Photoelectron spectroscopy of [Mo6X14](2-) dianions (X = Cl-I)

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388980%3A_____%2F19%3A00517353" target="_blank" >RIV/61388980:_____/19:00517353 - isvavai.cz</a>

Výsledek na webu

<a href="http://hdl.handle.net/11104/0302671" target="_blank" >http://hdl.handle.net/11104/0302671</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1063/1.5130185" target="_blank" >10.1063/1.5130185</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Photoelectron spectroscopy of [Mo6X14](2-) dianions (X = Cl-I)

Popis výsledku v původním jazyce

Photoelectron spectroscopy and theoretical investigations have been performed to systematically probe the intrinsic electronic properties of [Mo6X14]2- (X = halogen). All three PE spectra of gaseous [Mo6X14]2- (X = Cl, Br, I) dianions, which were generated by electrospray ionization, exhibit multiple resolved peaks in the recorded binding energy range. Theoretical investigations on the orbital structure and charge distribution were performed to support interpretation of the observed spectra and were further extended onto [Mo6F14]2-, a dianion that was not available for the experimental study. The measured adiabatic (ADE) and vertical detachment energies (VDE) for X = Cl-I were well reproduced by density functional theory calculations (accuracy ∼0.1 eV). Corresponding ADE/VDE values for the dianions were found to be 1.48/2.13 (calc.) and 2.30/2.65, 2.30/2.62, and 2.20/2.42 eV (all expt.) for X = F, Cl, Br, and I, respectively, showing an interesting buckled trend of electron binding energy (EBE) along the halogen series, i.e., EBE (F) ≪ EBE (Cl) ∼ EBE (Br) > EBE (I). Molecular orbital analyses indicate different mixing of metal and halogen atomic orbitals, which is strongly dependent on the nature of X, and suggest that the most loosely bound electrons are detached mainly from the metal core for X = F and Cl, but from halide ligands for X = Br and I. The repulsive Coulomb barrier (RCB), estimated from the photon energy dependent spectra, decreases with increasing halogen size, from 1.8 eV for X = Cl to 1.6 eV for X = I. Electrostatic potential modeling confirms the experimental RCB values and predicts that the most favorable electron detaching pathway should lie via the face-bridging halide ligands.

Název v anglickém jazyce

Photoelectron spectroscopy of [Mo6X14](2-) dianions (X = Cl-I)

Popis výsledku anglicky

Photoelectron spectroscopy and theoretical investigations have been performed to systematically probe the intrinsic electronic properties of [Mo6X14]2- (X = halogen). All three PE spectra of gaseous [Mo6X14]2- (X = Cl, Br, I) dianions, which were generated by electrospray ionization, exhibit multiple resolved peaks in the recorded binding energy range. Theoretical investigations on the orbital structure and charge distribution were performed to support interpretation of the observed spectra and were further extended onto [Mo6F14]2-, a dianion that was not available for the experimental study. The measured adiabatic (ADE) and vertical detachment energies (VDE) for X = Cl-I were well reproduced by density functional theory calculations (accuracy ∼0.1 eV). Corresponding ADE/VDE values for the dianions were found to be 1.48/2.13 (calc.) and 2.30/2.65, 2.30/2.62, and 2.20/2.42 eV (all expt.) for X = F, Cl, Br, and I, respectively, showing an interesting buckled trend of electron binding energy (EBE) along the halogen series, i.e., EBE (F) ≪ EBE (Cl) ∼ EBE (Br) > EBE (I). Molecular orbital analyses indicate different mixing of metal and halogen atomic orbitals, which is strongly dependent on the nature of X, and suggest that the most loosely bound electrons are detached mainly from the metal core for X = F and Cl, but from halide ligands for X = Br and I. The repulsive Coulomb barrier (RCB), estimated from the photon energy dependent spectra, decreases with increasing halogen size, from 1.8 eV for X = Cl to 1.6 eV for X = I. Electrostatic potential modeling confirms the experimental RCB values and predicts that the most favorable electron detaching pathway should lie via the face-bridging halide ligands.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10402 - Inorganic and nuclear chemistry

Projekt

<a href="/cs/project/GA18-05076S" target="_blank" >GA18-05076S: Biomateriály obsahující oktaedrické molybdenové klastry jako radiosensitizátory singletového kyslíku</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2019

Kód důvěrnosti údajů

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

Název periodika

Journal of Chemical Physics

ISSN

0021-9606

e-ISSN

—

Svazek periodika

151

Číslo periodika v rámci svazku

19

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

7

Strana od-do

194310

Kód UT WoS článku

000504060200028

EID výsledku v databázi Scopus

2-s2.0-85075481701