Anharmonic vibrational effects in linear and two-dimensional electronic spectra

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11320%2F17%3A10370356" target="_blank" >RIV/00216208:11320/17:10370356 - isvavai.cz</a>

Result on the web

<a href="http://dx.doi.org/10.1039/c7cp05189a" target="_blank" >http://dx.doi.org/10.1039/c7cp05189a</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/c7cp05189a" target="_blank" >10.1039/c7cp05189a</a>

Result language

angličtina

Original language name

Anharmonic vibrational effects in linear and two-dimensional electronic spectra

Original language description

For the description of vibrational effects in electronic spectra, harmonic vibrations are a convenient and widespread model. However, spectra of larger organic molecules in solution usually exhibit signs of vibrational anharmonicity, as revealed by deviation from the mirror image symmetry between linear absorption and emission spectra of the harmonic case. For perylene and terylene, two molecules with rigid Pi-electron systems and strong vibrational-electronic coupling, we employ a simple but effective theoretical model, which introduces cubic anharmonicity in the potentials of electronic surfaces. Vibrational anharmonicity is then readily quantified based on the experimentally measured peak ratio of the first vibronic progression peaks in linear absorption and emission. This method is straightforward but not applicable if emission from the initially excited state is short lived. For such a case, we employ two-dimensional electronic spectroscopy in the visible as a comprehensive time-resolved technique for the experimental determination of the vibrational anharmonicity of pinacyanol iodide, a solvated dye molecule exhibiting ultrafast excited state isomerization. We show that the ratio between certain cross peak amplitudes in two-dimensional electronic spectra is a direct measure of vibrational anharmonicity.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

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OECD FORD branch

10300 - Physical sciences

Project

Result was created during the realization of more than one project. More information in the Projects tab.

Continuities

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

Publication year

2017

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

—

Volume of the periodical

19

Issue of the periodical within the volume

36

Country of publishing house

GB - UNITED KINGDOM

Number of pages

9

Pages from-to

24752-24760

UT code for WoS article

000411606200038

EID of the result in the Scopus database

2-s2.0-85029837039