TY - JOUR
T1 - Evaluation of the exothermicity of the chemi-ionization reaction Nd + O → NdO + + e − and neodymium oxide, carbide, dioxide, and carbonyl cation bond energies
AU - Ghiassee, Maryam
AU - Kim, Jung Soo
AU - Armentrout, P. B.
N1 - Publisher Copyright:
© 2019 Author(s).
PY - 2019/4/14
Y1 - 2019/4/14
N2 - The exothermicity of the chemi-ionization reaction, Nd + O → NdO + + e − , has been indirectly determined by measuring the thermochemistry for reactions of the lanthanide metal neodymium cation (Nd + ) with O 2 , CO 2 , and CO and reactions of NdO + with CO, O 2 , and Xe. Guided ion beam tandem mass spectrometry was used to measure the kinetic energy dependent product ion cross sections for these reactions. NdO + is formed through a barrierless exothermic process when the atomic metal cation reacts with O 2 and CO 2 . All other reactions are observed to be endothermic. Analyses of the kinetic energy dependences of these cross sections yield 0 K bond dissociation energies (BDEs) for several species. The 0 K BDE for Nd + -O is determined to be 7.28 ± 0.10 eV from the average of four independent thresholds. This value is combined with the well-established Nd ionization energy to indicate an exothermicity of the title reaction of 1.76 ± 0.10 eV, which is lower and more precise than literature values. In addition, the Nd + -C, ONd + -O, and Nd + -CO BDEs are determined to be 2.61 ± 0.30, 2.12 ± 0.30, and 0.30 ± 0.21 eV. Additionally, theoretical BDEs of Nd + -O, Nd + -C, ONd + -O, and Nd + -CO are calculated at several levels for comparison with the experimental values. B3LYP calculations seriously underestimate the Nd + -O BDE, whereas MP2 and coupled-cluster with single, double-and perturbative triple excitations values are in reasonable agreement. Good agreement is generally obtained for Nd + -C, ONd + -O, and Nd + -CO BDEs as well.
AB - The exothermicity of the chemi-ionization reaction, Nd + O → NdO + + e − , has been indirectly determined by measuring the thermochemistry for reactions of the lanthanide metal neodymium cation (Nd + ) with O 2 , CO 2 , and CO and reactions of NdO + with CO, O 2 , and Xe. Guided ion beam tandem mass spectrometry was used to measure the kinetic energy dependent product ion cross sections for these reactions. NdO + is formed through a barrierless exothermic process when the atomic metal cation reacts with O 2 and CO 2 . All other reactions are observed to be endothermic. Analyses of the kinetic energy dependences of these cross sections yield 0 K bond dissociation energies (BDEs) for several species. The 0 K BDE for Nd + -O is determined to be 7.28 ± 0.10 eV from the average of four independent thresholds. This value is combined with the well-established Nd ionization energy to indicate an exothermicity of the title reaction of 1.76 ± 0.10 eV, which is lower and more precise than literature values. In addition, the Nd + -C, ONd + -O, and Nd + -CO BDEs are determined to be 2.61 ± 0.30, 2.12 ± 0.30, and 0.30 ± 0.21 eV. Additionally, theoretical BDEs of Nd + -O, Nd + -C, ONd + -O, and Nd + -CO are calculated at several levels for comparison with the experimental values. B3LYP calculations seriously underestimate the Nd + -O BDE, whereas MP2 and coupled-cluster with single, double-and perturbative triple excitations values are in reasonable agreement. Good agreement is generally obtained for Nd + -C, ONd + -O, and Nd + -CO BDEs as well.
UR - http://www.scopus.com/inward/record.url?scp=85064197821&partnerID=8YFLogxK
U2 - 10.1063/1.5091679
DO - 10.1063/1.5091679
M3 - Article
C2 - 30981257
AN - SCOPUS:85064197821
SN - 0021-9606
VL - 150
JO - Journal of Chemical Physics
JF - Journal of Chemical Physics
IS - 14
M1 - 144309
ER -