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¹H NMR: Complex Splitting01:13

¹H NMR: Complex Splitting

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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...
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Theories of Dissolution: The Danckwerts' Model and Interfacial Barrier Model01:09

Theories of Dissolution: The Danckwerts' Model and Interfacial Barrier Model

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Various dissolution theories provide insight into the factors that influence the dissolution rate. Danckwerts' Model suggests that turbulence, rather than a stagnant layer, characterizes the dissolution medium at the solid-liquid interface. In this model, the agitated solvent contains macroscopic packets that move to the interface via eddy currents, facilitating the absorption and delivery of the drug to the bulk solution. The regular replenishment of solvent packets maintains the...
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Real Gases: Effects of Intermolecular Forces and Molecular Volume Deriving Van der Waals Equation04:01

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Thus far, the ideal gas law, PV = nRT, has been applied to a variety of different types of problems, ranging from reaction stoichiometry and empirical and molecular formula problems to determining the density and molar mass of a gas. However, the behavior of a gas is often non-ideal, meaning that the observed relationships between its pressure, volume, and temperature are not accurately described by the gas laws.
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Phase Transitions: Vaporization and Condensation02:39

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The physical form of a substance changes on changing its temperature. For example, raising the temperature of a liquid causes the liquid to vaporize (convert into vapor). The process is called vaporization—a surface phenomenon. Vaporization occurs when the thermal motion of the molecules overcome the intermolecular forces, and the molecules (at the surface) escape into the gaseous state. When a liquid vaporizes in a closed container, gas molecules cannot escape. As these gas phase molecules...
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¹H NMR Signal Multiplicity: Splitting Patterns01:13

¹H NMR Signal Multiplicity: Splitting Patterns

6.5K
When protons A and X are coupled, their nuclear spin energy levels are slightly modified. This is because the energy required to excite proton A to a spin state parallel to proton X is slightly different from the energy required for it to become anti-parallel to spin X. Consequently, there are two possible excitation frequencies for A (A1 and A2), depending on the spin state of X, and vice versa. The mutual nature of coupling implies that the difference between frequencies A1 and A2, indicated...
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Molecular Orbital Theory II03:51

Molecular Orbital Theory II

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Molecular Orbital Energy Diagrams
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Related Experiment Video

Updated: Jan 4, 2026

Probing the Structure and Dynamics of Interfacial Water with Scanning Tunneling Microscopy and Spectroscopy
10:28

Probing the Structure and Dynamics of Interfacial Water with Scanning Tunneling Microscopy and Spectroscopy

Published on: May 27, 2018

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Tunneling Splittings in Water Clusters from Path Integral Molecular Dynamics.

C L Vaillant1, D J Wales2, S C Althorpe2

  • 1Laboratory of Theoretical Physical Chemistry , Institut des Sciences et Ingénierie Chimiques, École Polytechnique Fédérale de Lausanne (EPFL) , CH-1015 Lausanne , Switzerland.

The Journal of Physical Chemistry Letters
|November 5, 2019
PubMed
Summary

Path integral molecular dynamics (PIMD) accurately calculates tunneling splittings in water clusters. This method validates the MB-Pol surface and PIMD accuracy for complex molecular systems.

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Last Updated: Jan 4, 2026

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Area of Science:

  • * Quantum chemistry
  • * Molecular dynamics
  • * Spectroscopy

Background:

  • * Tunneling splittings are crucial for understanding molecular dynamics in clusters.
  • * Accurate theoretical methods are needed to compute these splittings.

Purpose of the Study:

  • * To calculate tunneling splittings in small water clusters (dimer, trimer, hexamer).
  • * To validate a new path integral molecular dynamics (PIMD) method and the MB-Pol potential energy surface.

Main Methods:

  • * Application of a recently developed path integral molecular dynamics (PIMD) method.
  • * Focus on ground-rotational-state tunneling motions in water clusters.

Main Results:

  • * PIMD predictions show excellent agreement with benchmark quantum and experimental results.
  • * Calculations validate both the MB-Pol surface and the accuracy of PIMD.

Conclusions:

  • * PIMD is a reliable method for calculating tunneling splittings.
  • * The favorable scaling of PIMD enables studies of larger, nonrigid molecular systems.