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

Abstract

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 Xmore » = 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.« less

Authors:
 [1];  [1];  [2]; ORCiD logo [2];  [1];  [3];  [4];  [1]; ORCiD logo [2]
  1. UNIVERSITY PROGRAMS
  2. BATTELLE (PACIFIC NW LAB)
  3. Universiteit van die Vrystaat
  4. Czech Academy of Sciences
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1577973
Report Number(s):
PNNL-SA-148045
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 19
Country of Publication:
United States
Language:
English

Citation Formats

Li, Renzhong, Yuan, Qinqin, Yang, Zheng, Apra, Edoardo, Li, Zhipeng, Azov, Vladimir A., Kirakci, Kaplan, Warneke, Jonas, and Wang, Xue-Bin. Photoelectron spectroscopy of [Mo6X14]2- dianions (X = Cl - I). United States: N. p., 2019. Web. doi:10.1063/1.5130185.
Li, Renzhong, Yuan, Qinqin, Yang, Zheng, Apra, Edoardo, Li, Zhipeng, Azov, Vladimir A., Kirakci, Kaplan, Warneke, Jonas, & Wang, Xue-Bin. Photoelectron spectroscopy of [Mo6X14]2- dianions (X = Cl - I). United States. doi:10.1063/1.5130185.
Li, Renzhong, Yuan, Qinqin, Yang, Zheng, Apra, Edoardo, Li, Zhipeng, Azov, Vladimir A., Kirakci, Kaplan, Warneke, Jonas, and Wang, Xue-Bin. Thu . "Photoelectron spectroscopy of [Mo6X14]2- dianions (X = Cl - I)". United States. doi:10.1063/1.5130185.
@article{osti_1577973,
title = {Photoelectron spectroscopy of [Mo6X14]2- dianions (X = Cl - I)},
author = {Li, Renzhong and Yuan, Qinqin and Yang, Zheng and Apra, Edoardo and Li, Zhipeng and Azov, Vladimir A. and Kirakci, Kaplan and Warneke, Jonas and Wang, Xue-Bin},
abstractNote = {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.},
doi = {10.1063/1.5130185},
journal = {Journal of Chemical Physics},
number = 19,
volume = 151,
place = {United States},
year = {2019},
month = {11}
}

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