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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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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Towards Energy–Efficient Direct Air Capture with Photochemically–Driven CO 2 Release and Solvent Regeneration

The intensive energy demands associated with solvent regeneration and CO 2 release in current direct air capture (DAC) technologies makes their deployment at the massive scales (GtCO 2 /year) required to positively impact the climate economically unfeasible. This challenge underscores the critical need to develop new DAC processes with significantly reduced energy costs. Recently, we developed a new approach to photochemically drive efficient release of CO 2 through an intermolecular proton transfer reaction by exploiting the unique properties of an indazole metastable-state photoacid (mPAH), opening a new avenue towards energy efficient on-demand CO 2 release and solvent regeneration using abundant solar energy instead of heat. In this Concept Article, we will describe the principle of our photochemically-driven CO 2 release approach for solvent-based DAC systems, discuss the essential prerequisites and conditions to realize this cyclable CO 2 release chemistry under ambient conditions. We outline the key findings of our approach, discuss the latest developments from other research laboratories, detail approaches used to monitor DAC systems in situ, and highlight experimental procedures for validating its feasibility. Finally, we conclude with a summary and outlook into the immediate challenges that must be addressed in order to fully exploit this novel photochemically-driven approach to DAC solvent regeneration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Signaling from below: rodents select for deeper fruiting truffles with stronger volatile emissions

Many plant and fungal species use volatile organic compounds (VOCs) as chemical signals to convey information about the location or quality of their fruits or fruiting bodies to animal dispersers. Identifying the environmental factors and biotic interactions that shape fruit selection by animals is key to understanding the evolutionary processes that underpin chemical signaling. Using four Elaphomyces truffle species, we explored the role of fruiting depth, VOC emissions, and protein content in selection by five rodent species. We used stable isotope analysis of nitrogen (δ15N) in truffles to estimate fruiting depth, proton-transfer-reaction mass spectrometry to determine volatile emission composition, and nitrogen concentrations to calculate digestible protein of truffles. We coupled field surveys of truffle availability with truffle spore loads in rodent scat to determine selection by rodents. Despite presumably easier access to the shallow fruiting species, E. americanus (0.5-cm depth) and E. verruculosus (2.5-cm depth), most rodents selected for truffles fruiting deeper in the soil, E. macrosporus (4.1-cm depth) and E. bartlettii (5.0-cm depth). The deeper fruiting species had distinct VOC profiles and produced significantly higher quantities of odiferous compounds. Myodes gapperi (southern red-backed vole), a fungal specialist, also selected for truffles with high levels of digestible protein, E. verruculosus and E. macrosporus. Our results highlight the importance of chemical signals in truffle selection by rodents and suggest that VOCs are under strong selective pressures relative to protein rewards. Strong chemical signals likely allow detection of truffles deep within the soil and reduce foraging effort by rodents. Finally, for rodents that depend on fungi as a major food source, protein content may also be important in selecting truffles.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Application of Atmospheric Gases and Particulate Matter to the Assessment of Urban Heat Island

Background: Urban heat island (UHI), where built areas are warmer compared to non-urban regions, increases human related diseases and mortality. A key challenge in UHI analysis is the designation of sites as urban or suburban/rural; however, the growing complexity of green spaces in urban areas and the predominance of the transportation sector in nonurban areas creates a dilemma for distinct delineation. Objectives: This study aims to utilize the variability of atmospheric components such as particulate matter (PM), inorganic gases, and volatile organic compounds (VOCs) as direct tracers of the degree of urbanization for ground-based measurements to fully comprehend UHI in convoluted regions with indistinct delineation of urban and nonurban environments. Methods: Atmospheric gases and aerosols were used as direct tracers of urbanization for UHI analysis. Inorganic gases and particulate matter were monitored in two sites in a southeastern US city with varying degrees of urbanization. VOCs were analyzed using a proton transfer reaction time-of-flight mass spectrometer. Results: The more-urbanized site exhibited warmer night conditions and elevated total oxidant levels, leading to the formation of nanometer-sized particles. Machine learning analysis revealed similar atmospheric pollutant profiles for both sites, suggesting comparable sources and variability. Biogenic VOCs were enhanced at the less-urbanized site; however, levels of anthropogenic aromatic VOCs were comparable for both sites. A comprehensive mass spectra analysis revealed distinct molecular backbones per site that further affirmed the applicability of VOCs as indicators of urbanization. Conclusion: This study concludes that VOCs provide more direct and accurate information than typical inorganic gases and PM parameters for characterizing the degree of urbanization. Further exploration of VOCs can enhance our understanding of UHI dynamics and its interaction with vegetation in urban green spaces.

