Mengxiao Liu | Searcharxiv

arXiv2022

ORBGRAND Is Almost Capacity-Achieving

Decoding via sequentially guessing the error pattern in a received noisy sequence has received attention recently, and ORBGRAND has been proposed as one such decoding algorithm that is capable of utilizing the soft information embedded in the received noisy sequence. An information theoretic study is conducted for ORBGRAND, and it is shown that the achievable rate of ORBGRAND using independent and identically distributed random codebooks almost coincides with the channel capacity, for an additive white Gaussian noise channel under antipodal input. For finite-length codes, improved guessing schemes motivated by the information theoretic study are proposed that attain lower error rates than ORBGRAND, especially in the high signal-to-noise ratio regime.

cs.IT↗

arXiv2021

Time- and Site-Resolved Kinetic NMR: Real-Time Monitoring of Off-Equilibrium Chemical Dynamics by 2D Spectrotemporal Correlations

Nuclear magnetic resonance (NMR) spectroscopy provides detailed information pertaining to dynamic processes through line-shape changes, which have been traditionally limited to equilibrium conditions. However, there is a wealth of information to be gained by studying chemical reactions under off-equilibrium conditions -- e.g., in states that arise upon mixing reactants that subsequently undergo chemical changes -- and in monitoring the formation of reaction products in real time. Herein, we propose and demonstrate a time-resolved kinetic NMR experiment that combines rapid mixing techniques, continuous flow, and single-scan spectroscopic imaging methods, leading in unison to a new 2D spectro-temporal NMR correlation which provides high-quality kinetic information of off-equilibrium dynamics. These kinetic 2D NMR spectra possess a spectral dimension conveying with high resolution the individual chemical sites, correlated with a time-independent, steady-state spatial axis that delivers unique information concerning temporal changes along the chemical reaction coordinate. A comprehensive description of the kinetic and spectroscopic features associated to these spectro-temporal NMR analyses is presented, factoring in the rapid-mixing, the flow and the spectroscopic NMR imaging. An experimental demonstration of this method's novel aspects was carried out using an enzymatically catalyzed reaction, leading to site- and time-resolved kinetic NMR data that are in excellent agreement with control experiments and literature values.

physics.chem-ph↗