Jove
Visualize
Contact Us

Related Concept Videos

IR Frequency Region: X–H Stretching01:24

IR Frequency Region: X–H Stretching

In IR spectroscopy, signals produced by the X−H bonds (such as C−H, O−H, or N−H) can be observed in the frequency range of  2700–4000 cm–1. The C−H stretching vibration forms sharp bands in the region 2850–3000 cm–1. The presence of the O−H stretching vibration leads to the forming of an absorption band in the frequency range 3650–3200 cm−1. At the same time, N−H stretching can be confirmed by absorption bands in the 3500–3100 cm−1 range. Even though both O−H and N−H bonds vibrate at a similar...
¹H NMR: Interpreting Distorted and Overlapping Signals01:02

¹H NMR: Interpreting Distorted and Overlapping Signals

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 slanted or...
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...
IR Frequency Region: Alkyne and Nitrile Stretching01:22

IR Frequency Region: Alkyne and Nitrile Stretching

Both alkyne (C≡C) and nitrile (C≡N) functional groups contain triple bonds and show stretching absorptions around the wavenumber range of 2100 to 2300 cm−1 in the diagnostic region of the IR spectra.
Comparing the stretching vibrational frequency of  C≡C triple bonds with that of double and single bonds, it is evident that C≡C triple bonds exhibit a higher stretching frequency than C=C double and C–C single bonds. Similarly, the C≡N triple bond exhibits higher stretching absorption than the C=N...
¹H NMR: Long-Range Coupling01:27

¹H NMR: Long-Range Coupling

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 π orbitals.
¹H NMR: Complex Splitting01:13

¹H NMR: Complex Splitting

A proton M that is coupled to a proton X results in doublet signals for M. However, NMR-active nuclei can be simultaneously coupled to more than one nonequivalent nucleus. When M is coupled to a second proton A, such as in styrene oxide, each peak in the doublet is split into another doublet.
Splitting diagrams or splitting tree diagrams are routinely used to depict such complex couplings. While drawing splitting diagrams, the splitting with the larger coupling constant is usually applied first.

You might also read

Related Articles

Articles linked to this work by shared authors, journal, and citation graph.

Sort by
Same author

Stability of Mono-Hydrated Ether Complexes in the Gas-Phase at Room Temperature.

The journal of physical chemistry. A·2026
Same author

Stealing from a distant neighbor: an unexpectedly fast long-span peroxy radical hydrogen-shift reaction in a long-chain diether.

Chemical science·2026
Same author

Simulated Photodissociation Dynamics of the N<sub>2</sub>O-H<sub>2</sub>O Complex and Its Atmospheric Relevance.

ACS omega·2026
Same author

Hydrogen Shift Reactions in Nonhydrocarbon Peroxy Radicals.

The journal of physical chemistry. A·2026
Same author

The Elusive Bound OH-Stretching First Overtone of Water Dimer.

The journal of physical chemistry. A·2026
Same author

Calculated Absorption Cross Sections and Photolysis Rates of Hydroperoxyaldehydes.

The journal of physical chemistry. A·2025
JoVE
x logofacebook logolinkedin logoyoutube logo
ABOUT JoVE
OverviewLeadershipBlogJoVE Help Center
AUTHORS
Publishing ProcessEditorial BoardScope & PoliciesPeer ReviewFAQSubmit
LIBRARIANS
TestimonialsSubscriptionsAccessResourcesLibrary Advisory BoardFAQ
RESEARCH
JoVE JournalMethods CollectionsJoVE Encyclopedia of ExperimentsArchive
EDUCATION
JoVE CoreJoVE BusinessJoVE Science EducationJoVE Lab ManualFaculty Resource CenterFaculty Site
Terms & Conditions of Use
Privacy Policy
Policies

Related Experiment Video

Updated: Jun 13, 2026

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
08:04

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids

Published on: May 27, 2020

XH-stretching overtone transitions calculated using explicitly correlated coupled cluster methods.

Joseph R Lane1, Henrik G Kjaergaard

  • 1Department of Chemistry, University of Waikato, Private Bag 3105, Hamilton 3240, New Zealand.

The Journal of Chemical Physics
|May 13, 2010
PubMed
Summary

We calculated molecular vibrations using advanced computational methods. Explicitly correlated coupled cluster theory with [CCSD(T)-F12] provides rapid basis set convergence but overestimates frequencies compared to experiments.

More Related Videos

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
12:11

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

Published on: April 8, 2020

Related Experiment Videos

Last Updated: Jun 13, 2026

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
08:04

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids

Published on: May 27, 2020

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
12:11

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

Published on: April 8, 2020

Area of Science:

  • Computational Chemistry
  • Molecular Spectroscopy
  • Quantum Chemistry

Background:

  • Accurate prediction of molecular vibrational frequencies is crucial for understanding chemical properties and reactions.
  • Traditional computational methods often face challenges with basis set convergence and accuracy.

Purpose of the Study:

  • To calculate XH-stretching fundamental and overtone transitions for small molecules.
  • To evaluate the performance of explicitly correlated coupled cluster theory [CCSD(T)-F12] against conventional methods.

Main Methods:

  • Utilized a local mode model for calculating vibrational transitions.
  • Employed explicitly correlated coupled cluster with single doubles and perturbative triples theory [CCSD(T)-F12] and VXZ-F12 basis sets.
  • Calculated potential energy curves and dipole moment functions.

Main Results:

  • Explicitly correlated [CCSD(T)-F12] methods show faster basis set convergence than conventional coupled cluster with single doubles and perturbative triples [CCSD(T)].
  • [CCSD(T)-F12] results with VTZ-F12 and VQZ-F12 basis sets closely match the [CCSD(T)] complete basis set limit.
  • Explicit correlation in [CCSD(T)-F12] reveals overestimation of vibrational frequencies inherent in the [CCSD(T)] method.

Conclusions:

  • Conventional [CCSD(T)] with augmented correlation-consistent basis sets (aug-cc-pVTZ or aug-cc-pVQZ) provides the best agreement with experimental XH-stretching frequencies.
  • Explicitly correlated methods highlight limitations of standard approximations in predicting vibrational spectra accurately.