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At least 235 records · Page 13

Data Imbalance, Uncertainty Quantification, and Transfer Learning in Data‐Driven Parameterizations: Lessons From the Emulation of Gravity Wave Momentum Transport in WACCM

Abstract Neural networks (NNs) are increasingly used for data‐driven subgrid‐scale parameterizations in weather and climate models. While NNs are powerful tools for learning complex non‐linear relationships from data, there are several challenges in using them for parameterizations. Three of these challenges are (a) data imbalance related to learning rare, often large‐amplitude, samples; (b) uncertainty quantification (UQ) of the predictions to provide an accuracy indicator; and (c) generalization to other climates, for example, those with different radiative forcings. Here, we examine the performance of methods for addressing these challenges using NN‐based emulators of the Whole Atmosphere Community Climate Model (WACCM) physics‐based gravity wave (GW) parameterizations as a test case. WACCM has complex, state‐of‐the‐art parameterizations for orography‐, convection‐, and front‐driven GWs. Convection‐ and orography‐driven GWs have significant data imbalance due to the absence of convection or orography in most grid points. We address data imbalance using resampling and/or weighted loss functions, enabling the successful emulation of parameterizations for all three sources. We demonstrate that three UQ methods (Bayesian NNs, variational auto‐encoders, and dropouts) provide ensemble spreads that correspond to accuracy during testing, offering criteria for identifying when an NN gives inaccurate predictions. Finally, we show that the accuracy of these NNs decreases for a warmer climate (4 × CO 2 ). However, their performance is significantly improved by applying transfer learning, for example, re‐training only one layer using ∼1% new data from the warmer climate. The findings of this study offer insights for developing reliable and generalizable data‐driven parameterizations for various processes, including (but not limited to) GWs.

54 ENVIRONMENTAL SCIENCES↗

Photodissociation of iso-propoxy (i-C 3 H 7 O) radical at 248 nm

Photodissociation of the i-C 3 H 7 O radical is investigated using fast beam photofragment translational spectroscopy. Neutral i-C 3 H 7 O radicals are produced through the photodetachment of a fast beam of i-C 3 H 7 O - anions and are subsequently dissociated at 248 nm (5.0 eV). Furthermore, the dominant product channels are CH 3 + CH 3 CHO and OH + C 3 H 6 with some contribution from H + C 3 H 6 O. The CH 3 and H loss channels are attributed to dissociation on the ground electronic state of i-C 3 H 7 O, but in a nonstatistical manner because calculated RRKM dissociation rates exceed the rate of energy randomization. Translational energy and angular distributions for OH loss are consistent with ground state dissociation, but the branching ratio for this channel is considerably higher than predicted from RRKM rate calculations. Additionally, i-C 3 H 7 O undergoes three-body fragmentation to CH 3 + CH 3 + HCO and CH 3 + CH 4 + CO. These three-body channels are attributed to dissociation of i-C 3 H 7 O to CH 3 + CH 3 CHO, followed by secondary dissociation of CH 3 CHO on its ground electronic state.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Probing the influence of ion-pairing on ligand-field excited-state dynamics

