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Constrained Nuclear-Electronic Orbital Transition State Theory Using Energy Surfaces with Nuclear Quantum Effects.
J Chem Theory Comput
January 2025
Theoretical Chemistry Institute and Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison, Wisconsin 53706, United States.
Hydrogen-atom transfer is crucial in a myriad of chemical and biological processes, yet the accurate and efficient description of hydrogen-atom transfer reactions and kinetic isotope effects remains challenging due to significant quantum effects on hydrogenic motion, especially tunneling and zero-point energy. In this paper, we combine transition state theory (TST) with the recently developed constrained nuclear-electronic orbital (CNEO) theory to propose a new transition state theory denoted CNEO-TST. We use CNEO-TST with CNEO density functional theory (CNEO-DFT) to predict reaction rate constants for two prototypical gas-phase hydrogen-atom transfer reactions and their deuterated isotopologic reactions.
View Article and Find Full Text PDFGeneralized Hydrodynamic Description of the Page Curve-like Dynamics of a Freely Expanding Fermionic Gas.
Phys Rev Lett
December 2024
International Centre for Theoretical Sciences, Tata Institute of Fundamental Research, Bangalore 560089, India.
We consider an analytically tractable model that exhibits the main features of the Page curve characterizing the evolution of entanglement entropy during evaporation of a black hole. Our model is a gas of noninteracting fermions on a lattice that is released from a box into the vacuum. More precisely, our Hamiltonian is a tight-binding model with a defect at the junction between the filled box and the vacuum.
View Article and Find Full Text PDFModeling of warm dense hydrogen via explicit real-time electron dynamics: Dynamic structure factors.
Phys Rev E
November 2024
Department of Physics, University of Oxford, Oxford OX1 3PU, United Kingdom.
We present two methods for computing the dynamic structure factor for warm dense hydrogen without invoking either the Born-Oppenheimer approximation or the Chihara decomposition, by employing a wave-packet description that resolves the electron dynamics during ion evolution. First, a semiclassical method is discussed, which is corrected based on known quantum constraints, and second, a direct computation of the density response function within the molecular dynamics. The wave-packet models are compared to PIMC and DFT-MD for the static and low-frequency behavior.
View Article and Find Full Text PDFIn this perspective we deal with the challenge of investigating nuclear quantum effects in solvated and condensed phase molecular systems in a computationally affordable way. To this end, semiclassical methods are promising theoretical approaches, as we demonstrate through vibrational spectroscopy and reaction kinetics. We show that quantum vibrational features can be found in hydrates of carbonyl compounds and microsolvated amino acids, and we report quantum estimates of the low-temperature reaction rate constant of a unimolecular reaction taking place in a noble-gas matrix.
View Article and Find Full Text PDFToward a Correct Description of Initial Electronic Coherence in Nonadiabatic Dynamics Simulations.
J Phys Chem Lett
November 2024
Hamburg Center for Ultrafast Imaging, Universität Hamburg and Max Planck Institute for the Structure and Dynamics of Matter, Luruper Chaussee 149, 22761 Hamburg, Germany.
The recent improvement in experimental capabilities for interrogating and controlling molecular systems with ultrafast coherent light sources calls for the development of theoretical approaches that can accurately and efficiently treat electronic coherence. However, the most popular and practical nonadiabatic molecular dynamics techniques, Tully's fewest-switches surface hopping and Ehrenfest mean-field dynamics, are unable to describe the dynamics proceeding from an initial electronic coherence. While such issues are not encountered with the analogous coupled-trajectory algorithms or numerically exact quantum dynamics methods, applying such techniques necessarily comes with a higher computational cost.
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