Related Experiment Video
Updated: Apr 14, 2026
12:11
Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
Published on: April 8, 2020
8.8K
Solvent-mediated internal conversion in diphenoxyethane-(H₂O)n clusters, n = 2-4
Patrick S Walsh1, Evan G Buchanan1, Joseph R Gord1
1Department of Chemistry, Purdue University, 560 Oval Drive, West Lafayette, Indiana 47907-2084, USA.
The Journal of Chemical Physics
|April 24, 2015
Summary
Solvent interactions with 1,2-diphenoxyethane (DPOE) water clusters modulate excited state splitting. Water clusters reveal how solvent mediates electronic energy conversion between chromophores, offering insights into Kasha
Area of Science:
- * Physical Chemistry
- * Spectroscopy
- * Chemical Physics
Background:
- * 1,2-diphenoxyethane (DPOE) is a flexible bichromophore with closely spaced excited states.
- * Solvent interactions significantly influence excited state splitting and vibronic coupling in DPOE.
- * Previous studies established the ground state infrared spectroscopy of DPOE-(H2O)n clusters (n=2-4).
Purpose of the Study:
- * Investigate the vibronic and excited state infrared spectroscopies of DPOE-(H2O)n clusters.
- * Determine how water cluster asymmetry affects the S1/S2 excited state splitting.
- * Explore the role of water clusters in mediating excited state interactions and internal conversion.
Main Methods:
- * Excited state resonant ion-dip infrared spectroscopy.
- * Spectroscopic analysis of DPOE-(H2O)n clusters (n=2-4).
- * Measurement at the electronic origins of the first two excited states (S1 and S2).
Main Results:
- * The degree of water cluster asymmetry directly correlates with the S1/S2 splitting magnitude.
- * Water cluster OH stretch spectra provide insights into the nature of the excited states.
- * Evidence of S2 state interaction with nearby S1 vibronic levels mediated by water clusters.
Conclusions:
- * Water clusters act as a solvent medium, influencing excited-state dynamics in DPOE.
- * The study provides a state-to-state perspective on internal conversion processes.
- * Demonstrates the crucial role of solvent in mediating electronic energy transfer, offering a molecular view of Kasha's rule.
Related Concept Videos
01:10Hydrolysis of Chlorobenzene to Phenol: Dow Process
4.4K
Simple aryl halides do not react with nucleophiles under normal conditions. However, the reaction can proceed under drastic conditions involving high temperatures and high pressure to give the substituted products. For example, chlorobenzene is converted to phenol using aqueous sodium hydroxide at 350 °C under high pressure by the Dow process. The reaction follows an elimination-addition mechanism involving a benzyne intermediate. Here, the chloride ion is...
4.4K
02:41Formation of Halohydrin from Alkenes
15.2K
An alkene, such as propene, reacts with bromine in the presence of water to yield a halohydrin. Halohydrins contain a halogen and a hydroxyl group attached to adjacent carbons. When the halogen is bromine, it is called a bromohydrin, while a chlorohydrin has chlorine as the halogen.
15.2K
![[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2Ffiles%2Fmedia%2Fscience-education%2Fscience-education-thumbs%2F12417.jpg&w=3840&q=75)
01:16[4+2] Cycloaddition of Conjugated Dienes: Diels–Alder Reaction
14.4K
The Diels–Alder reaction is an example of a thermal pericyclic reaction between a conjugated diene and an alkene or alkyne, commonly referred to as a dienophile. The reaction involves a concerted movement of six π electrons, four from the diene and two from the dienophile, forming an unsaturated six-membered ring. As a result, these reactions are classified as [4+2] cycloadditions.
14.4K
02:46Halogenation of Alkenes
21.4K
Halogenation is the addition of chlorine or bromine across the double bond in an alkene to yield a vicinal dihalide. The reaction occurs in the presence of inert and non-nucleophilic solvents, such as methylene chloride, chloroform, or carbon tetrachloride.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
Consider the bromination of cyclopentene. Molecular bromine is polarized in the proximity of the π electrons of cyclopentene. An electrophilic bromine atom adds across the double bond, forming a cyclic bromonium ion intermediate.
21.4K
01:28Stability of Conjugated Dienes
4.7K
Introduction
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
4.7K
02:30Stability of Substituted Cyclohexanes
17.6K
This lesson discusses the stability of substituted cyclohexanes with a focus on energies of various conformers and the effect of 1,3-diaxial interactions.
The two chair conformations of cyclohexanes undergo rapid interconversion at room temperature. Both forms have identical energies and stabilities, each comprising equal amounts of the equilibrium mixture. Replacing a hydrogen atom with a functional group makes the two conformations energetically non-equivalent.
For example, in...
The two chair conformations of cyclohexanes undergo rapid interconversion at room temperature. Both forms have identical energies and stabilities, each comprising equal amounts of the equilibrium mixture. Replacing a hydrogen atom with a functional group makes the two conformations energetically non-equivalent.
For example, in...
17.6K