Exploration of the photophysical and photochemical properties of transition metal complexes has driven ground-breaking advancements in solar energy conversion technologies, including photoredox catalysis. While significant research has been devoted to understanding excited state properties of second- and third-row transition metal complexes, earth-abundant first-row metal complexes have received comparatively little attention in this context until very recently. In particular, the role of ion-pairing – which has been identified as a potentially significant factor for Ir(III)-based photosensitizers – has not been examined with regard to its influence on the ligand-field excited states that dominate much of first-row photophysics. A key challenge in studying ion-pair interactions lies in quantifying the extent and nature of ion-pairing, particularly in non-aqueous media where the vast majority of photophysical studies are performed. Cobalt(III) polypyridyl complexes provide an attractive platform to address such questions due to their demonstrated potential for applications in photoredox catalysis involving ligand-field excited states. In the present study, we prepared a cobalt(III) polypyridyl complex, [Co(4,4′-OMebpy) 3 ](BAr F 4 ) 3 (where 4,4′-OMebpy is 4,4′-dimethoxy-2,2′-bipyridine and BAr F 4 is tetrakis(3,5-bis(trifluoromethyl)-phenyl)borate) to probe ion-pairing in non-aqueous solutions. Specifically, analysis of data acquired from both variable-temperature diffusion ordered spectroscopy (DOSY) NMR and 1-D rotating-frame nuclear Overhauser effect (ROE) experiments allowed us to identify and differentiate between solvent-separated ion pairs in high-dielectric media and contact ion pairs in a low-dielectric solvent. Time-resolved absorption spectroscopy was then used to measure ground-state recovery dynamics under these varying conditions of ion-pairing, the results of which revealed an increase in excited-state lifetime for contact ion-pairs that we suggest arises from a reduction in outer-sphere reorganization energy relative to conditions which favored solvent-separated ion pairs. We believe this study demonstrates that one can leverage broadly available NMR-based methods to understand ion-pairing in non-aqueous solutions, which in turn can provide a microscopic picture of intermolecular interactions that can impact the photophysical properties of transition metal-based chromophores.

Ghosh, Atanu [Michigan State University, East Lans↗

Tuneable electronic coupling in linked bis(cubane) cobalt-oxo clusters

A family of cobalt-oxo bis(cubane) complexes wherein each subunit is derived from the Co 4 O 4 cubane, a known water oxidation catalyst, was synthesized. Both 4,4′-bipyrdine and pyrazine were demonstrated to serve as viable bridging ligands. Through an analysis of their half-wave splitting potentials, it was determined that pyrazine-bridged bis(cubane)s exhibit inter-cubane electronic coupling, and that this coupling may be tuned through ligand substitution. Electrostatic contributions to the half-wave splitting potentials were evaluated and found to result in “non-conformist” behavior related to the ion-pairing ability of the electrolytes.

Maddi, Vincent J. P. [University of California, Be↗

Dicarbonyl[10,10-dimethyl-5,15-bis(pentafluorophenyl)biladiene]ruthenium(II): discovery of the first ruthenium tetrapyrrole cis -dicarbonyl complex by X-ray and electron diffraction

Dicarbon­yl[10,10-dimethyl-5,15-bis­(penta­fluoro­phen­yl)biladiene]ruthenium(II), [Ru(C 33 H 16 F 10 N 4 )(CO) 2 ] or Ru(CO) 2 [DMBil1], is the first reported ruthenium(II) cis-dicarbonyl tetra­pyrrole complex. The neutral complex sports two carbonyls and an oligo­tetra­pyrrolic biladiene ligand. Notably, the biladiene adopts a coordination geometry that is well distorted from square planar and much more closely approximates a seesaw arrangement. Accordingly, Ru(CO) 2 [DMBil1] is not only the first ruthenium cis-dicarbonyl with a tetra­pyrrole ligand, but also the first metal biladiene complex in which the tetra­pyrrole does not adopt a (pseudo-)square-planar coordination geometry. Ru(CO) 2 [DMBil1] is weakly luminescent, displaying λ em = 552 nm upon excitation at λ ex = 500 nm, supports two reversible 1 e – reductions at –1.45 and –1.73 V (versus Fc + /Fc), and has significant absorption features at 481 and 531 nm, suggesting suitability for photo­catalytic and photosensitization applications. While the structure of Ru(CO) 2 [DMBil1] was initially determined by X-ray diffraction, a traditionally acceptable quality structure could not be obtained (despite multiple attempts) because of consistently poor crystal quality. Furthermore, an independent structure obtained from electron diffraction experiments corroborates the structure of this unusual biladiene complex.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Materials Data on Ga2RhC4Cl7O4 by Materials Project