Air quality sensor↗
DOE OSTI2024

Air quality impacts from the development of unconventional oil and gas well pads: Air toxics and other volatile organic compounds

Unconventional oil and natural gas development (UOGD) has expanded rapidly across the United States in recent decades and raised concerns about associated air quality impacts. While significant effort has been made to quantify methane emissions, relatively few observations have been made of Volatile Organic Compounds (VOCs), especially during drilling and completion of new wells. Extensive air monitoring during development of several large, multi-well pads in Broomfield, Colorado, in the Denver-Julesburg Basin, provides a novel opportunity to examine changes in local air toxics and other VOC concentrations during well drilling and completions and production. These operations offer an especially useful case to study as several management practices were implemented to reduce emissions (e.g., electrified, grid-powered drill rigs and closed loop fluid handling systems to reduce truck traffic and limit fluid handling on the pad). With simultaneous measurements of methane and 50 VOCs from October 2018 to December 2022 at as many as 19 sites near well pads, in adjacent neighborhoods, and at a more distant reference location, we identify impacts from each phase of well development and production. Use of weekly, time-integrated canisters, a Proton Transfer Reaction Mass Spectrometer (PTR-MS), continuous photoionization detectors (PID) to trigger canister collection upon detection of VOC-rich plumes, and an instrumented vehicle, provided a powerful suite of measurements to characterize both transient plumes and longer-term changes in air quality. Prior to the start of well development, VOC gradients were small across Broomfield. Once drilling commenced, concentrations of oil and gas (O&G) related VOCs, including alkanes and aromatics, increased around active well pads. Concentration increases were clearly apparent during certain operations, including drilling, coil tubing/millout operations, and production tubing installation. Emissions of C 8 –C 10 n-alkanes during drilling operations highlighted the importance of VOC emissions from synthetic drilling mud chosen to reduce odor impacts. More than 90 samples were collected of transient plumes. Using composition measurements, meteorological data, and information about well pad activities, these plumes were connected with specific UOGD operations including drilling, flowback, and production equipment maintenance. The chemical signatures of these plumes differed by operation type (e.g., C 8 –C 10 n-alkanes constituted a larger fraction of measured VOCs in drilling-related plumes). Concentrations of individual, oil and gas-related VOCs in these plumes were often several orders of magnitude higher than in background air, with maximum ethane and benzene concentrations of 79,600 and 819 ppbv, respectively. Because these plumes typically impact a monitoring site for just several minutes, they are easily missed by slower-responding instruments. Study measurements highlight future emission mitigation opportunities during UOGD operations, including better control of emissions from shakers that separate drill cuttings from drilling mud, production separator maintenance operations, and periodic emptying of sand cans during flowback operations.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Diversifying hierarchical ionic assembly by docking cations to anions as salt bridges

Here, we expand the diversity of building blocks available for ionic assembly by introducing tertiary (3°) ammonium cations into anion complexes. We use proton transfer between 3° amines and organo-phosphoric acids to generate H-bonding cations (R 3 NH + ) and anions (RHPO 4 – ) that co-assemble with cyanostar macrocycles into assemblies with 2:2:2 stoichiometry. At the heart is a supramolecular dimer where phosphate anions form salt bridges by H-bonding with cations. Unlike conventional 4° ammonium cations, 3,000 commercial amines provide diversity for high-throughput screening of 72 combinations (9 nitrogen bases and 8 acids), producing 13 privileged partners for quantitative assembly. Yields depend on the solvent and sterics of salt bridge formation. Ten more nitrogen bases connect to fluorophores (pyrene), photocatalysts (quinoline), drugs (Cipralex, Zytiga), and ionic liquids (imidazole). The synthesis and examination of 82 new salts exemplify how acid-base chemistry can open a pipeline to a diversity of building blocks for exploring hierarchical ionic assembly.

