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1. Quadruple bonds in MoC: Accurate calculations and precise measurement of the dissociation energy of low-lying states of MoC

   https://doi.org/10.1063/5.0211422  

   Androutsopoulos, Alexandros; Tzeli, Demeter; Tomchak, Kimberly H; Morse, Michael D (June 2024, The Journal of Chemical Physics)

   Lian, Tianquan (Ed.)

   In the present work, the electronic structure and chemical bonding of the MoC X3Σ− ground state and the six lowest excited states, A3Δ, a1Γ, b5Σ−, c1Δ, d1Σ+, and e5Π, have been investigated in detail using multireference configuration interaction methods and basis sets, including relativistic effective core potentials. In addition, scalar relativistic effects have been considered in the second order Douglas–Kroll–Hess approximation, while spin–orbit coupling has also been calculated. Five of the investigated states, X3Σ−, A3Δ, a1Γ, c1Δ, and d1Σ+, present quadruple σ2σ2π2π2 bonds. Experimentally, the predissociation threshold of MoC was measured using resonant two-photon ionization spectroscopy, allowing for a precise measurement of the dissociation energy of the ground state. Theoretically, the complete basis set limit of the calculated dissociation energy with respect to the atomic ground state products, including corrections for scalar relativistic effects, De(D0), is computed as 5.13(5.06) eV, in excellent agreement with our measured value of D0(MoC) of 5.136(5) eV. Furthermore, the calculated dissociation energies of the states having quadruple bonds with respect to their adiabatic atomic products range from 6.22 to 7.23 eV. The excited electronic states A3Δ2 and c1Δ2 are calculated to lie at 3899 and 8057 cm−1, also in excellent agreement with the experimental values of DaBell et al., 4002.5 and 7834 cm−1, respectively. 

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2. Compensation between meridional flow components of the Atlantic MOC at 26° N

   https://doi.org/10.5194/os-12-481-2016  

   Frajka-Williams, E.; Meinen, C. S.; Johns, W. E.; Smeed, D. A.; Duchez, A.; Lawrence, A. J.; Cuthbertson, D. A.; McCarthy, G. D.; Bryden, H. L.; Baringer, M. O.; et al (January 2016, Ocean Science)

   null (Ed.)

   Abstract. From ten years of observations of the Atlantic meridional overturning circulation (MOC) at 26° N (2004–2014), we revisit the question of flow compensation between components of the circulation. Contrasting with early results from the observations, transport variations of the Florida Current (FC) and upper mid-ocean (UMO) transports (top 1000 m east of the Bahamas) are now found to compensate on sub-annual timescales. The observed compensation between the FC and UMO transports is associated with horizontal circulation and means that this part of the correlated variability does not project onto the MOC. A deep baroclinic response to wind-forcing (Ekman transport) is also found in the lower North Atlantic Deep Water (LNADW; 3000–5000 m) transport. In contrast, co-variability between Ekman and the LNADW transports does contribute to overturning. On longer timescales, the southward UMO transport has continued to strengthen, resulting in a continued decline of the MOC. Most of this interannual variability of the MOC can be traced to changes in isopycnal displacements on the western boundary, within the top 1000 m and below 2000 m. Substantial trends are observed in isopycnal displacements in the deep ocean, underscoring the importance of deep boundary measurements to capture the variability of the Atlantic MOC. 

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3. MOC: Multi-Objective Mobile CPU-GPU Co-Optimization for Power-Efficient DNN Inference

   https://doi.org/10.1109/ICCAD57390.2023.10323882  

   Wu, Yushu; Gong, Yifan; Zhan, Zheng; Yuan, Geng; Li, Yanyu; Wang, Qi; Wu, Chao; Wang, Yanzhi (October 2023, IEEE)
4. Role of Surface Oxygen in α-MoC Catalyst Stability and Activity under Electrooxidation Conditions

   https://doi.org/10.1021/acscatal.4c06544  

   Gautam, Ankit Kumar; Yu, Siying; He, Haozhen; Yang, Hong; Mironenko, Alexander V (April 2025, ACS Catalysis)

