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

Li, Renzhong; Yuan, Qinqin; Yang, Zheng; Apra, Edoardo; Li, Zhipeng; Azov, Vladimir A.; Kirakci, Kaplan; Warneke, Jonas; Wang, Xue-Bin

doi:10.1063/1.5130185

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

Journal Article · Thu Nov 21 00:00:00 EST 2019 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.5130185· OSTI ID:1577973

Li, Renzhong ^[1]; Yuan, Qinqin ^[1]; Yang, Zheng ^[2];

^[2]; Li, Zhipeng ^[1]; Azov, Vladimir A. ^[3]; Kirakci, Kaplan ^[4]; Warneke, Jonas ^[1];

^[2]

UNIVERSITY PROGRAMS
BATTELLE (PACIFIC NW LAB)
Universiteit van die Vrystaat
Czech Academy of Sciences

Photoelectron spectroscopy (PES) 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 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 experimental study. The measured adiabatic and vertical detachment energies (ADE/VDE) for X=Cl-I were well reproduced by DFT calculations (accuracy ~ 0.1eV). Corresponding 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, 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 modelling confirms the experimental RCB values and predicts that the most favorable electron detaching pathway should lie via the face-bridging halide ligands.

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Research Organization:: Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1577973

Report Number(s):: PNNL-SA-148045

Journal Information:: Journal of Chemical Physics, Vol. 151, Issue 19

Country of Publication:: United States

Language:: English

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