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Related Concept Videos

¹³C NMR: ¹H–¹³C Decoupling01:04

¹³C NMR: ¹H–¹³C Decoupling

The probability of having two carbon-13 atoms next to each other is negligible because of the low natural abundance of carbon-13. Consequently, peak splitting due to carbon-carbon spin-spin coupling is not observed in spectra. However, protons up to three sigma bonds away split the carbon signal according to the n+1 rule, resulting in complicated spectra.
A broadband decoupling technique is used to simplify these complex, sometimes overlapping, signals. Broadband decoupling relies on a...
Molecular Spectroscopy: Absorption and Emission01:14

Molecular Spectroscopy: Absorption and Emission

Molecules possess discrete energy levels called quantum states. Unlike atoms, which have simpler energy levels, molecules possess additional rotational and vibrational energy levels. Each energy level is separated by an energy gap, with the gaps between adjacent electronic, vibrational, and rotational levels varying significantly. The three types of energy levels in a diatomic molecule are shown in Figure 1.
UV–Vis Spectroscopy: Molecular Electronic Transitions01:16

UV–Vis Spectroscopy: Molecular Electronic Transitions

In Ultraviolet–Visible (UV–Vis) spectroscopy, the absorption of electromagnetic radiation is used to probe the electronic structure of molecules. This technique provides insights into molecular electronic transitions, particularly the movement of electrons between different molecular orbitals. Radiation is absorbed if the energy of the electromagnetic radiation passing through the molecule is precisely equal to the energy difference between the excited and ground states. During this process,...
IR Spectroscopy: Molecular Vibration Overview01:24

IR Spectroscopy: Molecular Vibration Overview

When Infrared (IR) radiation passes through a covalently bonded molecule, the bonds transition from lower to higher vibrational levels. The fundamental vibrational motions that result in infrared absorption can be classified as stretching or bending vibrations.
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IR Spectroscopy: Hooke's Law Approximation of Molecular Vibration01:16

IR Spectroscopy: Hooke's Law Approximation of Molecular Vibration

A covalently bonded heteronuclear diatomic molecule can be modeled as two vibrating masses connected by a spring. The vibrational frequency of the bond can be expressed using an equation derived from Hooke's law, which describes how the force applied to stretch or compress a spring is proportional to the displacement of the spring. In this case, the atoms behave like masses, and the bond acts like a spring.
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Atomic Absorption Spectroscopy: Interference01:25

Atomic Absorption Spectroscopy: Interference

Interference leads to systematic error in atomic absorption (AA) measurements by enhancing or diminishing the analytical signal or the background. These interferences can be grouped into three main categories: spectral interference, chemical interference, and physical interference.
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Related Experiment Video

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All-electronic Nanosecond-resolved Scanning Tunneling Microscopy: Facilitating the Investigation of Single Dopant Charge Dynamics
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All-electronic Nanosecond-resolved Scanning Tunneling Microscopy: Facilitating the Investigation of Single Dopant Charge Dynamics

Published on: January 19, 2018

Multidimensional vibrational spectroscopy for tunneling processes in a dissipative environment.

Akihito Ishizaki1, Yoshitaka Tanimura

  • 1Department of Physics, Graduate School of Science, Kyoto University, Kyoto 606-8502, Japan. ishizaki@kuchem.kyoto-u.ac.jp

The Journal of Chemical Physics
|July 23, 2005
PubMed
Summary

This study uses 2D-IR spectroscopy to observe tunneling dynamics in double-well systems. The technique can measure chemical reaction rates by analyzing vibrational excitation and relaxation.

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Area of Science:

  • Quantum dynamics
  • Spectroscopy
  • Chemical kinetics

Background:

  • Simulating and observing tunneling processes are challenging.
  • System-bath interactions (linear-linear and square-linear) influence relaxation dynamics (T1, T2, T2*).

Purpose of the Study:

  • To investigate double-well system dynamics under IR laser excitation.
  • To develop a method for observing tunneling dynamics and measuring reaction rates.

Main Methods:

  • Gaussian-Markovian quantum Fokker-Planck equation approach.
  • Fourier-Laplace transformation for Green function analysis.
  • Calculation of third-order two-dimensional infrared (2D-IR) signals.

Main Results:

  • Off-diagonal peaks in 2D-IR spectra reveal bath-induced vibrational dynamics.
  • The method directly evaluates tunneling reaction rate constants.
  • Reaction rates are shown to change with system-bath coupling and temperature.

Conclusions:

  • 2D-IR spectroscopy is a novel technique for measuring chemical reaction rates.
  • The study provides insights into tunneling dynamics influenced by system-bath interactions.
  • The developed approach offers a new way to probe quantum phenomena.