Jove
Visualize
Contact Us
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 Concept Videos

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...
Reaction Mechanisms: The Steady-State Approximation01:26

Reaction Mechanisms: The Steady-State Approximation

The steady-state approximation, also referred to as the quasi-steady-state approximation to differentiate it from a true steady state, is a widely used method for simplifying calculations in complex reaction mechanisms. This approach is particularly useful when dealing with multi-step reactions that involve reverse reactions or several steps, which can significantly increase mathematical complexity and make the reactions nearly unsolvable analytically.The steady-state approximation operates on...
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...
The Van der Waals Equation01:26

The Van der Waals Equation

The ideal gas law is based on two simplifying assumptions: first, that there are no intermolecular attractions between gas molecules, and second, that the volume occupied by the molecules themselves is negligible compared with the volume of the container. However, these assumptions don't hold up under all conditions - specifically, at high pressures and low temperatures, as gas tends to deviate from ideal gas behavior.The van der Waals equation is an enhanced version of the ideal gas law,...
Van der Waals Equation01:10

Van der Waals Equation

The ideal gas law is an approximation that works well at high temperatures and low pressures. The van der Waals equation of state (named after the Dutch physicist Johannes van der Waals, 1837−1923) improves it by considering two factors.
First, the attractive forces between molecules, which are stronger at higher densities and reduce the pressure, are considered by adding to the pressure a term equal to the square of the molar density multiplied by a positive coefficient a. Second, the volume...
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,...

You might also read

Related Articles

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

Sort by
Same author

Voltage fluctuations and probe frequency jitter in electric force microscopy of a conductor.

The Journal of chemical physics·2023
Same author

Noncontact Friction in Electric Force Microscopy over a Conductor with Nonlocal Dielectric Response.

The journal of physical chemistry. A·2022
Same author

2D electronic-vibrational spectroscopy with classical trajectories.

The Journal of chemical physics·2022
Same author

Two-dimensional vibronic spectroscopy with semiclassical thermofield dynamics.

The Journal of chemical physics·2022
Same author

Calculating Multidimensional Optical Spectra from Classical Trajectories.

Annual review of physical chemistry·2022
Same author

Two-dimensional vibrational-electronic spectra with semiclassical mechanics.

The Journal of chemical physics·2021

Related Experiment Video

Updated: May 12, 2026

Vibrational Spectra of a N719-Chromophore/Titania Interface from Empirical-Potential Molecular-Dynamics Simulation, Solvated by a Room Temperature Ionic Liquid
08:54

Vibrational Spectra of a N719-Chromophore/Titania Interface from Empirical-Potential Molecular-Dynamics Simulation, Solvated by a Room Temperature Ionic Liquid

Published on: January 25, 2020

An optimized semiclassical approximation for vibrational response functions.

Mallory Gerace1, Roger F Loring

  • 1Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, New York 14853, USA.

The Journal of Chemical Physics
|April 6, 2013
PubMed
Summary
This summary is machine-generated.

This study introduces an optimized mean-trajectory (OMT) approximation for calculating vibrational response functions. OMT accurately reproduces quantum dynamics for all time periods in multidimensional infrared spectroscopy.

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

ARL Spectral Fitting as an Application to Augment Spectral Data via Franck-Condon Lineshape Analysis and Color Analysis
07:11

ARL Spectral Fitting as an Application to Augment Spectral Data via Franck-Condon Lineshape Analysis and Color Analysis

Published on: August 19, 2021

Related Experiment Videos

Last Updated: May 12, 2026

Vibrational Spectra of a N719-Chromophore/Titania Interface from Empirical-Potential Molecular-Dynamics Simulation, Solvated by a Room Temperature Ionic Liquid
08:54

Vibrational Spectra of a N719-Chromophore/Titania Interface from Empirical-Potential Molecular-Dynamics Simulation, Solvated by a Room Temperature Ionic Liquid

Published on: January 25, 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

ARL Spectral Fitting as an Application to Augment Spectral Data via Franck-Condon Lineshape Analysis and Color Analysis
07:11

ARL Spectral Fitting as an Application to Augment Spectral Data via Franck-Condon Lineshape Analysis and Color Analysis

Published on: August 19, 2021

Area of Science:

  • Quantum mechanics
  • Spectroscopy
  • Chemical physics

Background:

  • Calculating vibrational response functions is crucial for multidimensional infrared spectroscopy.
  • Fully quantum calculations are impractical, while classical methods are inaccurate.
  • Semiclassical approximations bridge this gap by using classical information for quantum effects.

Purpose of the Study:

  • To develop an improved semiclassical method for calculating vibrational response functions.
  • To address the limitations of the existing mean-trajectory (MT) approximation, particularly for the waiting-time period.
  • To enhance the accuracy of semiclassical methods in multidimensional infrared spectroscopy.

Main Methods:

  • Developed an optimized mean-trajectory (OMT) approximation.
  • Elucidated the connection between the MT approximation and double-sided Feynman diagrams (2FD).
  • Derived OMT systematically based on the relationship between 2FD and semiclassical paths.

Main Results:

  • The optimized mean-trajectory (OMT) approximation accurately reproduces quantum dynamics for all three propagation times (t1, t2, t3) of the third-order vibrational response function.
  • OMT overcomes the qualitative inaccuracies of the previous MT approximation for the waiting-time (t2) evolution.
  • The method effectively uses classical mechanical inputs to capture complex quantum vibrational dynamics.

Conclusions:

  • The optimized mean-trajectory (OMT) approximation provides a quantitatively accurate and computationally feasible method for multidimensional infrared spectroscopy.
  • OMT represents a significant advancement in semiclassical methods for vibrational dynamics.
  • This work enables more reliable theoretical predictions of spectroscopic observables.