arXiv subjects

Mukesh Singh

Publications and source records attributed to Mukesh Singh.

5 recordsLinked to original sources

arXiv2026

Policy-Masked Private Experts: Auditable and Reversible Capability Access Control in Sparse MoE Models

Most language-model access controls regulate behavior while leaving the same computation available to every request. We study a different systems question: can trusted authorization determine which newly trained parameters are reachable by the forward pass? Policy-Masked Private Experts freezes a pretrained sparse Mixture-of-Experts (MoE) model, trains a disjoint expert branch, and selects the public or private pool before top-k routing. The resulting claim is narrow but testable: under the declared trusted computing base (TCB), an unauthorized request executes no private expert. It does not imply that the public model lacks the same semantic capability. We test this separation between execution control and task utility in Qwen3-30B-A3B and DeepSeek-V2-Lite. Three Qwen BF16 seeds update all 32 private experts while the public fingerprint remains unchanged. Across 64 adversarial scenarios and 96 deny/fail-closed events, unauthorized private execution is zero; independent hooks exactly match 11,616 routed private rows and allow-deny-allow recovery is exact. On two prospectively frozen Qwen benchmarks, the private branch improves exact tool use by 5.0 percentage points (pp) (five versus zero discordances; one-sided Holm p = 0.03125, corresponding two-sided exact p = 0.0625) and 21.3 pp (percentile-bootstrap 95% CI [13.3, 29.3], Holm p = 0.000031). Three arm-blinded model evaluators retain a positive external effect of 18.7 pp (95% CI [9.3, 28.0]). A parameter-matched Lora has similar external utility, but a post-hoc request gate leaves 1,225 adapter calls under deny; the disjoint expert branch leaves none. DeepSeek reproduces the route invariant and gains 27.0 pp. A valid sealed evaluation is near-neutral. These results support auditable, reversible control over a trained parameter path, while showing that useful transfer remains distribution dependent.

cs.CR↗

arXiv2023

High Capacity Hydrogen Storage on Zirconium decorated γ-graphyne: A systematic first-principles study

In this work, we investigate the hydrogen-storage properties of Zr-decorated $γ$-graphyne monolayer employing Density Functional Theory (DFT) for green energy storage. We predict that each Zr atom decorated on graphyne sheet (2D) can adsorb up to seven H$_2$ molecules with an average adsorption energy of -0.44 eV/H$_2$, leading to a hydrogen gravimetric density of 7.95 wt%, and desorption temperature of 574 K, particularly suited to fuel-cell applications. Decorated Zr atom strongly attached to graphyne due to charge transfer from Zr to graphyne sheet. Hydrogen molecules adsorb on Zr decorated graphyne with Kubas type of interaction. The 4.05 eV diffusion energy barrier between Zr decorated position, and its neighboring pores may avoid the metal-metal (Zr-Zr) clustering. The stability of Zr+$γ$-graphyne is confirmed by performing ab-initio molecular dynamics simulations at room temperature and at estimated average desorption temperature. Hence, our calculations show Zr functionalized on $γ$-graphyne could be a promising solid-state hydrogen storage material.

cond-mat.mtrl-sci↗

arXiv2023

Improving Hydrogen evolution catalytic activity of 2D carbon allotrope Biphenylene with B, N, P doping: Density Functional Theory Investigations

Using a first principles approach, we studied the hydrogen evolution reaction activity of newly synthesized biphenylene and B, N, P decorated biphenylene sheet. hydrogen evolution reaction activity of pristine biphenylene sheet is not encouraging, as it is similar to pristine graphene. The Gibbs free energy and overpotential of P(N) doped on biphenylene sheet are 0.022 (-0.092) eV and 22 (92) mV, respectively. The reported Gibbs free energy and overpotential of Pt are 0.9 eV and 90 mV. Hence doping of P(N) atom on top of biphenylene sheet improves hydrogen evolution reaction activity much better (near to) Pt metal. We analyzed the adsorption mechanism of dopants (B, N, P) and hydrogen with Bader charge analysis and density of states analysis. P and N-decoration on biphenylene sheet change its electronic structure so that one obtains improved hydrogen evolution reaction activity for P and N-doped biphenylene sheet. Furthermore, the stability of N, P decorated biphenylene at room temperature with ab initio molecular dynamics and formation energy near that of biphenylene indicate experimental feasibility. We have compared all our best hydrogen evolution reaction activity results in the reaction coordinate and volcano plots of pristine, B, N, and P-doped BPh sheets. They indicate that P-doped biphenylene is a metal-free, powerful catalyst for hydrogen evolution reaction activities.