RhGa2Cl7(CO)4 crystallizes in the triclinic P-1 space group. The structure is zero-dimensional and consists of eight formaldehyde molecules, two rhodium molecules, and two Ga2Cl7 clusters. In each Ga2Cl7 cluster, there are two inequivalent Ga3+ sites. In the first Ga3+ site, Ga3+ is bonded to four Cl1- atoms to form corner-sharing GaCl4 tetrahedra. There are a spread of Ga–Cl bond distances ranging from 2.16–2.38 Å. In the second Ga3+ site, Ga3+ is bonded to four Cl1- atoms to form corner-sharing GaCl4 tetrahedra. There are a spread of Ga–Cl bond distances ranging from 2.17–2.32 Å. There are seven inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a single-bond geometry to one Ga3+ atom. In the second Cl1- site, Cl1- is bonded in a single-bond geometry to one Ga3+ atom. In the third Cl1- site, Cl1- is bonded in a single-bond geometry to one Ga3+ atom. In the fourth Cl1- site, Cl1- is bonded in a single-bond geometry to one Ga3+ atom. In the fifth Cl1- site, Cl1- is bonded in a bent 120 degrees geometry to two Ga3+ atoms. In the sixth Cl1- site, Cl1- is bonded in a single-bond geometry to one Ga3+ atom. In the seventh Cl1- site, Cl1- is bonded in a single-bond geometry to one Ga3+ atom.

36 MATERIALS SCIENCE↗

Materials Data on ReC4IO4 by Materials Project

ReI(CO)4 crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of thirty-two formaldehyde molecules and four ReI clusters. In each ReI cluster, there are two inequivalent Re3+ sites. In the first Re3+ site, Re3+ is bonded in a 2-coordinate geometry to two I1- atoms. There are one shorter (2.87 Å) and one longer (2.88 Å) Re–I bond lengths. In the second Re3+ site, Re3+ is bonded in a 2-coordinate geometry to two I1- atoms. There are one shorter (2.86 Å) and one longer (2.87 Å) Re–I bond lengths. There are two inequivalent I1- sites. In the first I1- site, I1- is bonded in a 2-coordinate geometry to two Re3+ atoms. In the second I1- site, I1- is bonded in a distorted water-like geometry to two Re3+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on Fe2TeWC10SeO10 by Materials Project

WFe2C6TeSeO6(CO)4 crystallizes in the triclinic P-1 space group. The structure is one-dimensional and consists of eight formaldehyde molecules and one WFe2C6TeSeO6 ribbon oriented in the (1, 0, 0) direction. In the WFe2C6TeSeO6 ribbon, W2+ is bonded in a 2-coordinate geometry to one Te2- and one Se2- atom. The W–Te bond length is 2.79 Å. The W–Se bond length is 2.61 Å. There are two inequivalent Fe3+ sites. In the first Fe3+ site, Fe3+ is bonded in a 5-coordinate geometry to three C+1.60+, one Te2-, and one Se2- atom. There is one shorter (1.77 Å) and two longer (1.81 Å) Fe–C bond length. The Fe–Te bond length is 2.57 Å. The Fe–Se bond length is 2.42 Å. In the second Fe3+ site, Fe3+ is bonded in a 5-coordinate geometry to three C+1.60+, one Te2-, and one Se2- atom. There is one shorter (1.77 Å) and two longer (1.80 Å) Fe–C bond length. The Fe–Te bond length is 2.57 Å. The Fe–Se bond length is 2.43 Å. There are six inequivalent C+1.60+ sites. In the first C+1.60+ site, C+1.60+ is bonded in a distorted single-bond geometry to one Fe3+ and one O2- atom. The C–O bond length is 1.16 Å. In the second C+1.60+ site, C+1.60+ is bonded in a linear geometry to one Fe3+ and one O2- atom. The C–O bond length is 1.16 Å. In the third C+1.60+ site, C+1.60+ is bonded in a distorted linear geometry to one Fe3+ and one O2- atom. The C–O bond length is 1.16 Å. In the fourth C+1.60+ site, C+1.60+ is bonded in a distorted linear geometry to one Fe3+ and one O2- atom. The C–O bond length is 1.16 Å. In the fifth C+1.60+ site, C+1.60+ is bonded in a distorted single-bond geometry to one Fe3+ and one O2- atom. The C–O bond length is 1.16 Å. In the sixth C+1.60+ site, C+1.60+ is bonded in a linear geometry to one Fe3+ and one O2- atom. The C–O bond length is 1.16 Å. Te2- is bonded in a 2-coordinate geometry to one W2+, two Fe3+, and three O2- atoms. There are a spread of Te–O bond distances ranging from 3.43–3.72 Å. Se2- is bonded in a 2-coordinate geometry to one W2+ and two Fe3+ atoms. There are six inequivalent O2- sites. In the first O2- site, O2- is bonded in a single-bond geometry to one C+1.60+ atom. In the second O2- site, O2- is bonded in a single-bond geometry to one C+1.60+ atom. In the third O2- site, O2- is bonded in a single-bond geometry to one C+1.60+ and one Te2- atom. In the fourth O2- site, O2- is bonded in a single-bond geometry to one C+1.60+ and one Te2- atom. In the fifth O2- site, O2- is bonded in a single-bond geometry to one C+1.60+ and one Te2- atom. In the sixth O2- site, O2- is bonded in a single-bond geometry to one C+1.60+ atom.

