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Woodward–Hoffmann Selection Rules and Microscopic Reversibility01:34

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Electrocyclic reactions, cycloadditions, and sigmatropic rearrangements are concerted pericyclic reactions that proceed via a cyclic transition state. These reactions are stereospecific and regioselective. The stereochemistry of the products depends on the symmetry characteristics of the interacting orbitals and the reaction conditions. Accordingly, pericyclic reactions are classified as either symmetry-allowed or symmetry-forbidden. Woodward and Hoffmann presented the selection criteria for...
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Time scaling of signals is a crucial concept in signal processing that affects the Fourier series representation without altering its coefficients. The process modifies the fundamental frequency, thereby changing how the series represents the signal over time. This principle is essential in various applications, including audio and image processing, where signal manipulation is frequent. Understanding function symmetries is fundamental to simplifying the Fourier series.
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Symmetry in Maxwell's Equations01:28

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Once the fields have been calculated using Maxwell's four equations, the Lorentz force equation gives the force that the fields exert on a charged particle moving with a certain velocity. The Lorentz force equation combines the force of the electric field and of the magnetic field on the moving charge. Maxwell's equations and the Lorentz force law together encompass all the laws of electricity and magnetism. The symmetry that Maxwell introduced into his mathematical framework may not be...
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The equation of an ellipse centered at the origin defines all points whose distances from the center maintain a constant ratio between the horizontal and vertical axes. This equation results in a smooth, closed curve that extends further along the x-axis than the y-axis, giving it a horizontal orientation. Such an ellipse demonstrates three kinds of symmetry: across the x-axis, across the y-axis, and about the origin. These symmetries are essential in understanding the graph's structure and...
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Properties of Fourier series I01:20

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The Fourier series is a powerful tool in signal processing and communications, allowing periodic signals to be expressed as sums of sine and cosine functions. A foundational property of the Fourier series is linearity. If we consider two periodic signals, their linear combination results in a new signal whose Fourier coefficients are simply the corresponding linear combinations of the original signals' coefficients. This property is crucial in applications like frequency modulation (FM) radio,...
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Spin systems where the difference in chemical shifts of the coupled nuclei is greater than ten times J are called first-order spin systems. These nuclei are weakly coupled, and their chemical shifts and coupling constant can generally be estimated from the well-separated signals in the spectrum.
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Related Experiment Video

Updated: Apr 18, 2026

Time Multiplexing Super Resolving Technique for Imaging from a Moving Platform
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On surface hopping and time-reversal.

Joseph E Subotnik1, Young Min Rhee

  • 1Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104, United States.

The Journal of Physical Chemistry. A
|January 31, 2015
PubMed
Summary

Reversing time for Tully-style fewest switches surface hopping (FSSH) dynamics is possible for short durations. However, time-reversed FSSH dynamics become unstable with multiple hops, correlating with forward-time algorithm stability.

Area of Science:

  • Quantum dynamics
  • Computational chemistry
  • Surface hopping algorithms

Background:

  • Tully-style fewest switches surface hopping (FSSH) is a widely used method for simulating non-adiabatic dynamics.
  • Individual FSSH trajectories are inherently time-reversible only in the absence of quantum mechanical jumps (surface hops).
  • The collective behavior of FSSH trajectory swarms offers potential for time-reversal, despite individual stochasticity.

Purpose of the Study:

  • To develop and investigate the methodology for inverting the time dynamics of FSSH trajectory swarms.
  • To analyze the stability of time-reversed FSSH dynamics, particularly concerning the impact of multiple hopping events.
  • To establish a correlation between the instability of backward-time FSSH and the stability of the forward-time algorithm.

Main Methods:

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  • Simulating ensembles of FSSH trajectories under various conditions.
  • Implementing algorithms for reversing the time evolution of these trajectory swarms.
  • Analyzing the stability and accuracy of the time-reversed dynamics as a function of time and hopping events.

Main Results:

  • Demonstrated successful time-inversion of FSSH dynamics for short simulation periods.
  • Observed significant instability in time-reversed FSSH dynamics with an increasing number of surface hopping events.
  • Identified a correlation between the observed instability in backward-time FSSH and the inherent stability characteristics of the forward-time FSSH algorithm.

Conclusions:

  • Time-reversal of FSSH dynamics is feasible but limited by instabilities arising from multiple surface hops.
  • The stability of time-reversed FSSH provides insights into the forward-time algorithm's behavior and limitations.
  • Further research may explore modifications to FSSH to enhance the stability of time-reversed dynamics.