Probing the Dipole-Bound State in the 9-Phenanthrolate Anion by Photodetachment Spectroscopy, Resonant Two-Photon Photoelectron Imaging, and Resonant Photoelectron Spectroscopy

Yuan, Dao-Fu; Zhang, Yue-Rou; Qian, Chen-Hui; Liu, Yuan; Wang, Lai-Sheng

doi:10.1021/acs.jpca.1c01563

Title: Probing the Dipole-Bound State in the 9-Phenanthrolate Anion by Photodetachment Spectroscopy, Resonant Two-Photon Photoelectron Imaging, and Resonant Photoelectron Spectroscopy

Journal Article · Fri Apr 02 00:00:00 EDT 2021 · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory

DOI:https://doi.org/10.1021/acs.jpca.1c01563· OSTI ID:1775307

^[1]; Zhang, Yue-Rou ^[1]; Qian, Chen-Hui ^[1]; Liu, Yuan ^[2];

^[1]

Brown Univ., Providence, RI (United States)
Brown Univ., Providence, RI (United States); Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)

Valence-bound anions with a dipolar core can support dipole-bound states (DBSs) below the electron detachment threshold. The highly diffuse DBS observed is usually of σ symmetry with an s-like orbital. Recently, a π-type DBS was observed experimentally in the 9-anthrolate anion (9AT^–) and it was shown to be stabilized due to the large anisotropic polarizability of the 9AT core. To confirm the general existence of π-DBS and its structural dependence, here we report an investigation of the 9-phenanthrolate anion (9PT^–), which has a different structure and lower symmetry than 9AT^–. Photodetachment spectroscopy revealed a DBS 257 cm^-1 below the detachment threshold of 9PT^– at 19,627 cm^-1 (2.4334 eV). Resonant two-photon photoelectron imaging indeed showed a π symmetry for the DBS. Similar to that observed in 9AT^–, the π-DBS in 9PT^– is also stabilized by the anisotropic polarizability of the 9PT core and accessed via non-adiabatic population transfer from the initially populated σ-DBS. Photodetachment spectroscopy unveiled nine above-threshold vibrational resonances of the DBS, resulting in nine highly non-Franck-Condon resonant photoelectron spectra by tuning the detachment laser to the vibrational resonances. In conclusion, the combination of photodetachment spectroscopy and resonant photoelectron spectroscopy allowed frequencies for nine vibrational modes of the 9-phenathroxy radical to be measured, including the six lowest frequency bending modes.

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Research Organization:: Brown Univ., Providence, RI (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0018679

OSTI ID:: 1775307

Journal Information:: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Vol. 125; ISSN 1089-5639

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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