36 MATERIALS SCIENCE↗

Materials Data on Fe2MoC10(SeO5)2 by Materials Project

MoFe2C6(SeO3)2(CO)4 crystallizes in the triclinic P-1 space group. The structure is one-dimensional and consists of eight formaldehyde molecules and one MoFe2C6(SeO3)2 ribbon oriented in the (1, 0, 0) direction. In the MoFe2C6(SeO3)2 ribbon, Mo2+ is bonded in a 2-coordinate geometry to two Se2- atoms. Both Mo–Se bond lengths are 2.61 Å. There are two inequivalent Fe3+ sites. In the first Fe3+ site, Fe3+ is bonded to three C+1.60+ and two Se2- atoms to form distorted edge-sharing FeC3Se2 square pyramids. There are a spread of Fe–C bond distances ranging from 1.77–1.82 Å. There are one shorter (2.40 Å) and one longer (2.41 Å) Fe–Se bond lengths. In the second Fe3+ site, Fe3+ is bonded to three C+1.60+ and two Se2- atoms to form distorted edge-sharing FeC3Se2 square pyramids. There is one shorter (1.77 Å) and two longer (1.81 Å) Fe–C bond length. Both Fe–Se bond lengths are 2.41 Å. There are six inequivalent C+1.60+ sites. In the first C+1.60+ site, C+1.60+ is bonded in a distorted single-bond geometry to one Fe3+ and one O2- atom. The C–O bond length is 1.16 Å. In the second C+1.60+ site, C+1.60+ is bonded in a distorted single-bond geometry to one Fe3+ and one O2- atom. The C–O bond length is 1.16 Å. In the third C+1.60+ site, C+1.60+ is bonded in a distorted linear geometry to one Fe3+ and one O2- atom. The C–O bond length is 1.16 Å. In the fourth C+1.60+ site, C+1.60+ is bonded in a distorted linear geometry to one Fe3+ and one O2- atom. The C–O bond length is 1.16 Å. In the fifth C+1.60+ site, C+1.60+ is bonded in a linear geometry to one Fe3+ and one O2- atom. The C–O bond length is 1.16 Å. In the sixth C+1.60+ site, C+1.60+ is bonded in a linear geometry to one Fe3+ and one O2- atom. The C–O bond length is 1.16 Å. There are two inequivalent Se2- sites. In the first Se2- site, Se2- is bonded in a 2-coordinate geometry to one Mo2+ and two Fe3+ atoms. In the second Se2- site, Se2- is bonded in a 2-coordinate geometry to one Mo2+, two Fe3+, and two O2- atoms. There are one shorter (3.47 Å) and one longer (3.61 Å) Se–O bond lengths. There are six inequivalent O2- sites. In the first O2- site, O2- is bonded in a single-bond geometry to one C+1.60+ atom. In the second O2- site, O2- is bonded in a single-bond geometry to one C+1.60+ and one Se2- atom. In the third O2- site, O2- is bonded in a single-bond geometry to one C+1.60+ atom. In the fourth O2- site, O2- is bonded in a single-bond geometry to one C+1.60+ atom. In the fifth O2- site, O2- is bonded in a single-bond geometry to one C+1.60+ atom. In the sixth O2- site, O2- is bonded in a single-bond geometry to one C+1.60+ and one Se2- atom.

