Non-ergodic fragmentation upon collision-induced activation of cysteine-water cluster cations

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F23%3A00569023" target="_blank" >RIV/61388955:_____/23:00569023 - isvavai.cz</a>

Výsledek na webu

<a href="https://hdl.handle.net/11104/0340307" target="_blank" >https://hdl.handle.net/11104/0340307</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d2cp04172c" target="_blank" >10.1039/d2cp04172c</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Non-ergodic fragmentation upon collision-induced activation of cysteine-water cluster cations

Popis výsledku v původním jazyce

Cysteine-water cluster cations Cys(H2O)(3,6)(+) and Cys(H2O)(3,6)H+ are assembled in He droplets and probed by tandem mass spectrometry with collision-induced activation. Benchmark experimental data for this biologically important system are complemented with theory to elucidate the details of the collision-induced activation process. Experimental energy thresholds for successive release of water are compared to water dissociation energies from DFT calculations showing that clusters do not only fragment exclusively by sequential emission of single water molecules but also by the release of small water clusters. Release of clustered water is observed also in the ADMP (atom centered density matrix propagation) molecular dynamics model of small Cys(H2O)(3)(+) and Cys(H2O)(3)H+ clusters. For large clusters Cys(H2O)(6)(+) and Cys(H2O)(6)H+ the less computationally demanding statistical Microcanonical Metropolis Monte-Carlo method (M3C) is used to model the experimental fragmentation patterns. We are able to detail the energy redistribution in clusters upon collision activation. In the present case, about two thirds of the collision energy redistribute via an ergodic process, while the remaining one third is transferred into a non-ergodic channel leading to ejection of a single water molecule from the cluster. In contrast to molecular fragmentation, which can be well described by statistical models, modelling of collision-induced activation of weakly bound clusters requires inclusion of non-ergodic processes.

Název v anglickém jazyce

Non-ergodic fragmentation upon collision-induced activation of cysteine-water cluster cations

Popis výsledku anglicky

Cysteine-water cluster cations Cys(H2O)(3,6)(+) and Cys(H2O)(3,6)H+ are assembled in He droplets and probed by tandem mass spectrometry with collision-induced activation. Benchmark experimental data for this biologically important system are complemented with theory to elucidate the details of the collision-induced activation process. Experimental energy thresholds for successive release of water are compared to water dissociation energies from DFT calculations showing that clusters do not only fragment exclusively by sequential emission of single water molecules but also by the release of small water clusters. Release of clustered water is observed also in the ADMP (atom centered density matrix propagation) molecular dynamics model of small Cys(H2O)(3)(+) and Cys(H2O)(3)H+ clusters. For large clusters Cys(H2O)(6)(+) and Cys(H2O)(6)H+ the less computationally demanding statistical Microcanonical Metropolis Monte-Carlo method (M3C) is used to model the experimental fragmentation patterns. We are able to detail the energy redistribution in clusters upon collision activation. In the present case, about two thirds of the collision energy redistribute via an ergodic process, while the remaining one third is transferred into a non-ergodic channel leading to ejection of a single water molecule from the cluster. In contrast to molecular fragmentation, which can be well described by statistical models, modelling of collision-induced activation of weakly bound clusters requires inclusion of non-ergodic processes.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GX21-26601X" target="_blank" >GX21-26601X: Zkoumání a transformace hmoty elektrony v kapalných mikrotryskách</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2023

Kód důvěrnosti údajů

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

Název periodika

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

1463-9084

Svazek periodika

25

Číslo periodika v rámci svazku

7

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

11

Strana od-do

5361-5371

Kód UT WoS článku

000915527500001

EID výsledku v databázi Scopus

2-s2.0-85148250181