TY - JOUR
T1 - Lowerature Magnetism in Nanoscale Gold Revealed through Variableerature Magnetic Circular Dichroism Spectroscopy
AU - Herbert, Patrick J.
AU - Window, Phillip
AU - Ackerson, Christopher J.
AU - Knappenberger, Kenneth L.
N1 - Funding Information:
This work was supported by an award from the National Science Foundation to K.L.K., under Grant Number CHE-1806222, and a grant from the National Science Foundation (CHE-1455099) to C.J.A.
Publisher Copyright:
© 2018 American Chemical Society.
PY - 2019/1/17
Y1 - 2019/1/17
N2 - The lowerature (0.35-4.2 K) steady-state electronic absorption of the monolayer-protected cluster (MPC) Au 102 (pMBA) 44 was studied using magnetic circular dichroism (MCD) spectroscopy to investigate previously reported lowerature (<50 K) magnetism in d 10 nanogold systems. Variableerature variable-field analysis of resolvable MCD extinction components revealed two distinct magnetic anisotropic behaviors. A low-energy, diamagnetic component was correlated to excitation from states localized to the passivating ligands. A high-energy, paramagnetic component was attributed to excitation from the d-band of the Au core. The temperature dependence of the magnetic anisotropy for each component is discussed in terms of previously reported structural parameters of the atomically precise Au 102 (pMBA) 44 MPC. It is concluded that temperature-sensitive structure-dependent Au d-d orbital interactions result in the promotion of 5d-band electrons to the 6sp-band via orbital rehybridization, inducing a 15× increase in the Landé g-factor over the temperature range spanning from 0.35 to 4.2 K.
AB - The lowerature (0.35-4.2 K) steady-state electronic absorption of the monolayer-protected cluster (MPC) Au 102 (pMBA) 44 was studied using magnetic circular dichroism (MCD) spectroscopy to investigate previously reported lowerature (<50 K) magnetism in d 10 nanogold systems. Variableerature variable-field analysis of resolvable MCD extinction components revealed two distinct magnetic anisotropic behaviors. A low-energy, diamagnetic component was correlated to excitation from states localized to the passivating ligands. A high-energy, paramagnetic component was attributed to excitation from the d-band of the Au core. The temperature dependence of the magnetic anisotropy for each component is discussed in terms of previously reported structural parameters of the atomically precise Au 102 (pMBA) 44 MPC. It is concluded that temperature-sensitive structure-dependent Au d-d orbital interactions result in the promotion of 5d-band electrons to the 6sp-band via orbital rehybridization, inducing a 15× increase in the Landé g-factor over the temperature range spanning from 0.35 to 4.2 K.
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U2 - 10.1021/acs.jpclett.8b03473
DO - 10.1021/acs.jpclett.8b03473
M3 - Article
C2 - 30582816
AN - SCOPUS:85060168446
SN - 1948-7185
VL - 10
SP - 189
EP - 193
JO - Journal of Physical Chemistry Letters
JF - Journal of Physical Chemistry Letters
IS - 2
ER -