We present a new interpretation of the decoherence correction in surface hopping by examining the inconsistency of the traditional time-dependent Schrödinger equation and propose an elegant decoherence correction algorithm to deal with wave packet branching. In contrast to the widely used approaches based on decoherence rates, our branching corrected surface hopping (BCSH) resets the wavefunction directly after wave packet branching is identified through prediction of trajectory reflection. The appealing simplicity and reliability of BCSH are demonstrated in a series of widely studied one-dimensional and two-dimensional scattering models using exact quantum solutions and existing surface hopping approaches as references. The BCSH approach exhibits a high performance in all investigated systems, showing good potential for applications in general nonadiabatic dynamics simulations.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1063/1.5090927 | DOI Listing |
J Phys Chem A
January 2025
Department of Chemistry and Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455-0431, United States.
The energy gaps, spin-orbit coupling (SOC), and admixture coefficients over a series of the configurations are evaluated by the SA-CASSCF/6-31G, SA-CASSCF/6-31G*, SA-CASSCF/ANO-RCC-VDZP, and MS-CASPT2/ANO-RCC-VDZP to reveal the extent of the inaccuracy of the SA-CASSCF. By comparing the mean absolute errors for the energy gaps and the admixture coefficient magnitudes (ACMs) measured between the SA-CASSCF/6-31G, SA-CASSCF/6-31G*, or SA-CASSCF/ANO-RCC-VDZP and the MS-CASPT2/ANO-RCC-VDZP, the SA-CASSCF/6-31G is selected as the electronic structure method in the nonadiabatic molecular dynamics simulation. The major components of the ACMs of the SA-CASSCF/6-31G and MS-CASPT2/ANO-RCC-VDZP are identified and compared; we find that the ACMs are underestimated by the SA-CASSCF/6-31G, which is verified by the reasonable triplet quantum yield simulated by the trajectory surface hopping and the calibrated SA-CASSCF/6-31G.
View Article and Find Full Text PDFJ Chem Phys
January 2025
Department of Chemistry, School of Science, Westlake University, Hangzhou, Zhejiang 310024, China.
One key challenge in the study of nonadiabatic dynamics in open quantum systems is to balance computational efficiency and accuracy. Although Ehrenfest dynamics (ED) is computationally efficient and well-suited for large complex systems, ED often yields inaccurate results. To address these limitations, we improve the accuracy of the traditional ED by adding a random force (E + σ).
View Article and Find Full Text PDFJ Phys Chem Lett
January 2025
SCNU Environmental Research Institute, Guangdong Provincial Key Laboratory of Chemical Pollution and Environmental Safety & MOE Key Laboratory of Environmental Theoretical Chemistry, School of Environment, South China Normal University, Guangzhou 510006, China.
Two-dimensional (2D) electronic spectra of the phenylene ethynylene dendrimer with 2-ring and 3-ring branches were evaluated by combining the on-the-fly trajectory surface hopping nonadiabatic dynamics and the doorway-window simulation protocol. The ground state bleach (GSB), stimulated emission (SE), and excited-state absorption (ESA) contributions to the 2D signal were obtained and carefully analyzed. The results demonstrate that the ultrafast intramolecular nonadiabatic excited-state energy transfer (EET) from the 2-ring to the 3-ring units is comprehensively characterized by the SE and ESA signals.
View Article and Find Full Text PDFSports Biomech
January 2025
School of Kinesiology, Auburn University, Auburn, AL, USA.
An athlete's performance and musculoskeletal health hinges on their ability to adapt their movements to varying environmental constraints. However, research has yet to offer a thorough understanding of whether coordination variability is altered in response to different synthetic and natural turf surfaces. The purpose of this study was to investigate lower extremity coordination variability during hopping and running on four turf surfaces-three synthetic and one natural.
View Article and Find Full Text PDFNat Commun
January 2025
State Key Laboratory of Integrated Optoelectronics, College of Electronic Science and Engineering, Jilin University, Changchun, P. R. China.
Photoluminescence is one of the most intriguing properties of metal nanoclusters derived from their molecular-like electronic structure, however, achieving high photoluminescence quantum yield (PLQY) of metal core-dictated fluorescence remains a formidable challenge. Here, we report efficient suppression of the total structural vibrations and rotations, and management of the pathways and rates of the electron transfer dynamics to boost a near-unity absolute PLQY, by decorating progressive addition of cations. Specifically, with the sequential addition of Zn, Ag, and Tb into the 3-mercaptopropionic acids capped Au nanoclusters (NCs), the low-frequency vibration of the metal core progressively decreases from 144.
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!