36 MATERIALS SCIENCE↗

Materials Data on OsC4ClO4 by Materials Project

OsCl(CO)4 is Cubic alpha N2-derived structured and crystallizes in the orthorhombic P2_12_12_1 space group. The structure is zero-dimensional and consists of eight chloroosmium molecules and thirty-two formaldehyde molecules.

36 MATERIALS SCIENCE↗

Materials Data on TcC4IO4 by Materials Project

TcI(CO)4 crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of thirty-two formaldehyde molecules and four TcI clusters. In each TcI cluster, there are two inequivalent Tc1+ sites. In the first Tc1+ site, Tc1+ is bonded in a 2-coordinate geometry to two I1- atoms. There are one shorter (2.84 Å) and one longer (2.85 Å) Tc–I bond lengths. In the second Tc1+ site, Tc1+ is bonded in a 2-coordinate geometry to two I1- atoms. There are one shorter (2.86 Å) and one longer (2.87 Å) Tc–I bond lengths. There are two inequivalent I1- sites. In the first I1- site, I1- is bonded in a distorted L-shaped geometry to two Tc1+ atoms. In the second I1- site, I1- is bonded in a 2-coordinate geometry to two Tc1+ atoms.

36 MATERIALS SCIENCE↗

Materials Data on Al2RhC4Cl7O4 by Materials Project

RhAl2Cl7(CO)4 crystallizes in the triclinic P-1 space group. The structure is zero-dimensional and consists of eight formaldehyde molecules, two rhodium molecules, and two Al2Cl7 clusters. In each Al2Cl7 cluster, there are two inequivalent Al3+ sites. In the first Al3+ site, Al3+ is bonded to four Cl1- atoms to form corner-sharing AlCl4 tetrahedra. There are a spread of Al–Cl bond distances ranging from 2.12–2.30 Å. In the second Al3+ site, Al3+ is bonded to four Cl1- atoms to form corner-sharing AlCl4 tetrahedra. There are a spread of Al–Cl bond distances ranging from 2.13–2.26 Å. There are seven inequivalent Cl1- sites. In the first Cl1- site, Cl1- is bonded in a single-bond geometry to one Al3+ atom. In the second Cl1- site, Cl1- is bonded in a bent 120 degrees geometry to two Al3+ atoms. In the third Cl1- site, Cl1- is bonded in a single-bond geometry to one Al3+ atom. In the fourth Cl1- site, Cl1- is bonded in a single-bond geometry to one Al3+ atom. In the fifth Cl1- site, Cl1- is bonded in a single-bond geometry to one Al3+ atom. In the sixth Cl1- site, Cl1- is bonded in a single-bond geometry to one Al3+ atom. In the seventh Cl1- site, Cl1- is bonded in a single-bond geometry to one Al3+ atom.

36 MATERIALS SCIENCE↗

Materials Data on FeHg2C6S2(NO2)2 by Materials Project

Fe(Hg(NCS))2(CO)4 crystallizes in the tetragonal I4_1/a space group. The structure is one-dimensional and consists of eight ferrum molecules; thirty-two formaldehyde molecules; and four Hg(NCS) ribbons oriented in the (0, 0, 1) direction. In each Hg(NCS) ribbon, Hg2+ is bonded in an L-shaped geometry to one N3- and one S2- atom. The Hg–N bond length is 2.90 Å. The Hg–S bond length is 2.61 Å. C+1.83+ is bonded in a distorted linear geometry to one N3- and one S2- atom. The C–N bond length is 1.18 Å. The C–S bond length is 1.66 Å. N3- is bonded in a distorted single-bond geometry to one Hg2+ and one C+1.83+ atom. S2- is bonded in a water-like geometry to one Hg2+ and one C+1.83+ atom.