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

Acetone to isobutene conversion on Zn x Ti y O z : Effects of TiO 2 facet

In this study, liquid-phase chemical grafting method was used to graft Zn onto TiO 2 with preferentially exposed (1 0 1) or (0 0 1) facet. The obtained Zn x Ti y O z materials were characterized using various techniques (e.g., XRD, Raman, DRIFTS etc.) and evaluated for the acetone-to-isobutene reaction. It was found that over TiO 2 (0 0 1), both terminal and bridging hydroxyls were readily titrated by Zn deposition, whereas a substantial amount of bridging hydroxyls on TiO 2 (1 0 1) remained. Although dominant Zn-O-terminated surface was obtained on two Zn x Ti y O z samples, bridging hydroxyls with high H-D exchange reactivity were observed on Zn x Ti y O z (1 0 1) compared with Zn x Ti y O z (0 0 1). The bridging hydroxyls showing rapid proton transfer efficiently stabilizes a transition state of diacetone alcohol intramolecular rearrangement for isobutene production as opposed to the diacetone alcohol dehydration.

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

Nanochannel electrodes facilitating interfacial transport for PEM water electrolysis

Proton-exchange membrane water electrolyzers (PEMWEs) are a promising technology for green hydrogen production; however, interfacial transport behaviors are poorly understood, hindering device performance and longevity. Here, we first utilized finite-gap electrolyzer to demonstrate the possibility of proton transfer through water in PEMWEs. The measured high-frequency resistances (HFRs) exhibit a linear trend with increasing gap distance, where extrapolation shows a lower value compared with HFRs in regular zero-gap electrolyzers, indicating that ohmic resistance could be further reduced. We introduce nanochannels to facilitate mass transport, as evidenced by both liquid-fed and vapor-fed electrolysis. Nanochannel electrodes achieve a voltage reduction of 190 mV at 9 A·cm –2 compared with the Ir-PTEs without nanochannels. Furthermore, nanochannel electrodes show negligible degradation through 100,000 accelerated-stress tests and over 2,000 h of operation at 1.8 A·cm –2 with a decay rate of 11.66 μV·h –1 . These results provide new insights into localized transport dynamics for PEMWEs and highlight the significance of interfacial engineering for electrochemical devices.

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

Finely tuning the microporosity in phosphoric acid doped triptycene-containing polybenzimidazole membranes for highly permselective helium and hydrogen recovery

High-performance polymer membranes with well-defined microporosity and size-sieving ability are especially attractive for helium and hydrogen recovery. Here, in this study, we report novel macromolecular engineering of polybenzimidazole (PBI) membranes that integrate hierarchical triptycene units for high permeability and polyprotic acid doping for size sieving via controllable manipulation of microporous architecture. The triptycene moieties disrupt chain packing and introduce additional configurational free volume, leading to significantly boosted He and H 2 permeabilities compared to previously reported PBI membranes. The acid doping resulted in crosslinked PBI membranes via hydrogen bonding and proton transfer with dramatically enhanced gas selectivities. Via adjusting the H 3 PO 4 -doping level, triptycene-based polybenzimidazole (TPBI) composite membranes (TPBI-(H 3 PO 4 ) x ) exhibit the highest gas selectivities for He enrichment (i.e., α(He/CH 4 ) = 7052 ± 156) and H 2 purification (i.e., α(H 2 /CH 4 ) = 5128 ± 110) among existing polymeric gas separation membranes. Additionally, under mixed-gas conditions at 150 °C, the TPBI-(H 3 PO 4 ) 0.98 membrane displays a H 2 permeability of 46.7 Barrer and a H 2 /CO 2 selectivity of 16, far beyond the Robeson's 2008 upper bound for H 2 /CO 2 separation. The facile and diverse tunability and excellent gas separation performance make TPBI-(H 3 PO 4 ) x membranes highly attractive for helium and hydrogen separation.

