Femtosecond polarization resolved spectroscopy: A tool for determination of the three-dimensional orientation of electronic transition dipole moments and identification of configurational isomers

Moritz Theisen, Martin Linke, Max Kerbs, Henk Fidder, Mohamed Madjet, Angelica Zacarias, Karsten Heyne

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

A method is presented that combines femtosecond polarization resolved UV/visible pump-IR probe spectroscopy and density functional theory calculations in determining the three-dimensional orientation of an electronic transition dipole moment (tdm) within the molecular structure. The method is demonstrated on the approximately planar molecule coumarin 314 (C314) dissolved in acetonitrile, which can exist in two ground state configurations: the E - and the Z -isomer. Based on an exhaustive search analysis on polarization resolved measurement data for four different vibrational modes, it is concluded that C314 in acetonitrile is the E -isomer. The electronic tdm vector for the electronic S0 → S1 transition is determined and the analysis shows that performing the procedure for four vibrational modes instead of the minimally required three reduces the 1σ probability area from 2.34% to 2.24% of the solution space. Moreover, the fastest rotational correlation time τc for the C314 E -isomer is determined to be 26±2 ps.

Original languageEnglish
Article number124511
JournalJournal of Chemical Physics
Volume131
Issue number12
DOIs
Publication statusPublished - 8 Oct 2009
Externally publishedYes

Fingerprint

Dipole moment
Isomers
Spectrum Analysis
dipole moments
isomers
Spectroscopy
Polarization
acetonitrile
vibration mode
polarization
electronics
spectroscopy
Molecular Structure
Ground state
Molecular structure
Density functional theory
molecular structure
Pumps
pumps
density functional theory

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry
  • Medicine(all)

Cite this

Femtosecond polarization resolved spectroscopy : A tool for determination of the three-dimensional orientation of electronic transition dipole moments and identification of configurational isomers. / Theisen, Moritz; Linke, Martin; Kerbs, Max; Fidder, Henk; Madjet, Mohamed; Zacarias, Angelica; Heyne, Karsten.

In: Journal of Chemical Physics, Vol. 131, No. 12, 124511, 08.10.2009.

Research output: Contribution to journalArticle

@article{f5e57ac374874a66a7d4e81c2a50a3cc,
title = "Femtosecond polarization resolved spectroscopy: A tool for determination of the three-dimensional orientation of electronic transition dipole moments and identification of configurational isomers",
abstract = "A method is presented that combines femtosecond polarization resolved UV/visible pump-IR probe spectroscopy and density functional theory calculations in determining the three-dimensional orientation of an electronic transition dipole moment (tdm) within the molecular structure. The method is demonstrated on the approximately planar molecule coumarin 314 (C314) dissolved in acetonitrile, which can exist in two ground state configurations: the E - and the Z -isomer. Based on an exhaustive search analysis on polarization resolved measurement data for four different vibrational modes, it is concluded that C314 in acetonitrile is the E -isomer. The electronic tdm vector for the electronic S0 → S1 transition is determined and the analysis shows that performing the procedure for four vibrational modes instead of the minimally required three reduces the 1σ probability area from 2.34{\%} to 2.24{\%} of the solution space. Moreover, the fastest rotational correlation time τc for the C314 E -isomer is determined to be 26±2 ps.",
author = "Moritz Theisen and Martin Linke and Max Kerbs and Henk Fidder and Mohamed Madjet and Angelica Zacarias and Karsten Heyne",
year = "2009",
month = "10",
day = "8",
doi = "10.1063/1.3236804",
language = "English",
volume = "131",
journal = "Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics Publising LLC",
number = "12",

}

TY - JOUR

T1 - Femtosecond polarization resolved spectroscopy

T2 - A tool for determination of the three-dimensional orientation of electronic transition dipole moments and identification of configurational isomers

AU - Theisen, Moritz

AU - Linke, Martin

AU - Kerbs, Max

AU - Fidder, Henk

AU - Madjet, Mohamed

AU - Zacarias, Angelica

AU - Heyne, Karsten

PY - 2009/10/8

Y1 - 2009/10/8

N2 - A method is presented that combines femtosecond polarization resolved UV/visible pump-IR probe spectroscopy and density functional theory calculations in determining the three-dimensional orientation of an electronic transition dipole moment (tdm) within the molecular structure. The method is demonstrated on the approximately planar molecule coumarin 314 (C314) dissolved in acetonitrile, which can exist in two ground state configurations: the E - and the Z -isomer. Based on an exhaustive search analysis on polarization resolved measurement data for four different vibrational modes, it is concluded that C314 in acetonitrile is the E -isomer. The electronic tdm vector for the electronic S0 → S1 transition is determined and the analysis shows that performing the procedure for four vibrational modes instead of the minimally required three reduces the 1σ probability area from 2.34% to 2.24% of the solution space. Moreover, the fastest rotational correlation time τc for the C314 E -isomer is determined to be 26±2 ps.

AB - A method is presented that combines femtosecond polarization resolved UV/visible pump-IR probe spectroscopy and density functional theory calculations in determining the three-dimensional orientation of an electronic transition dipole moment (tdm) within the molecular structure. The method is demonstrated on the approximately planar molecule coumarin 314 (C314) dissolved in acetonitrile, which can exist in two ground state configurations: the E - and the Z -isomer. Based on an exhaustive search analysis on polarization resolved measurement data for four different vibrational modes, it is concluded that C314 in acetonitrile is the E -isomer. The electronic tdm vector for the electronic S0 → S1 transition is determined and the analysis shows that performing the procedure for four vibrational modes instead of the minimally required three reduces the 1σ probability area from 2.34% to 2.24% of the solution space. Moreover, the fastest rotational correlation time τc for the C314 E -isomer is determined to be 26±2 ps.

UR - http://www.scopus.com/inward/record.url?scp=70349617803&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=70349617803&partnerID=8YFLogxK

U2 - 10.1063/1.3236804

DO - 10.1063/1.3236804

M3 - Article

C2 - 19791898

AN - SCOPUS:70349617803

VL - 131

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 12

M1 - 124511

ER -