Understanding the Effects of Climate on Airfield Pavement Deterioration Rates

Over the past two decades, pavement engineers at the Air Force Civil Engineer Center have noticed the majority of identified distresses from PCI airfield surveys are climate related. To verify these trends, a comprehensive analysis of the current airfield pavement distress database was accomplished based on a climate region perspective. A four-zone regional climatic model was created for the United States using geospatial interpolation techniques and climate data acquired from WeatherBank Inc. Once the climatic regional model was developed, the climate information for each installation was imported into the Air Force pavement distress database within PAVER. Utilizing the pavement condition prediction modeling function in PAVER, pavement deterioration models were created for every pavement family at each base in each climatic zone. This was done to generate a list of bases that may have multiple pavement families with rates of deterioration that are better or worse than the regional rates of deterioration. The average regional rates of deterioration for each pavement family were found to be within the parameters of conventional wisdom observed in Asphalt Concrete (AC) and Portland Cement Concrete (PCC). The results of the pairwise comparisons using the Student\u27s T-test determined the Freeze-Dry climate region deterioration rates for the PCC pavement family were statistically different than the other three regions. No significant statistical differences were observed in the AC pavement comparisons. This analysis established a foundation to investigate and identify variables causing the rates of deterioration at specific installations to differ from the regional rates of deterioration

[UF6](2-): A molecular hexafluorido actinide(IV) complex with compensating spin and orbital magnetic moments

The first structurally characterized hexafluorido complex of a tetravalent actinide ion, the [UF6]2- anion, is reported in the (NEt4)2[UF6]2H2O salt (1). The weak magnetic response of 1 results from both U(IV) spin and orbital contributions, as established by combining X-ray magnetic circular dichroism (XMCD) spectroscopy and bulk magnetization measurements. The spin and orbital moments are virtually identical in magnitude, but opposite in sign, resulting in an almost perfect cancellation, which is corroborated by ab initio calculations. This work constitutes the first experimental demonstration of a seemingly non-magnetic molecular actinide complex carrying sizable spin and orbital magnetic moments

Magneto-structural correlations in arsenic- and selenium-ligated dysprosium single-molecule magnets

The structures and magnetic properties of the arsenic- and selenium-ligated dysprosium single-molecule magnets (SMMs) [Cp'3Dy(AsH2Mes)] (3-Dy), [(h5-Cp02Dy){m-As(H)Mes}]3 (4-Dy), [Li(thf)4]2[(h5-Cp02Dy)3(m3-AsMes)3Li] ([Li(thf)4]2[5-Dy]), and [(h5-Cp02Dy){m-SeMes}]3 (6-Dy) are described. The arsenic-ligated complexes 4-Dy and 5-Dy are the first SMMs to feature ligands with metalloid elements as the donor atoms. The arsenide-ligated complex 4-Dy and the selenolate-ligated complex 6-Dy show large anisotropy barriers in the region of 250 cm�1 in zero d.c. field, increasing to 300 cm�1 upon 5% magnetic dilution. Theoretical studies reveal that thermal relaxation in these SMMs occurs via the second-excited Kramers' doublet. In contrast, the arsinidene-ligated SMM 5-Dy gives a much smaller barrier of 23 cm�1, increasing to 35 cm�1 upon dilution. The field-dependence of the magnetization for 4-Dy and 5-Dy at 1.8 K show unusual plateaus around 10 kOe, which is due to the dominance of arsenic-mediated exchange over the dipolar exchange. The effects of the exchange interactions are more pronounced in 5-Dy, which is a consequence of a small but significant increase in the covalent contribution to the predominantly ionic dysprosium-arsenic bonds. Whereas the magnetically non-dilute dysprosium SMMs show only very narrow magnetization versus field hysteresis loops at 1.8 K, the impact of magnetic dilution is dramatic, with butterfly-shaped loops being observed up to 5.4 K in the case of 4-Dy. Our findings suggest that ligands with heavier p-block element donor atoms have considerable potential to be developed more widely for applications in molecular magnetism

Coercive Fields Exceeding 30 T in the Mixed-Valence Single-Molecule Magnet (CpiPr5)2Ho2I3.