42 ENGINEERING↗
DOE OSTI2024

Bedroom Concentrations and Emissions of Volatile Organic Compounds during Sleep

Because humans spend about one-third of their time asleep in their bedrooms and are themselves emission sources of volatile organic compounds (VOCs), it is important to specifically characterize the composition of the bedroom air that they experience during sleep. This work uses real-time indoor and outdoor measurements of volatile organic compounds (VOCs) to examine concentration enhancements in bedroom air during sleep and to calculate VOC emission rates associated with sleeping occupants. Gaseous VOCs were measured with proton-transfer reaction time-of-flight mass spectrometry during a multiweek residential monitoring campaign under normal occupancy conditions. Results indicate high emissions of nearly 100 VOCs and other species in the bedroom during sleeping periods as compared to the levels in other rooms of the same residence. Air change rates for the bedroom and, correspondingly, emission rates of sleeping-associated VOCs were determined for two bounding conditions: (1) air exchange between the bedroom and outdoors only and (2) air exchange between the bedroom and other indoor spaces only (as represented by measurements in the kitchen). VOCs from skin oil oxidation and personal care products were present, revealing that many emission pathways can be important occupant-associated emission factors affecting bedroom air composition in addition to direct emissions from building materials and furnishings.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

An Easily Prepared Monomeric Cobalt(II) Tetrapyrrole Complex That Efficiently Promotes the 4e – /4H + Peractivation of O 2 to Water

The selective 4e – /4H + reduction of dioxygen to water is an important reaction that takes place at the cathode of fuel cells. Monomeric aromatic tetrapyrroles (such as porphyrins, phthalocyanines, and corroles) coordinated to Co(II) or Co(III) have been considered as oxygen reduction catalysts due to their low cost and relative ease of synthesis. Furthermore, these systems have been repeatedly shown to be selective for O 2 reduction by the less desired 2e – /2H + pathway to yield hydrogen peroxide. Herein, we report the initial synthesis and study of a Co(II) tetrapyrrole complex based on a nonaromatic isocorrole scaffold that is competent for 4e – /4H + oxygen reduction reaction (ORR). This Co(II) 10,10-dimethyl isocorrole (Co[10-DMIC]) is obtained in just four simple steps and has excellent yield from a known dipyrromethane synthon. Evaluation of the steady state spectroscopic and redox properties of Co[10-DMIC] against those of Co porphyrin (cobalt 5,10,15,20-tetrakis(pentafluorophenyl)porphyrin, [Co(TPFPP)]) and corrole (cobalt 5,10,15-tris(pentafluorophenyl)corrole triphenylphosphine, Co[TPFPC](PPh 3 )) homologues demonstrated that the spectroscopic and electrochemical properties of the isocorrole are distinct from those displayed by more traditional aromatic tetrapyrroles. Further, the investigation of the ORR activity of Co[10-DMIC] using a combination of electrochemical and chemical reduction studies revealed that this simple, unadorned monomeric Co(II) tetrapyrrole is ~85% selective for the 4e – /4H + reduction of O 2 to H 2 O over the more kinetically facile 2e – /2H + process that delivers H 2 O 2 . In contrast, the same ORR evaluations conducted for the Co porphyrin and corrole homologues demonstrated that these traditional aromatic systems catalyze the 2e – /2H + conversion of O 2 to H 2 O 2 with near complete selectivity. Despite being a simple, easily prepared, monomeric tetrapyrrole platform, Co[10-DMIC] supports an ORR catalysis that has historically only been achieved using elaborate porphyrinoid-based architectures that incorporate pendant proton-transfer groups or ditopic molecular clefts or that impose cofacially oriented O 2 binding sites. Accordingly, Co[10-DMIC] represents the first simple, unadorned, monomeric metalloisocorrole complex that can be easily prepared and shows a privileged performance for the 4e – /4H + peractivation of O 2 to water as compared to other simple cobalt containing tetrapyrroles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Synthesis of Hangman Chlorins

Two complementary rational synthetic routes have been developed in order to synthesize hangman chlorins, which differ with regard to the order of the installation (pre- and post-formation of the chlorin macrocycle) and position of the xanthene backbone about the chlorin periphery. The versatility of the synthetic method is demonstrated with the preparation of ten new hangman chlorins bearing a xanthene backbone and a pendant carboxylic acid. Cyclic voltammograms of hangman chlorins exhibit a hangman effect derived from intermolecular proton transfer. In conclusion, this hangman effect is manifested in catalytic hydrogen evolution production.

