In general, for many-dimensional and many-state nonadiabatic dynamics composed of slow and fast modes, we geometrically decompose the nonadiabatic interactions by means of the method of singular value decomposition. Each pair of the left and right singular vectors connecting the slow (nuclear) and fast (electronic) modes gives rise to a one-dimensional collective coordinate, and the sum of them amounts to the total nonadiabatic interaction. The analysis identifies how efficiently the slow modes, thus decomposed, can induce a transition in their fast counterparts. We discuss the notions of nonadiabatic resonance and nonadiabatic chaos in terms of the decomposition.
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http://dx.doi.org/10.1063/5.0186816 | DOI Listing |
J Magn Reson
January 2025
Center for Magnetic Resonance Research, University of Minnesota, 2021 6th Street SE, Minneapolis, MN 55455, USA. Electronic address:
In this work the effect of the geometric phase on time evolution of the density matrix was evaluated during nonadiabatic radiofrequency (RF) pulses with Sine amplitude modulation (AM) and Cosine frequency modulation (FM) functions of the RAFF (Relaxations Along a Fictitious Field) family, and the polarization between two energy level ½ spin system coupled by dipolar interaction was evaluated during the application of RF irradiation. The dependencies of the diagonal density matrix elements and the polarization on the rotational correlation times and the time during RF pulses were evaluated. The general treatment of the density matrix elements along with the polarization generated during RF pulses was unavailable thus far, and for the first time was here derived for the nonadiabatic case of the RAFF pulses.
View Article and Find Full Text PDFJ Am Chem Soc
January 2025
Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States.
Ribonucleotide reductase (RNR) is essential for DNA synthesis and repair in all living organisms. The mechanism of RNR requires long-range radical transport through a proton-coupled electron transfer (PCET) pathway spanning two different protein subunits. Herein, the direct PCET reaction between the interfacial tyrosine residues, Y356 and Y731, is investigated with a vibronically nonadiabatic theory that treats the transferring proton and all electrons quantum mechanically.
View Article and Find Full Text PDFJ Phys Chem Lett
January 2025
Inner Mongolia Key Laboratory of Rare Earth Catalysis, College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot 010021, People's Republic of China.
Focusing on Au/BiOCl, we investigated the effects of the metal-support interaction (MSI) on the photogenerated charge carrier separation using nonadiabatic molecular dynamic simulations combined with time-domain density functional theory. Our results show that the time scales of electron transfer from the Au cluster to BiOCl are distinct depending on the intensity of MSI. Oxygen vacancy (OV) can enhance the interaction between the Au cluster and BiOCl, leading to a stronger nonadiabatic (NA) coupling in Au/BiOCl with an OV system compared to that in a pristine Au/BiOCl system.
View Article and Find Full Text PDFSci Rep
January 2025
School of Physics and Information Technology, Shaanxi Normal University, Xi'an, 710062, Shaanxi, People's Republic of China.
Electron-nuclear coupling plays a crucial role in strong laser induced molecular dissociation dynamics. The interplay between electronic and nuclear degrees of freedom determines the pathways and outcomes of molecular fragmentation. However, a full quantum mechanical treatment of electron-nuclear dynamics is computationally intensive.
View Article and Find Full Text PDFJ Chem Phys
January 2025
MOE Key Laboratory for Non-Equilibrium Synthesis and Modulation of Condensed Matter, School of Physics, Xi'an Jiaotong University, Xi'an 710049, People's Republic of China.
Endohedral and exohedral fullerenes have both been employed as electron acceptors in polymer solar cells (PSCs). However, their differences in hot-electron relaxation dynamics remain unclear. Previous studies have shown that the location of a single atom, whether inside or outside the fullerene cage, results in significant differences in charge distribution.
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