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Related Concept Videos

IR Spectroscopy: Hooke's Law Approximation of Molecular Vibration01:16

IR Spectroscopy: Hooke's Law Approximation of Molecular Vibration

1.3K
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...
1.3K
IR Spectroscopy: Molecular Vibration Overview01:24

IR Spectroscopy: Molecular Vibration Overview

2.3K
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...
2.3K
¹H NMR: Long-Range Coupling01:27

¹H NMR: Long-Range Coupling

1.7K
The coupling interactions of nuclei across four or more bonds are usually weak, with J values less than 1 Hz. While these are usually not observed in spectra, the presence of multiple bonds along the coupling pathway can result in observable long-range coupling.
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene...
1.7K
NMR Spectroscopy: Spin–Spin Coupling01:08

NMR Spectroscopy: Spin–Spin Coupling

1.4K
The spin state of an NMR-active nucleus can have a slight effect on its immediate electronic environment. This effect propagates through the intervening bonds and affects the electronic environments of NMR-active nuclei up to three bonds away; occasionally, even farther. This phenomenon is called spin–spin coupling or J-coupling. Coupling interactions are mutual and result in small changes in the absorption frequencies of both nuclei involved. While nuclei of the same element are involved...
1.4K
¹H NMR: Interpreting Distorted and Overlapping Signals01:02

¹H NMR: Interpreting Distorted and Overlapping Signals

1.0K
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...
1.0K
Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)01:22

Spin–Spin Coupling: Three-Bond Coupling (Vicinal Coupling)

1.1K
Vicinal or three-bond coupling is commonly observed between protons attached to adjacent carbons. Here, nuclear spin information is primarily transferred via electron spin interactions between adjacent C‑H bond orbitals. This generally favors the antiparallel arrangement of spins, so 3J values are usually positive.
The extent of coupling depends on the C‑C bond length, the two H‑C‑C angles, any electron-withdrawing substituents, and the dihedral angle between the...
1.1K

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Author Spotlight: Advances in Nanoscale Infrared Spectroscopy to Explore Multiphase Polymeric Systems
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Vibrational Coupling Infrared Nanocrystallography.

Richard L Puro1, Thomas P Gray1, Tsitsi A Kapfunde2

  • 1Department of Physics and JILA, University of Colorado, Boulder, Colorado 80309, United States.

Nano Letters
|February 5, 2024
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Summary
This summary is machine-generated.

Vibrational coupling nanocrystallography (VCNC) now quantitatively maps molecular order and interactions. This technique links nano-FTIR spectra to X-ray crystallography for nanoscale insights into molecular systems.

Keywords:
crystallographyinfrared spectroscopyscattering scanning near-field optical microscopy (s-SNOM)transition dipole couplingvibrational exciton

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Area of Science:

  • Spectroscopy
  • Crystallography
  • Materials Science

Background:

  • Molecular vibrations exhibit coupling, forming collective states sensitive to local molecular order.
  • This coupling offers spectroscopic access to the low-frequency intermolecular energy landscape.
  • Vibrational coupling nanocrystallography (VCNC) provides nanometer-scale information on molecular disorder and domain formation.

Purpose of the Study:

  • To develop a quantitative model for VCNC by correlating nano-FTIR collective vibrational spectra with X-ray crystallography data.
  • To establish a framework for deriving local molecular order without prior knowledge of transition dipole magnitude or crystal structure.
  • To expand the applicability of VCNC for analyzing molecular interactions and nanoscale phenomena.

Main Methods:

  • Development of a quantitative model linking nano-FTIR collective vibrational spectra to molecular crystal structures.
  • Experimental validation using a metal-organic porphyrin complex with a carbonyl ligand as a probe vibration.
  • Integration of X-ray crystallography for structural reference.

Main Results:

  • A validated quantitative model for VCNC has been established.
  • The model successfully relates nano-FTIR spectra to crystal structure.
  • The approach was experimentally confirmed on a specific molecular system.

Conclusions:

  • The developed framework enhances VCNC as a powerful tool for nanoscale analysis.
  • It enables precise measurement of low-energy molecular interactions and wave function delocalization.
  • This method is applicable to a broad range of molecular systems for studying disorder and domain formation.