Nonadiabatic dynamics of floppy hydrogen bonded complexes: the case of the ionized ammonia dimer

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F16%3A43902483" target="_blank" >RIV/60461373:22340/16:43902483 - isvavai.cz</a>

Result on the web

<a href="http://pubs.rsc.org/en/content/articlelanding/2016/cp/c6cp02714h#!divAbstract" target="_blank" >http://pubs.rsc.org/en/content/articlelanding/2016/cp/c6cp02714h#!divAbstract</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/C6CP02714H" target="_blank" >10.1039/C6CP02714H</a>

Result language

angličtina

Original language name

Nonadiabatic dynamics of floppy hydrogen bonded complexes: the case of the ionized ammonia dimer

Original language description

In the case of the ammonia dimer, we address the following questions: how ultrafast ionization dynamics is controlled by hydrogen bonding and whether we can control the products via selective ionization of a specific electron. We use quantum chemical calculations and ab initio non-adiabatic molecular dynamics simulations to model the femtosecond dynamics of the ammonia dimer upon ionization. The role of nuclear quantum effects and thermal fluctuations in predicting the structure of the dimer is emphasized; it is shown that the minimum energy and vibrationally averaged structures are rather different. The ground state structure subsequently controls the ionization dynamics. We describe reaction pathways, electronic population transfers and reaction yields with respect to ionization from different molecular orbitals. The simulations showed that the ionized ammonia dimer is highly unstable and its decay rate is primarily driven by the position of the electron hole. In the case of ground state ionization (i.e. the HOMO electron is ionized), the decay is likely to be preceded by a proton transfer (PT) channel yielding NH4+ and NH2. fragments. The PT is less intense and slower compared with the ionized water dimer. After ionizing deeper lying electrons, mainly NH3+. and NH3 fragments are formed. Overall, our results show that the ionization dynamics of the ammonia and water dimers differ due to the nature of the hydrogen bond in these systems.

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

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

2016

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

18

Issue of the periodical within the volume

červen 2016

Country of publishing house

GB - UNITED KINGDOM

Number of pages

11

Pages from-to

20422-20432

UT code for WoS article

000381428600046

EID of the result in the Scopus database

2-s2.0-84979943962