Mixed-valence dilanthanide complexes of the type (CpiPr5)2Ln2I3 (CpiPr5 = pentaisopropylcyclopentadienyl; Ln = Gd, Tb, Dy) featuring a direct Ln-Ln σ-bonding interaction have been shown to exhibit well-isolated high-spin ground states and, in the case of the Tb and Dy variants, a strong axial magnetic anisotropy that gives rise to a large magnetic coercivity. Here, we report the synthesis and characterization of two new mixed-valence dilanthanide compounds in this series, (CpiPr5)2Ln2I3 (1-Ln; Ln = Ho, Er). Both compounds feature a Ln-Ln bonding interaction, the first such interaction in any molecular compounds of Ho or Er. Like the Tb and Dy congeners, both complexes exhibit high-spin ground states arising from strong spin-spin coupling between the lanthanide 4f electrons and a single σ-type lanthanide-lanthanide bonding electron. Beyond these similarities, however, the magnetic properties of the two compounds diverge. In particular, 1-Er does not exhibit observable magnetic blocking or slow magnetic relaxation, while 1-Ho exhibits magnetic blocking below 28 K, which is the highest temperature among Ho-based single-molecule magnets, and a spin reversal barrier of 556(4) cm-1. Additionally, variable-field magnetization data collected for 1-Ho reveal a coercive field of greater than 32 T below 8 K, more than 6-fold higher than observed for the bulk magnets SmCo5 and Nd2Fe14B, and the highest coercive field reported to date for any single-molecule magnet or molecule-based magnetic material. Multiconfigurational calculations, supported by far-infrared magnetospectroscopy data, reveal that the stark differences in magnetic properties of 1-Ho and 1-Er arise from differences in the local magnetic anisotropy of the lanthanide centers

Slow magnetic relaxation in dinuclear dysprosium and holmium phenoxide bridged complexes: A Dy2single molecule magnet with a high energy barrier

Slow magnetic relaxation in dinuclear dysprosium and holmium phenoxo bridged complexes: a Dy2 single molecule magnet with a high energy barrier Matilde Fondo,a,* Julio Corredoira-Vázquez,a Ana M. García-Deibe,a Jesús Sanmartín-Matalobos,a Silvia Gómez-Coca,b Eliseo Ruizb and Enrique Colacioc Dinuclear [M(H3L1,2,4)]2 (M = Dy, Dy2; M = Ho, Ho2) complexes were isolated and recrystallised in pyridine. The crystal structures of Dy2·2THF and the pyridine adducts Dy2·2Py and Ho2·2Py show that the complexes are dinuclear, with unsupported double phenoxo bridges, and that the N4O4 environment of the LnIII centres is distorted triangular dodecahedral. The magnetic analysis of Dy2 and Ho2 shows that Dy2 is a single molecular magnet (SMM), with a thermal-activated zero-field effective energy barrier (Ueff) of 367.7 K, the largest barrier shown by double unsupported phenoxo-bridged dinuclear dysprosium complexes. Ho2 is one of the scarce dinuclear complexes showing slow relaxation of the magnetisation, although it does not even show field-induced SMM behaviour. Ab initio calculations were done in order to shed light on the magnetic anisotropy of the complexes and the magnetic relaxation pathways, which support the experimental magnetic results