08 HYDROGEN↗
DOE OSTI2020

Probing orientation-specific charge-dipole interactions between hexafluoroisopropanol and halides: A joint photoelectron spectroscopy and theoretical study

The interactions between hexafluoroisopropanol (HFIP) and halogen anions X? (F?, Cl?, Br?, and I?) have been investigated by negative ion photoelectron spectroscopy (NIPES) and ab initio calculations. The measured NIPE spectrum of each [HFIP·X]? (X = Cl, Br, and I) complex shows the identical pattern to the corresponding X? by shifting to the high electron binding energy side, indicative of formation of [HFIP···X?] structure, in which X? interacts with HFIP via charge-dipole interactions. However, the spectrum of [HFIP·F]? appears completely different from that of F?, and is more similar to the spectrum of the deprotonated HFIP anion (HFIP?H?). The geometry and electron density calculations indicate that a neutral HF molecule is formed upon HFIP interacting with F? via proton transfer, rendering a stable structure of [HFIP?H···HF]?. Two conformers of [HFIP?H·HF]? with HFIP being in synperiplanar and antiperiplanar configurations, respectively, are observed, providing direct experimental evidences to show the distinctly different and orientation-specific interactions between HFIP and halide anions.

Wang, Lei↗
DOE OSTI2021

Hydrolysis of Small Oxo/Hydroxo Molecules Containing High Oxidation State Actinides (Th, Pa, U, Np, Pu): A Computational Study

The energetics of hydrolysis reactions for high oxidation states of oxo/hydroxo monomeric actinide species (Th IV O 2 , Pa IV O 2 , U IV O 2 , Pa V O 2 (OH), U V O 2 (OH), U VI O 3 , Np VI O 3 , Np VII O 3 (OH), and Pu VII O 3 (OH)) were calculated at the CCSD(T) level. The first step is the formation of a Lewis acid/base adduct with H 2 O (hydration), followed by a proton transfer to form a dihydroxide molecule (hydrolysis); this process is repeated until all oxo groups are hydrolyzed. The physisorption (hydration) for each H 2 O addition was predicted to be exothermic, ca. -20 kcal/mol. The hydrolysis products are preferred energetically over the hydration products for the +IV and +V oxidation states. The compounds with An VI are a turning point in terms of favoring hydration over hydrolysis. For An VII O 3 (OH), hydration products are preferred, and only two waters can bind; the complete hydrolysis process is now endothermic, and the oxidation state for the An in An(OH) 7 is +VI with two OH groups each having one-half an electron. The natural bond order charges and the reaction energies provide insights into the nature of the hydrolysis/hydration processes. The actinide charges and bond ionicity generally decrease across the period. Here, the ionic character decreases as the oxidation state and coordination number increase so that covalency increases moving to the right in the actinide period.

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

Thermal and Catalytic Decomposition of 2-Hydroxyethylhydrazine and 2-Hydroxyethylhydrazinium Nitrate Ionic Liquid

To develop chemical kinetics models for the combustion of ionic liquid-based monopropellants, identification of the elementary steps in the thermal and catalytic decomposition of components such as 2-hydroxyethylhydrazinium nitrate (HEHN) is needed but is currently not well understood. The first decomposition step in protic ionic liquids such as HEHN is typically the proton transfer from the cation to the anion, resulting in the formation of 2-hydroxyethylhydrazine (HEH) and HNO 3 . In the first part of this investigation, the high-temperature thermal decomposition of HEH is probed with flash pyrolysis (<1400 K) and vacuum ultraviolet (10.45 eV) photoionization time-of-flight mass spectrometry (VUV-PI-TOFMS). Next, the investigation into the thermal and catalytic decomposition of HEHN includes two mass spectrometric techniques: (1) tunable VUV-PI-TOFMS (7.4-15 eV) and (2) ambient ionization mass spectrometry utilizing both plasma and laser ionization techniques whereby HEHN is introduced onto a heated inert or iridium catalytic surface and the products are probed. The products can be identified by their masses, their ionization energies, and their collision-induced fragmentation patterns. Further, formation of product species indicates that catalytic surface recombination is an important reaction process in the decomposition mechanism of HEHN. The products and their possible elementary reaction mechanisms are discussed.

