UV-Light-Induced Vibrational Coherences: The Key to Understand Kasha Rule Violation in trans-Azobenzene

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11320%2F18%3A10391467" target="_blank" >RIV/00216208:11320/18:10391467 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.1021/acs.jpclett.8b00152" target="_blank" >https://doi.org/10.1021/acs.jpclett.8b00152</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpclett.8b00152" target="_blank" >10.1021/acs.jpclett.8b00152</a>

Jazyk výsledku

angličtina

Název v původním jazyce

UV-Light-Induced Vibrational Coherences: The Key to Understand Kasha Rule Violation in trans-Azobenzene

Popis výsledku v původním jazyce

We combine sub-20 fs transient absorption spectroscopy with state-of-the-art computations to study the ultrafast photoinduced dynamics of trans-azobenzene (AB). We are able to resolve the lifetime of the pi pi* state, whose decay within ca. 50 fs is correlated to the buildup of the n pi* population and to the emergence of coherences in the dynamics, to date unobserved. Nonlinear spectroscopy simulations call for the CNN in-plane bendings as the active modes in the subps photoinduced coherent dynamics out of the pi pi* state. Radiative to kinetic energy transfer into these modes drives the system to a high-energy planar n pi*/ground state conical intersection, inaccessible upon direct excitation of the lie state, that triggers an ultrafast (0.45 ps) nonproductive decay of the n pi* state and is thus responsible for the observed Kasha rule violation in UV excited trans-AB. On the other hand, cis-AB is built only after intramolecular vibrational energy redistribution and population of the NN torsional mode.

Název v anglickém jazyce

UV-Light-Induced Vibrational Coherences: The Key to Understand Kasha Rule Violation in trans-Azobenzene

Popis výsledku anglicky

We combine sub-20 fs transient absorption spectroscopy with state-of-the-art computations to study the ultrafast photoinduced dynamics of trans-azobenzene (AB). We are able to resolve the lifetime of the pi pi* state, whose decay within ca. 50 fs is correlated to the buildup of the n pi* population and to the emergence of coherences in the dynamics, to date unobserved. Nonlinear spectroscopy simulations call for the CNN in-plane bendings as the active modes in the subps photoinduced coherent dynamics out of the pi pi* state. Radiative to kinetic energy transfer into these modes drives the system to a high-energy planar n pi*/ground state conical intersection, inaccessible upon direct excitation of the lie state, that triggers an ultrafast (0.45 ps) nonproductive decay of the n pi* state and is thus responsible for the observed Kasha rule violation in UV excited trans-AB. On the other hand, cis-AB is built only after intramolecular vibrational energy redistribution and population of the NN torsional mode.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10300 - Physical sciences

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2018

Kód důvěrnosti údajů

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

Název periodika

Journal of Physical Chemistry Letters

ISSN

1948-7185

e-ISSN

—

Svazek periodika

9

Číslo periodika v rámci svazku

7

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

8

Strana od-do

1534-1541

Kód UT WoS článku

000429626900012

EID výsledku v databázi Scopus

2-s2.0-85044990472