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Related Concept Videos

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.
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...
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.
According to Hooke's law, the vibrational frequency is directly proportional to the...
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,...
Raman Spectroscopy: Overview01:20

Raman Spectroscopy: Overview

The underlying principle of Raman spectroscopy is based on the interaction between light and matter, specifically molecules' inelastic scattering of photons. When a monochromatic beam of light, typically from a laser source, interacts with a sample, most scattered light has the same frequency as the incident light. This is known as Rayleigh scattering.
However, a small fraction of the scattered light exhibits a frequency shift due to the exchange of energy between the incident photons and the...
IR Spectrum Peak Splitting: Symmetric vs Asymmetric Vibrations01:08

IR Spectrum Peak Splitting: Symmetric vs Asymmetric Vibrations

Identical bonds within a polyatomic group can stretch symmetrically (in-phase) or asymmetrically (out-of-phase). Similar to hydrogen bonding, these vibrations also influence the shape of the IR peak. Generally, asymmetric stretching frequencies are higher than symmetric stretching frequencies. For example, primary amines exhibit two distinct IR peaks between 3300–3500 cm−1 corresponding to the symmetric and asymmetric N-H stretching, while secondary amines exhibit a single stretching vibration...
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.

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Related Experiment Video

Updated: May 7, 2026

Multimodal Nonlinear Hyperspectral Chemical Imaging Using Line-Scanning Vibrational Sum-Frequency Generation Microscopy
08:49

Multimodal Nonlinear Hyperspectral Chemical Imaging Using Line-Scanning Vibrational Sum-Frequency Generation Microscopy

Published on: December 1, 2023

Reorientation-induced spectral diffusion in vibrational sum-frequency-generation spectroscopy.

Christopher A Rivera1, Amanda J Souna, John S Bender

  • 1Department of Chemistry & Biochemistry, ‡Institute for Physical Science and Technology, §Maryland NanoCenter, ∥Center for Nanophysics and Advanced Materials, ⊥Chemical Physics Program, University of Maryland , College Park, MD 20742.

The Journal of Physical Chemistry. B
|October 4, 2013
PubMed
Summary

Reorientation-induced spectral diffusion (RISD) significantly impacts vibrational sum-frequency-generation (VSFG) line shapes by making them time-dependent. This effect influences spectra regardless of polarization, as demonstrated with liquid acetonitrile at a silica interface.

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Last Updated: May 7, 2026

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Interfacial Molecular-level Structures of Polymers and Biomacromolecules Revealed via Sum Frequency Generation Vibrational Spectroscopy
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06:34

In Situ Monitoring of Diffusion of Guest Molecules in Porous Media Using Electron Paramagnetic Resonance Imaging

Published on: September 2, 2016

Area of Science:

  • Surface Science
  • Spectroscopy
  • Physical Chemistry

Background:

  • Dynamic processes are crucial for understanding line shapes in nonlinear spectroscopies like vibrational sum-frequency-generation (VSFG).
  • Molecular reorientation can influence VSFG signals, but its impact on spectral line shape, especially when transition frequencies depend on orientation, requires further investigation.

Purpose of the Study:

  • To analyze the influence of molecular reorientation on VSFG spectra when vibrational transition frequencies are orientation-dependent.
  • To investigate the phenomenon of reorientation-induced spectral diffusion (RISD) and its effect on VSFG line shapes.
  • To assess the contribution of RISD to VSFG spectra using a model system.

Main Methods:

  • Analysis of VSFG spectra considering orientation-dependent vibrational transition frequencies.
  • Modeling reorientation-induced spectral diffusion (RISD).
  • Experimental assessment using liquid acetonitrile at a silica interface and comparison with simulations.

Main Results:

  • Reorientation-induced spectral diffusion (RISD) causes time-dependent spectral line shapes in VSFG.
  • RISD affects the line shape irrespective of the probed Raman transition's polarization.
  • Experimental VSFG spectra show substantial RISD contribution, particularly at delay times comparable to or longer than the probe pulse duration.

Conclusions:

  • RISD is a significant factor influencing VSFG line shapes, especially when transition frequencies are linked to molecular orientation.
  • The findings are consistent with a two-state RISD model incorporating orientational distributions from molecular dynamics simulations.
  • Understanding RISD is essential for accurate interpretation of VSFG spectra in dynamic interfacial systems.