   Transition metal carbides are attractive, low-cost alternatives to Pt group metals, exhibiting multifunctional acidic, basic, and metallic sites for catalysis. Their widespread applications are often impeded by a high surface affinity for oxygen, which blocks catalytic sites. However, recent reports indicate that the α-MoC phase is a stable and effective cocatalyst for reactions in oxidative or aqueous environments. In this work, we elucidate the factors affecting the stability and catalytic activity of α-MoC under mild electrooxidation conditions (0–0.8 V SHE) using density functional theory calculations, kinetics-informed surface Pourbaix diagram analysis, electronic structure analysis, and cyclic voltammetry. Both computational and experimental data indicate that α-MoC is significantly more resistant to electrooxidation by H2O than β-Mo2C. This higher stability is attributed to structural and kinetic factors, as the Mo-terminated α-MoC surface disfavors substitutional oxidation of partially exposed, less oxophilic C* atoms by hindering CO/CO2 removal. The α-MoC surface exposes H2O-protected [MoC2O2] and [MoC(CO)O2] oxycarbidic motifs available for catalysis in a wide potential window. At higher potentials, they convert to unstable [Mo(CO)2O2], resulting in material degradation. Using formic acid as a probe molecule, we obtain evidence for Pt-like O*-mediated O–H and C–H bond activation pathways. The largest kinetic barrier, observed for the C–H bond activation, correlates with the hydrogen affinity of the site in the order O*/Mofcc > O*/Ctop > O*/Motop. To mitigate the site-blocking effect of surface-bound H2O and bidentate formate, doping with Pt was investigated computationally to make the surface less oxophilic and more carbophilic, indicating a possible design strategy toward more active and selective carbide electrocatalysts. 

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5. The Effect of Southern Ocean Topography on the Global MOC and Abyssal Water Mass Distribution

   https://doi.org/10.1175/JPO-D-23-0253.1  

   Monkman, Tatsu; Jansen, Malte F (December 2024, Journal of Physical Oceanography)

   We investigate the role of Southern Ocean topography and wind stress in the deep and abyssal ocean overturning and water mass composition using a suite of idealized global ocean circulation models. Specifically, we address how the presence of a meridional ridge in the vicinity of Drake Passage and the formation of an associated Southern Ocean gyre influence the water mass composition of the abyssal cell. Our experiments are carried out using a numerical representation of the global ocean circulation in an idealized two-basin geometry under varying wind stress and Drake Passage ridge height. In the presence of a low Drake Passage ridge, the overall strength of the meridional overturning circulation is primarily influenced by wind stress, with a topographically induced weakening of the middepth cell and concurrent strengthening of the abyssal cell occurring only after ridge height passes 2500 m. Passive tracer experiments show that a strengthening middepth cell leads to increased abyssal ventilation by North Atlantic water masses, as more North Atlantic Deep Water (NADW) enters the Southern Ocean and then spreads into the Indo-Pacific. We repeat our tracer experiments without restoring in the high-latitude Southern Ocean in order to identify the origin of water masses that circulate through the Southern Ocean before sinking into the abyss as Antarctic Bottom Water. Our results from these “exchange” tracer experiments show that an increasing ridge height in Drake Passage and the concurrent gyre spinup lead to substantially decreased NADW-origin waters in the abyssal ocean, as more surface waters from north of the Antarctic Circumpolar Current (ACC) are transferred into the Antarctic Bottom Water formation region. Significance StatementThe objective of this study is to investigate how topographic features in the Southern Ocean can affect the overall structure of Earth’s large-scale ocean circulation and the distribution of water masses in the abyssal ocean. We focus on the Southern Ocean because the region is of central importance for exchange between the Atlantic and Indo-Pacific Ocean basins and for CO₂and heat uptake into the abyssal ocean. Our results indicate that Southern Ocean topography plays a major role in the overall circulation by 1) controlling the direct transfer of abyssal waters from the Atlantic to the Indo-Pacific via its influence on the Atlantic meridional overturning circulation and 2) controlling the coupling between the abyssal ocean and surface waters north of the Antarctic Circumpolar Current via the Southern Ocean gyre. 

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