Photochemistry of Nitrophenol Molecules and Clusters: Intra- vs Intermolecular Hydrogen Bond Dynamics

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F16%3A43902482" target="_blank" >RIV/60461373:22340/16:43902482 - isvavai.cz</a>

Alternative codes found

RIV/61388955:_____/16:00460163

Result on the web

<a href="http://pubs.acs.org/doi/abs/10.1021/acs.jpca.6b04459" target="_blank" >http://pubs.acs.org/doi/abs/10.1021/acs.jpca.6b04459</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpca.6b04459" target="_blank" >10.1021/acs.jpca.6b04459</a>

Result language

angličtina

Original language name

Photochemistry of Nitrophenol Molecules and Clusters: Intra- vs Intermolecular Hydrogen Bond Dynamics

Original language description

We investigate both experimentally and theoretically the structure and photodynamics of nitrophenol molecules and clusters, addressing the question how the molecular photodynamics can be controlled by specific inter- and intramolecular interactions. Using quantum chemical calculations, we demonstrate the structural and energetic differences between clusters of 2-nitrophenol and 4-nitrophenol, using phenol as a reference system. The calculated structures are supported by mass spectrometry. The mass spectra of 2-nitrophenol clusters provide an evidence for a stacked structure compared to a strong O-H...O hydrogen bonding for 4-nitrophenol aggregates. We further investigate the photodynamics of nitrophenol molecules and clusters by means of velocity map imaging of the H-fragment generated upon 243 nm photodissociation. The experiments are complemented by ab initio calculations which demonstrate distinct photophysics of phenol, 2-nitrophenol, 4-nitrophenol. The measured H-fragment kinetic energy distributions (KEDs) from 2-nitrophenol molecules are compared to the KEDs from phenol. The comparison points to the intramolecular O-H...O hydrogen bond in 2-nitrophenol, stimulating fast internal conversion into the ground electronic state. This reaction channel is marked by exclusive appearance of slow statistical hydrogen fragments in 2-nitrophenol, which contrasts with fast hydrogen atoms observed for phenol. The photodissociation of 2-nitrophenol clusters yields a fraction of H-fragments with higher kinetic energies than the isolated molecules. These fragments originate from the caging effect in the clusters leading to multiphoton dissociation of molecules excited by the previous photons. We also propose a new ab initio based value for the O-H bond dissociation enthalpy in 2-nitrophenol (4.25 eV), which is in excellent agreement with the maximum measured H-fragment kinetic energy.

Czech name

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Czech description

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Type

J_x - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)

CEP classification

CF - Physical chemistry and theoretical chemistry

OECD FORD branch

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Project

<a href="/en/project/GA15-12386S" target="_blank" >GA15-12386S: Dynamics and (Photo)Chemistry of Pollutants at the Ice/Air and Water/Air Interfaces by Experiment and Theory</a><br>

Continuities

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

Publication year

2016

Confidentiality

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

Name of the periodical

Journal of Physical Chemistry A

ISSN

1089-5639

e-ISSN

—

Volume of the periodical

120

Issue of the periodical within the volume

24

Country of publishing house

US - UNITED STATES

Number of pages

8

Pages from-to

"4139?4146"

UT code for WoS article

000378663200007

EID of the result in the Scopus database

2-s2.0-84975824390