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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.
According to Hooke's law, the vibrational frequency is directly proportional to the...
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...
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 Frequency Region: Alkene and Carbonyl Stretching01:29

IR Frequency Region: Alkene and Carbonyl Stretching

Double bonds in alkenes and carbonyl compounds exhibit stretching frequencies in the diagnostic region of the IR spectrum. In addition, alkenes exhibit vinylic C–H stretching and C–H out-of-plane bending absorptions that are useful for identifying substitution patterns.
Stretching frequencies are affected by several factors, such as resonance, inductive effects, ring strain, dipole moment, and hydrogen bonding. Consequently, the stretching frequency of the carbonyl double bond varies in...
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...
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...

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Updated: Jul 17, 2026

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

Efficient correlation-corrected vibrational self-consistent field computation of OH-stretch frequencies using a

David M Benoit1

  • 1Nachwuchsgruppe Theorie-SFB 569, Albert-Einstein-Allee 11, University of Ulm, D-89081 Ulm, Germany. david.benoit@uni-ulm.de

The Journal of Chemical Physics
|January 4, 2007
PubMed
Summary

A new computational method enables accurate and fast direct correlation-corrected vibrational self-consistent field (CC-VSCF) calculations for large molecules. This approach significantly reduces computational cost while maintaining high accuracy for predicting vibrational frequencies.

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Area of Science:

  • Computational Chemistry
  • Quantum Chemistry
  • Molecular Spectroscopy

Background:

  • Accurate prediction of vibrational frequencies is crucial for understanding molecular properties and reactions.
  • Traditional methods like direct correlation-corrected vibrational self-consistent field (CC-VSCF) are computationally expensive for large molecular systems.
  • Efficient computational schemes are needed to study vibrational modes in complex molecules.

Purpose of the Study:

  • To develop a novel computational scheme for fast and accurate direct CC-VSCF calculations.
  • To enable the prediction of specific vibrational modes in large molecular systems.
  • To reduce the computational scaling of CC-VSCF methods.

Main Methods:

  • Systematic selection of vibrational mode-mode coupling terms for sparse potential energy surface construction.
  • Screening procedure for correlation-correction contributions to further reduce computational scaling.
  • Application to compute OH-stretch frequencies in five aliphatic alcohols using various basis sets.

Main Results:

  • The proposed method achieves a computational scaling two orders of magnitude lower than standard CC-VSCF.
  • The accuracy of the calculated OH-stretch frequencies is comparable to standard CC-VSCF methods.
  • Investigated the impact of pseudopotential and all-electron basis sets on potential energy surfaces and frequencies.

Conclusions:

  • The new computational scheme offers a significant speed-up for direct CC-VSCF calculations.
  • The method provides an accurate and efficient way to predict vibrational frequencies in large molecules.
  • This approach facilitates the study of vibrational properties in complex chemical systems.