36 MATERIALS SCIENCE↗

Materials Data on CuC4S4(NO6)2 by Materials Project

CuS4(NO4)2(CO)4 crystallizes in the triclinic P-1 space group. The structure is zero-dimensional and consists of four formaldehyde molecules and one CuS4(NO4)2 cluster. In the CuS4(NO4)2 cluster, Cu2+ is bonded in an octahedral geometry to six O2- atoms. There are four shorter (1.86 Å) and two longer (2.60 Å) Cu–O bond lengths. N3+ is bonded in a bent 150 degrees geometry to two S atoms. There is one shorter (1.56 Å) and one longer (1.60 Å) N–S bond length. There are two inequivalent S sites. In the first S site, S is bonded in a water-like geometry to one N3+ and one O2- atom. The S–O bond length is 1.47 Å. In the second S site, S is bonded in a bent 120 degrees geometry to one N3+ and one O2- atom. The S–O bond length is 1.49 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a single-bond geometry to one S atom. In the second O2- site, O2- is bonded in a distorted bent 150 degrees geometry to one Cu2+ and one S atom. In the third O2- site, O2- is bonded in a 1-coordinate geometry to one Cu2+ and one O2- atom. The O–O bond length is 1.35 Å. In the fourth O2- site, O2- is bonded in a 1-coordinate geometry to one Cu2+ and one O2- atom.

36 MATERIALS SCIENCE↗

Materials Data on MnC5O8 by Materials Project

MnCO4(CO)4 crystallizes in the orthorhombic Pbca space group. The structure is zero-dimensional and consists of thirty-two formaldehyde molecules and eight MnCO4 clusters. In each MnCO4 cluster, Mn2+ is bonded in a tetrahedral geometry to four O2- atoms. There are a spread of Mn–O bond distances ranging from 1.58–1.83 Å. C+2.80+ is bonded in a single-bond geometry to one O2- atom. The C–O bond length is 1.31 Å. There are four inequivalent O2- sites. In the first O2- site, O2- is bonded in a bent 120 degrees geometry to one Mn2+ and one C+2.80+ atom. In the second O2- site, O2- is bonded in a single-bond geometry to one Mn2+ atom. In the third O2- site, O2- is bonded in a single-bond geometry to one Mn2+ atom. In the fourth O2- site, O2- is bonded in a single-bond geometry to one Mn2+ atom.

36 MATERIALS SCIENCE↗

Materials Data on NbC4N3O13 by Materials Project

(NbCO7)2(N2)3(CO2)4(CO)2O2 crystallizes in the monoclinic P2/c space group. The structure is zero-dimensional and consists of twelve ammonia molecules, eight carbon dioxide molecules, four formaldehyde molecules, two hydrogen peroxide molecules, and four NbCO7 clusters. In each NbCO7 cluster, Nb5+ is bonded in a 1-coordinate geometry to six O2- atoms. There are a spread of Nb–O bond distances ranging from 1.74–2.31 Å. C4+ is bonded in a linear geometry to two O2- atoms. There is one shorter (1.17 Å) and one longer (1.18 Å) C–O bond length. There are seven inequivalent O2- sites. In the first O2- site, O2- is bonded in a 1-coordinate geometry to one Nb5+ and one O2- atom. The O–O bond length is 1.41 Å. In the second O2- site, O2- is bonded in a 1-coordinate geometry to one Nb5+ and one O2- atom. In the third O2- site, O2- is bonded in a 1-coordinate geometry to one Nb5+ and one O2- atom. The O–O bond length is 1.40 Å. In the fourth O2- site, O2- is bonded in a single-bond geometry to one C4+ atom. In the fifth O2- site, O2- is bonded in a 1-coordinate geometry to one Nb5+ and one O2- atom. In the sixth O2- site, O2- is bonded in a distorted linear geometry to one Nb5+ and one C4+ atom. In the seventh O2- site, O2- is bonded in a single-bond geometry to one Nb5+ atom.

36 MATERIALS SCIENCE↗