TY - JOUR
T1 - Temporary Anions of Benzoxazole in Charge-Transfer Cluster Photodetachment
AU - Feng, Beverly
AU - Cordova, Sydney
AU - Fang, Connor
AU - Sanov, Andrei
N1 - Publisher Copyright:
© 2024 American Chemical Society.
PY - 2024/10/10
Y1 - 2024/10/10
N2 - The photoelectron spectra of cluster anions of superoxide (O2-) solvated by one molecule of benzoxazole (BzOx) reveal two competing photodetachment mechanisms: a direct photoemission from the solvated cluster core and an indirect pathway involving temporary anion states of benzoxazole accessed via the O2-·BzOx → O2·BzOx- charge-transfer transitions. Benzoxazole is a bicyclic unsaturated organic molecule that does not form permanent anions. However, its low-lying vacant π* orbitals permit a resonant capture of the electron emitted from the O2- cluster core. The non-Hermitian theory using a complex absorbing potential predicts the existence of two BzOx- π* resonances within the experimental energy range: resonance A (π1*) at 0.891 eV and resonance B (π2*) at 1.76 eV, relative to the onset of the BzOx + e- continuum at the ground-state geometry of neutral BzOx. Within the clusters, the O2·BzOx- charge-transfer states are partially stabilized relative to the free-electron limit by interactions with the O2 molecule. These interactions depend on the electronic states of both species. The theory predicts that at the O2-·BzOx cluster geometry, the O2(X3Σg-)·BzOx-(A) and O2(a1Δg)·BzOx-(A) states lie at 0.56 and 0.47 eV (vertically) above the respective neutral states. The O2(3Σg-)·BzOx-(B) resonance is found 1.43 eV (vertically) above O2(X3Σg-)·BzOx. Intense signatures of both BzOx- resonances and the three above-mentioned charge-transfer cluster states, O2(X3Σg-)·BzOx-(A), O2(a1Δg)·BzOx-(A), and O2(3Σg-)·BzOx-(B) are observed in the 355 nm (3.495 eV) and 532 nm (2.330 eV) photoelectron spectra of the O2-·BzOx cluster anion.
AB - The photoelectron spectra of cluster anions of superoxide (O2-) solvated by one molecule of benzoxazole (BzOx) reveal two competing photodetachment mechanisms: a direct photoemission from the solvated cluster core and an indirect pathway involving temporary anion states of benzoxazole accessed via the O2-·BzOx → O2·BzOx- charge-transfer transitions. Benzoxazole is a bicyclic unsaturated organic molecule that does not form permanent anions. However, its low-lying vacant π* orbitals permit a resonant capture of the electron emitted from the O2- cluster core. The non-Hermitian theory using a complex absorbing potential predicts the existence of two BzOx- π* resonances within the experimental energy range: resonance A (π1*) at 0.891 eV and resonance B (π2*) at 1.76 eV, relative to the onset of the BzOx + e- continuum at the ground-state geometry of neutral BzOx. Within the clusters, the O2·BzOx- charge-transfer states are partially stabilized relative to the free-electron limit by interactions with the O2 molecule. These interactions depend on the electronic states of both species. The theory predicts that at the O2-·BzOx cluster geometry, the O2(X3Σg-)·BzOx-(A) and O2(a1Δg)·BzOx-(A) states lie at 0.56 and 0.47 eV (vertically) above the respective neutral states. The O2(3Σg-)·BzOx-(B) resonance is found 1.43 eV (vertically) above O2(X3Σg-)·BzOx. Intense signatures of both BzOx- resonances and the three above-mentioned charge-transfer cluster states, O2(X3Σg-)·BzOx-(A), O2(a1Δg)·BzOx-(A), and O2(3Σg-)·BzOx-(B) are observed in the 355 nm (3.495 eV) and 532 nm (2.330 eV) photoelectron spectra of the O2-·BzOx cluster anion.
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U2 - 10.1021/acs.jpca.4c05043
DO - 10.1021/acs.jpca.4c05043
M3 - Article
C2 - 39329186
AN - SCOPUS:85205914954
SN - 1089-5639
VL - 128
SP - 8717
EP - 8731
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
IS - 40
ER -