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UV–Vis Spectroscopy: Molecular Electronic Transitions01:16

UV–Vis Spectroscopy: Molecular Electronic Transitions

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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...
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UV–Vis Spectroscopy of Conjugated Systems01:32

UV–Vis Spectroscopy of Conjugated Systems

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Organic compounds with conjugated double bonds show strong absorption features in the UV–visible region of the electromagnetic spectrum attributed to π → π* electronic excitations. Generally, a UV–vis absorption spectrum is recorded as a plot of absorbance vs wavelength. The wavelength of maximum absorbance, which manifests as a peak in the absorption spectrum, is denoted as λmax.
One of the factors influencing λmax is the extent...
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Molecular Spectroscopy: Absorption and Emission01:14

Molecular Spectroscopy: Absorption and Emission

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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.
1.7K
¹H NMR: Interpreting Distorted and Overlapping Signals01:02

¹H NMR: Interpreting Distorted and Overlapping Signals

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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.
As Δν decreases and the signals move closer, the doublets appear increasingly distorted. The intensities of the inner lines increase at the cost of those of the outer lines as the signals are...
991
IR Spectroscopy: Hooke's Law Approximation of Molecular Vibration01:16

IR Spectroscopy: Hooke's Law Approximation of Molecular Vibration

1.2K
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.
According to Hooke's law, the vibrational frequency is directly proportional to...
1.2K
IR Spectroscopy: Molecular Vibration Overview01:24

IR Spectroscopy: Molecular Vibration Overview

1.8K
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.
Stretching vibrations are vibrational motions that occur along the bond line, changing the bond length or distance between two bonded atoms. They are further distinguished as symmetric or asymmetric. In symmetric stretching, the...
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Updated: May 27, 2025

High Resolution Phonon-assisted Quasi-resonance Fluorescence Spectroscopy
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Nonlinear optical spectroscopy of open quantum systems.

Haoran Sun1, Upendra Harbola2, Shaul Mukamel3

  • 1Department of Chemistry and Biochemistry, University of California San Diego, La Jolla, California 92093, USA.

The Journal of Chemical Physics
|February 19, 2025
PubMed
Summary

Single-molecule spectroscopy and molecular electronics intersect, revealing connections between optical spectroscopy and nonequilibrium Green's functions. Analyzing open quantum systems requires the Green's function framework for accurate molecular electronics research.

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Area of Science:

  • Physical Chemistry
  • Molecular Electronics
  • Spectroscopy

Background:

  • Nanoscale experimental techniques enable single-molecule spectroscopy on current-carrying junctions.
  • This research bridges optical spectroscopy and molecular electronics.
  • Existing methods for molecular electronics often use nonequilibrium Green's functions (NEGF).

Purpose of the Study:

  • To pedagogically compare standard nonlinear optical spectroscopy with the NEGF method.
  • To highlight similarities and differences between these theoretical frameworks.
  • To establish the necessity of the Green's function framework for optical spectroscopy of open quantum systems.

Main Methods:

  • Perturbation theory expansion of standard nonlinear optical spectroscopy.
  • Perturbative diagrammatic formulation of NEGF.
  • Comparative analysis of the two theoretical approaches.

Main Results:

  • Identified similarities and differences between optical spectroscopy and NEGF perturbation theories.
  • Demonstrated the applicability of Green's function formalism to optical spectroscopy.
  • Provided a unified theoretical perspective.

Conclusions:

  • The Green's function framework offers a more general and robust approach for analyzing optical spectroscopy in open quantum systems.
  • This comparison enhances understanding at the intersection of optical spectroscopy and molecular electronics.
  • Future research in molecular electronics can benefit from this integrated theoretical perspective.