing, and 3) placing the water PCM on the external loop. The model showed that the water PCHX could not be used as a drop-in replacement for the wax PCHX. It did not freeze fully during the eclipse owing to its low freezing point. To obtain equivalent performance, 40% more radiator area than the Orion baseline was required. The study shows that, although water PCHXs are attractive at a component level, system level effects mean that they are not the best choice for LLO.

Navarro, Moses↗
DOE OSTI2024

Ectopic Production of 3,4-Dihydroxybenzoate in Planta Affects Cellulose Structure and Organization

Lignocellulosic biomass is a highly sustainable and largely carbon dioxide neutral feedstock for the production of biofuels and advanced biomaterials. Although thermochemical pretreatment is typically used to increase the efficiency of cell wall deconstruction, genetic engineering of the major plant cell wall polymers, especially lignin, has shown promise as an alternative approach to reduce biomass recalcitrance. Poplar trees with reduced lignin content and altered composition were previously developed by overexpressing bacterial 3-dehydroshikimate dehydratase (QsuB) enzyme to divert carbon flux from the shikimate pathway. In this work, three transgenic poplar lines with increasing QsuB expression levels and different lignin contents were studied using small-angle neutron scattering (SANS) and wide-angle X-ray scattering (WAXS). SANS showed that although the cellulose microfibril cross-sectional dimension remained unchanged, the ordered organization of the microfibrils progressively decreased with increased QsuB expression. This was correlated with decreasing total lignin content in the QsuB lines. WAXS showed that the crystallite dimensions of cellulose microfibrils transverse to the growth direction were not affected by the QsuB expression, but the crystallite dimensions parallel to the growth direction were decreased by ~20%. Cellulose crystallinity was also decreased with increased QsuB expression, which could be related to high levels of 3,4-dihydroxybenzoate, the product of QsuB expression, disrupting microfibril crystallization. In addition, the cellulose microfibril orientation angle showed a bimodal distribution at higher QsuB expression levels. Altogether, this study provides new structural insights into the impact of ectopic synthesis of small-molecule metabolites on cellulose organization and structure that can be used for future efforts aimed at reducing biomass recalcitrance.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2026

Formation of Non-Doped Cubic Lithium Lanthanum Zirconium Oxide Nanofibers: Insights from In Situ Synchrotron X-Ray Scattering

This study investigates the formation mechanism of non-doped cubic lithium lanthanum zirconium oxide (c-LLZO) nanofibers using in situ synchrotron X-ray scattering techniques. Electrospun polymer precursor nanofibers were annealed at temperatures up to 800 °C, enabling real-time tracking of phase transitions via simultaneous small-angle X-ray scattering (SAXS), wide-angle X-ray scattering (WAXS), and evolved CO 2 gas analysis. The results reveal a three-step transformation pathway: polymer decomposition, formation of La 2 Zr 2 O 7 (LZO), and direct conversion of LZO to c-LLZO without intermediate tetragonal phases detected within the sensitivity of our in situ WAXS measurement. Cryo-electron energy loss spectroscopy (EELS) further elucidates the role of lithium diffusion, showing Li enrichment at fiber surfaces and Li deficiency in the interior, which stabilizes the cubic phase. This Li segregation effect in nanostructured LLZO materials extends beyond the previously reported size effect. This work advances the understanding of c-LLZO formation mechanisms and provides practical insights for optimizing synthesis routes to achieve phase-pure c-LLZO for solid-state battery applications.

LLZO phase stability↗
DOE OSTI2026

Telomere-to-telomere assemblies of chromosome 10 reveal complex adaptive variation of 3-ketoacyl-CoA-synthases in Populus trichocarpa likely driven by Helitrons

The model woody plant Populus trichocarpa displays an atypical alkene-diverse wax cuticle likely driven by copy number variation (CNV) of 3-ketoacyl-CoA synthases ( KCS ), which has been difficult to confirm with short-read assemblies. Long-read sequencing enables the development of telomere-to-telomere resources to detect cryptic variation, including CNVs, which are currently missed. Integrating this information can improve genomic prediction for breeding and provide insights into the evolutionary basis of important traits. Our analysis of 78 long-read haplotypes from chromosome 10 identified more than twice as many KCS genes as previously reported, and numerous intragenic non-synonymous substitutions. Random Forest predictive models highlighted the importance of Potri.010G079500 in producing very long chain alkenes; however, its absence did not predict previously reported alkene-deficient phenotypes. Instead, alkene levels are best predicted by the combinations of KCS copies. Additionally, amino acid substitutions clustered around ligand and donor binding pockets, suggesting they contribute to differing wax cuticle composition. Finally, each KCS gene and copy was linked to a Helitron transposon. A phylogenetic analysis suggests Helitrons are the evolutionary mechanism for generating KCS tandem arrays. Long-read generated telomere-to-telomere assemblies of P. trichocarpa chromosome 10 revealed large-effect loci critical to genetic studies that are unattainable from short-reads. This new resource produced novel insights into genome structure and function, and a novel mechanism for generating tandem gene duplication. Our results highlight that, given current challenges in annotation and assembly, detailed and focused long-read sequences are key to interpreting complex genomic regions that contain tandem copy number variants.