Single molecule magnetic behaviour in lanthanide naphthalenesulfonate complexes

The use of 2-naphthalenesulfonate (NAS) ligand in lanthanide chemistry afforded a family of isostructural mononuclear lanthanide complexes with formula [Ln(NAS)2(H2O)6](NAS)·3H2O [Ln = Tb (1), Dy (2), Er (3), Yb (4)]. Crystallographic studies determine a square antiprismatic geometry (D4d) for the Ln centre and crystallization in unprecedented chiral space group. The latter was further confirmed by the observation of Cotton effects in single crystal circular dichroism (CD) spectra. Static and dynamic magnetic measurements identify weak intermolecular dipolar interactions in 2, and such effects can be waived by dilution, which was noted by the detection of zero-field single molecule magnet (SMM) behaviour and hysteresis loop in the magnetically diluted sample (5). Compounds 2-4 exhibit SMM behaviours with energy barriers of 53, 32 and 45 K, respectively. To the best of our knowledge, these complexes provide the first examples of pure 4f sulfonate-based SMMs

Influencing the properties of dysprosium single-molecule magnets with phosphine, phosphide and phosphinidene ligands

Single-molecule magnets are a type of coordination compound that can retain magnetic information at low temperatures. Single-molecule magnets based on lanthanides have accounted for many important advances, including systems with very large energy barriers to reversal of the magnetization, and a di-terbium complex that displays magnetic hysteresis up to 14 K and shows strong coercivity. Ligand design is crucial for the development of new single-molecule magnets: organometallic chemistry presents possibilities for using unconventional ligands, particularly those with soft donor groups. Here we report dysprosium single-molecule magnets with neutral and anionic phosphorus donor ligands, and show that their properties change dramatically when varying the ligand from phosphine to phosphide to phosphinidene. A phosphide-ligated, trimetallic dysprosium single-molecule magnet relaxes via the second-excited Kramers’ doublet, and, when doped into a diamagnetic matrix at the single-ion level, produces a large energy barrier of 256 cm1 and magnetic hysteresis up to 4.4 K

Exploring the solid state and solution structural chemistry of the utility amide potassium hexamethyldisilazide (KHMDS)

The structural chemistry of eleven donor complexes of the important Brønsted base potassium 1,1,1,3,3,3-hexamethyldisilazide (KHMDS) has been studied. Depending on the donor, each complex adopted one of four general structural motifs. Specifically, in this study the donors employed were toluene (to give polymeric 1 and dimeric 2), THF (dimeric 3), N,N,N',N'-tetramethylethylenediamine (TMEDA) (dimeric 4), (R,R)-N,N,N',N'-tetramethyl-1,2-diaminocyclohexane [(R,R)-TMCDA] (dimeric 5), 12-crown-4 (dimeric 6), N,N,N',N'-tetramethyldiaminoethyl ether (TMDAE) (tetranuclear dimeric 8 and monomeric 10), N,N,N',N',N''-pentamethyldiethylentriamine (PMDETA) (tetranuclear dimeric 7), tris[2-dimethyl(amino)ethyl]amine (Me6TREN) (tetranuclear dimeric 9) and tris{2-(2-methoxyethoxy)ethyl}amine (TMEEA) (monomeric 11). The complexes were also studied in solution by 1H and 13C NMR spectroscopy as well as DOSY NMR spectroscopy

Organometallic neptunium(III) complexes

Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metal–ligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on UIII and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to NpIV. Here we report the synthesis of three new NpIII organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that NpIII complexes could act as single-molecule magnets, and that the lower oxidation state of NpII is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key NpIII orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements

Slow magnetic relaxation in homoleptic trispyrazolylborate complexes of neodymium(iii) and uranium(iii)

Lanthanide- and actinide-based single-molecule magnets are rapidly gaining prominence due to the unique properties of f-orbitals, yet no direct comparison of slow magnetic relaxation of an isostructural and valence isoelectronic lanthanide and actinide complex exists. We present the dynamic magnetic properties of two f-element single-molecule magnets, NdTp(3) and UTp(3) (Tp(-) = trispyrazolylborate), demonstrating that, although neither complex displays the full anisotropy barrier predicted from its electronic structure, relaxation is slower in the uranium congener. Magnetic dilution studies performed with NdTp(3) reveal that, while intermolecular interactions partially account for the faster relaxation dynamics, they are not uniquely responsible