PMID- 34972374
OWN - NLM
STAT- PubMed-not-MEDLINE
DCOM- 20220103
LR  - 20220103
IS  - 1089-7690 (Electronic)
IS  - 0021-9606 (Linking)
VI  - 155
IP  - 24
DP  - 2021 Dec 28
TI  - Cryo spectroscopy of N(2) on cationic iron clusters.
PG  - 244305
LID - 10.1063/5.0064966 [doi]
AB  - Infrared photodissociation (IR-PD) spectra of iron cluster dinitrogen adsorbate 
      complexes [Fe(n)(N(2))(m)](+) for n = 8-20 reveal slightly redshifted IR active 
      bands in the region of 2200-2340 cm(-1). These bands mostly relate to stretching 
      vibrations of end-on coordinated N(2) chromophores, a mu(1,end) end-on binding 
      motif. Density Functional Theory (DFT) modeling and detailed analysis of n = 13 
      complexes are consistent with an icosahedral Fe(13) (+) core structure. The first 
      adsorbate shell closure at (n,m) = (13,12)-as recognized by the accompanying 
      paper on the kinetics of N(2) uptake by cationic iron clusters-comes with 
      extensive IR-PD band broadening resulting from enhanced couplings among adjacent 
      N(2) adsorbates. DFT modeling predicts spin quenching by N(2) adsorption as 
      evidenced by the shift of the computed spin minima among possible spin states 
      (spin valleys). The IR-PD spectrum of (17,1) surprisingly reveals an absence of 
      any structure but efficient non-resonant fragmentation, which might indicate some 
      weakly bound (roaming) N(2) adsorbate. The multiple and broad bands of (17,m) for 
      all other cases than (17,1) and (17,7) indicate a high degree of variation in 
      N(2) binding motifs and couplings. In contrast, the (17,7) spectrum of six sharp 
      bands suggests pairwise equivalent N(2) adsorbates. The IR-PD spectra of (18,m) 
      reveal additional features in the 2120-2200 cm(-1) region, which we associate 
      with a mu(1,side) side-on motif. Some additional features in the (18,m) spectra at 
      high N(2) loads indicate a mu(1,tilt) tilted end-on adsorption motif.
FAU - Strassner, Annika
AU  - Strassner A
AUID- ORCID: 0000000200718421
AD  - Fachbereich Chemie and Forschungszentrum OPTIMAS, Technische Universitat 
      Kaiserslautern, 67663 Kaiserslautern, Germany.
FAU - Wiehn, Christopher
AU  - Wiehn C
AD  - Fachbereich Chemie and Forschungszentrum OPTIMAS, Technische Universitat 
      Kaiserslautern, 67663 Kaiserslautern, Germany.
FAU - Klein, Matthias P
AU  - Klein MP
AUID- ORCID: 0000000174323054
AD  - Fachbereich Chemie and Forschungszentrum OPTIMAS, Technische Universitat 
      Kaiserslautern, 67663 Kaiserslautern, Germany.
FAU - Fries, Daniela V
AU  - Fries DV
AUID- ORCID: 0000000305237077
AD  - Fachbereich Chemie and Forschungszentrum OPTIMAS, Technische Universitat 
      Kaiserslautern, 67663 Kaiserslautern, Germany.
FAU - Dillinger, Sebastian
AU  - Dillinger S
AD  - Fachbereich Chemie and Forschungszentrum OPTIMAS, Technische Universitat 
      Kaiserslautern, 67663 Kaiserslautern, Germany.
FAU - Mohrbach, Jennifer
AU  - Mohrbach J
AD  - Fachbereich Chemie and Forschungszentrum OPTIMAS, Technische Universitat 
      Kaiserslautern, 67663 Kaiserslautern, Germany.
FAU - Prosenc, Marc H
AU  - Prosenc MH
AUID- ORCID: 0000000325190114
AD  - Fachbereich Chemie and Forschungszentrum OPTIMAS, Technische Universitat 
      Kaiserslautern, 67663 Kaiserslautern, Germany.
FAU - Armentrout, P B
AU  - Armentrout PB
AUID- ORCID: 0000000329536039
AD  - Department of Chemistry, University of Utah, Salt Lake City, Utah 84112, USA.
FAU - Niedner-Schatteburg, Gereon
AU  - Niedner-Schatteburg G
AUID- ORCID: 0000000172406673
AD  - Fachbereich Chemie and Forschungszentrum OPTIMAS, Technische Universitat 
      Kaiserslautern, 67663 Kaiserslautern, Germany.
LA  - eng
PT  - Journal Article
PL  - United States
TA  - J Chem Phys
JT  - The Journal of chemical physics
JID - 0375360
SB  - IM
EDAT- 2022/01/02 06:00
MHDA- 2022/01/02 06:01
CRDT- 2022/01/01 05:09
PHST- 2022/01/01 05:09 [entrez]
PHST- 2022/01/02 06:00 [pubmed]
PHST- 2022/01/02 06:01 [medline]
AID - 10.1063/5.0064966 [doi]
PST - ppublish
SO  - J Chem Phys. 2021 Dec 28;155(24):244305. doi: 10.1063/5.0064966.