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

Triple Emission of 5'-( para -R-Phenylene)vinylene-2-(2'-hydroxyphenyl)benzoxazole (PVHBO). Part II: Emission from Anions

This paper is the second part of a study on the effects of a substituted 5'-phenylenevinylene (PV) functionality on the emission properties of 2-(2'-hydroxyphenyl)benzoxazole (HBO)-a dye that is known for excited-state intramolecular proton transfer. The topical compounds are referred to as PVHBOs, each of which is a structural fusion of HBO and a 4-hydroxy-4'-R-stilbene fluorophore that occurs at the hydroxyphenyl moiety. Therefore, the resulting fusion fluorophore manifests the properties of one component or the other, as governed by its interactions with the environment. In part I (the preceding paper), PVHBOs are divided into two groups depending on whether the R substituent is electron-donating/neutral (group I) or electron-withdrawing (group II). The difference in absorption and emission properties between groups I and II is explained based on observations from spectroscopic experiments (both steady-state and time-resolved) and quantum chemical calculations. In the current paper, the same set of tools is applied to characterize the photophysical properties of the conjugate bases-that is, the anions-of PVHBOs. The emission energy of the anion of any group I compound, where the R substituent is either electron-donating or neutral, is situated between those of the neutral enol and keto forms. The emission of the anion of any given group II compound, on the other hand, has a lower energy than both the enol and keto emissions. In this work, the frontier molecular orbitals (i.e., HOMO, LUMO, and LUMO + 1) of a PVHBO localized on either HBO or stilbenoid are impacted by the substituent R and the solvent/additive differently, which leads to the differences in the optical properties of group I and II PVHBOs in both neutral and anion forms.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Structure and Stability of Pristine and Carboxylate-Covered Anatase TiO 2 (001) in Aqueous Environment

The interactions of carboxylic acids and water with TiO 2 surfaces are important in applications ranging from solar cells to biomedical devices. Here we focus on the aqueous interface with the minority (001) surface of anatase TiO 2 (A-001) and the behavior of adsorbed formic and acetic acid monolayers at this interface. We investigated the structure and stability of the pristine reconstructed and formic/acetic acid covered A-001 surfaces in contact with water using density functional theory (DFT) calculations and ab initio molecular dynamics (AIMD) simulations. The (1 × 4) reconstruction of the pristine surface is found to be stable in aqueous environment, within the time scale of our simulation. Here, carboxylic acids adsorb in deprotonated bidentate (BD) form on A-001, with the dissociated proton transferred to a surface oxygen to form a bridging hydroxyl. Of the two possible configurations, BD bridging and BD straddling, of the adsorbed species, the latter is found to rapidly transform to a monodentate structure during our simulations. Further investigation of mixed acetate–formate monolayers on A-001 in water indicates that also BD bridging species can become unstable at the boundaries between formate and acetate-covered regions, transforming to a monodentate form that does not prevent water adsorption on the TiO 2 surface.

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

Guanosine Dianions Hydrated by One to Four Water Molecules

Intermolecular interactions as those present in molecule…water complexes may profoundly influence the physico-chemical properties of molecules. Here, we carried out an experimentally-computational study on the doubly-deprotonated guanosine monophosphate…water clusters, [dGMP-2H] 2- •nH 2 O (n=1–4), using a combination of negative anion photoelectron spectroscopy (NIPES) with molecular dynamics (MD) and quantum chemical (QM) calculations. Successive addition of water molecules to [dGMP-2H] 2- increases the experimental adiabatic detachment (ADE) and vertical detachment energy (VDE) by 0.5 to 0.1 eV, depending on the cluster size. In order to choose the representative conformations, we combined MD simulations with a clustering procedure to identify low energy geometries for which ADEs and VDEs were computed at the CAM-B3LYP/6-31++G(d,p) level. Our results demonstrate that the assumed approach lead to the sound geometries and energetics of the studied micro-solvates since the calculated ADEs and VDEs are in pretty good agreement with the experimental characteristics. The evolution of hydrogen bonding with cluster size indicates possibility of the occurrence of proton transfer for clusters comprising a larger number of water molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