cond-mat.mtrl-sci↗

arXiv2023

Highly Efficient Hydrogen Storage of Sc Decorated Biphenylene Monolayer near Ambient-temperature: An Ab-initio Simulation

The energy demands for the growing development of society need to be catered with alternative and green fuels like hydrogen energy for a lasting and sustainable culture. One essential component of the hydrogen economy is the efficiency of its storage. We have studied the hydrogen-storage capability on a recently synthesized Biphenylene (BPh) decorated with Sc using the first-principles density functional theory (DFT) and ab-initio molecular dynamics (AIMD) techniques. Scandium attaches BPh sheet strongly with binding energy -3.84 eV, and single Sc decorated on BPh can absorb a maximum of five H$_2$ molecules resulting in a high gravimetric weight percentage of 11.07, which is significantly higher than DoE's ultimate criteria (6.5 wt%). Using van't Hoff equation, strongly and weakly attached hydrogens correspond to desorption temperatures of 200 K and 397 K with an average of 305 K. The high binding of Sc to BPh is due to charge donation of 3d orbital of Sc to 2p orbital of C. The interactions between absorbed H$_2$ and BPh+Sc are due to charge transfer from 3d-orbital of Sc to $σ$* bond of H$_2$ molecules and backdonation from $σ$ bond of H$_2$ to empty 3d-orbital of Sc known as Kubas type interaction. Furthermore, phonon and AIMD simulation confirm BPh+Sc stability, and the presence of an energy barrier shows no probability of Sc-Sc clustering on BPh. So theoretically stable BPh+Sc showing high gravimetric weight percentage with an average 305 K desorption temperature, might be a potential candidate for solidstage hydrogen devices.

cond-mat.mtrl-sci↗

arXiv2022

An Ab-initio study of the Y decorated 2D holey graphyne for hydrogen storage application

Expanding pollution and rapid consumption of natural reservoirs (gas, oil, and coal) led humankind to explore alternative energy fuels like hydrogen fuel. Solid-state hydrogen storage is most desirable because of its usefulness in the onboard vehicle. In this work, we explored the yttrium decorated ultra porous, two-dimensional holey-graphyne for hydrogen storage. Using the first principles DFT simulations, we predict that yttrium doped holey graphyne can adsorb up to seven hydrogen molecules per yttrium atom resulting in a gravimetric hydrogen weight percentage of 9.34, higher than the target of 6.5 wt% set by the US Department of Energy (DoE). The average binding energy per H$_2$ and desorption temperature come out to be -0.34 eV and ~ 438 K, respectively. Yttrium atom is bonded strongly on HGY sheet due to charge transfer from Y 4d orbital to C 2p orbital whereas the adsorption of H$_2$ molecule on Y is due to Kubas-type interactions involving charge donation from H 1s orbital to Y 3d orbital and back donation with net charge gain by H 1s orbital. Furthermore, sufficient energy barriers for metal atom diffusion have been found to prevent the clustering of transition metal (yttrium) on the HGY sheet. The stability of the system at higher temperatures is analyzed using Ab-initio molecular dynamics (AIMD) method and the system is found to be stable at room and the highest desorption temperature. Stability of the system at higher temperatures, presence of adequate diffusion energy barrier to prevent metal-metal clustering, high gravimetric wt% of H$_2$ uptake with suitable binding energy, and desorption temperature signifies that Y-doped HGY is a promising material to fabricate high capacity hydrogen storage devices.

cond-mat.mtrl-sci↗