09 BIOMASS FUELS↗
DOE OSTI2025

Ectopic expression of pectate lyase PtxtPL1-27 in aspen affects leaf cuticle development

Cuticle - a hydrophobic barrier of cutin and waxes covering the outer cell wall surface of plants - enables survival in terrestrial habitats. However, it is not understood how the hydrophobic cuticle precursors travel through the homogalacturonan-rich hydrophilic cell wall. To elucidate the role of homogalacturonan in cuticle development, we disrupted its integrity by overexpressing a pectate lyase, PtxtPL1-27, in aspen. PtxtPL1-27 had pleiotropic effects on shoot development, including the reduction of cuticle thickness and changes in cutin and wax composition, but the expression of cutin biosynthetic genes was little affected. Despite a reduction in homogalacturonan content in the leaves, labeling with the homogalacturonan-specific antibody JIM5 in the outer epidermal cell wall layer increased and displayed an altered pattern. Moreover, the ultrastructure of cell walls was changed concomitant with lipid accumulation. We propose that the disruption of homogalacturonan integrity affected the cutinsome-dependent transport and polymerization of cutin monomers in the cell wall.

Plant Biology↗
DOE OSTI2025

Capture of volatile RuO 4 from oxidized simulated used nuclear fuel solutions

Ruthenium is a challenging fission product in used nuclear fuel (UNF) reprocessing due to its complex redox chemistry, variable speciation in nitric acid, partial extractability, and volatility. This work presents a strategy for Ru removal based on the volatilization of RuO 4 using the strong oxidant sodium bismuthate, followed by RuO 2 deposition onto various substrates. Among the materials tested, polymer-based substrates such as polyolefin wax film (Parafilm®), exhibited superior performance, achieving up to near-quantitative Ru removal from solution. After dissolution of the substrate, 99.6% of the Ru was recovered as RuO 2 . The deposition mechanism onto the polyolefin wax film involves both physisorption and chemical reaction through oxidative cleavage of olefinic bonds within the polymer. In contrast, on inorganic substrates such as Al foil, RuO 4 undergoes incomplete surface adsorption and reduction, as confirmed by FTIR and XPS analyses. This approach remains effective under conditions of simulated oxidation of UNF solutions, selectively removing Ru while leaving other fission products in solution. As a result, capture of RuO 4 offers a practical and efficient strategy for ruthenium decontamination and recovery, offering a route for integration into existing UNF reprocessing flowsheets to enhance overall process safety and performance.

Ruthenium↗
DOE OSTI2024

Catalytic Upgrading of Pyrolysis Condensables from Postconsumer Polyolefins Using HZSM-5

The conversion of plastic wastes to monomeric olefins is an attractive means for achieving a plastic circular economy. In our study, a fluidized bed reactor converts post-consumer waste high-density polyethylene (HDPE) and polypropylene (PP) to mostly condensed pyrolysis waxes and some oils, preventing carbon loss to gases. The pyrolysis condensables were upgraded to light olefins (C 2 –C 5 ) at carbon yields greater than 76 wt % using the HZSM-5 zeolite catalyst at a post pyrolysis process that employed a micropyrolyzer. These results were comparable to olefin monomer yields from direct ex situ catalytic pyrolysis of the original waste plastics without condensing the vapors, highlighting the potential applicability of this approach in plastic waste recycling. Our results suggest that a centralized catalytic upgrading facility fed by pyrolysis condensables sourced from distributed thermochemical processing plants is a promising pathway to a circular economy. Such an approach enables utilization of available catalytic cracking infrastructure while focusing on setting up distributed thermochemical processing plants close to material recovery facilities. As a result, the energy-dense pyrolysis waxes are more suitable for transportation, contributing to the overall scalability and economic viability of the proposed distributed approach.

10 SYNTHETIC FUELS↗
DOE OSTI2025

Characterizing Ultrafast Intersystem Crossing Pathways in Molecular Pt Dimers Using Time-Resolved Wide-Angle X-ray Scattering

Vibronic coupling between transition metal charge transfer states is a potential mechanism for enhancing the intersystem crossing (ISC) rate. Vibronic coupling-driven ISC has been observed in Pt­(II) dimer complexes, where the trajectory across excited-state pathways is tuned by atomic displacements via Pt–Pt stretching vibrations. Time-resolved wide-angle X-ray scattering (TR-WAXS) was utilized to quantify the Pt–Pt contraction following metal–metal-to-ligand charge transfer (MMLCT) excitation in Pt dimers with different bridging ligands. Both complexes exhibit Pt–Pt bond formation with a decrease in Pt–Pt distance of ∼ 0.25 Å and coherent vibrational wavepackets (CVWPs) encoded in the Pt–Pt contraction of both dimers. However, the complexes exhibit different time-dependent evolution of their CVWPs. Analysis of interference patterns between different CVWPs is used to track the trajectory across the excited-state surfaces. Furthermore, this work demonstrates that the interference between CVWPs in ultrafast TR-WAXS encodes indirect information regarding electronic excited-states to reveal the Pt dimer bridge-dependent ISC mechanism.

Computational chemistry↗