Mode-Specific Autodetachment Dynamics of an Excited Non-valence Quadrupole-Bound State

2022

Chem. Sci.

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Section: Methodsmentioning

confidence: 99%

Dynamic role of the correlation effect revealed in the exceptionally slow autodetachment rates of the vibrational Feshbach resonances in the dipole-bound state

2022

Chem. Sci.

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“…Details of the electrospray ionization and photoelectron imaging (ESI-PEI) apparatus were described elsewhere. 46 combined with a retro-reflector (UBBR2.5-1UV, Newport). Laser intensities were measured using a set of laser power meter (FieldMaxII-TO, Coherent) and power sensor (PM10, Coherent).…”

Section: Methodsmentioning

confidence: 99%

“…The NBS levels above the detachment threshold mainly decay by the rovibrational autodetachment process. According to our recent real-time dynamics studies on DBS and QBS 45,46 , the Fermi-Golden rule provides the nice platform for the description of both absolute and relative autodetachment rates.…”

mentioning

confidence: 99%

Observation of the Ponderomotive Effect in Non-Valence Bound States of Polyatomic Molecular Anions

Noh

et al. 2021

Preprint

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The ponderomotive effect in the non-valence bound states has been experimentally demonstrated for the first time, giving the great promise for the manipulation of the polyatomic molecules by the dynamic Stark effect. Entire quantum levels of the dipole-bound state (DBS) and quadruple-bound state (QBS) of the phenoxide (or 4-bromophenoxide) and 4-cyanophenoxide anions, respectively, show the clear-cut ponderomotive blue-shifts in the presence of the spatiotemporally overlapped non-resonant picosecond control laser pulse. The quasi-free electron in the QBS is found to be more vulnerable to the external oscillating electromagnetic field compared to that in the DBS, suggesting that the non-valence orbital of the former is more diffusive and thus more polarizable compared to that of the latter.

“…Details of the electrospray ionization-photoelectron imaging (ESI-PEI) apparatus have been described elsewhere. 42 1mM concentration of the phenol and 4-XPhOH (X = -Cl, -Br, TCI chemicals) were dissolved in the 9:1 methanol/water solution without further purifications.…”

Section: Methodsmentioning

confidence: 99%

Dynamic Role of the Correlation Effect Revealed in the Exceptionally Slow Autodetachment Rates of the Vibrational Feshbach Resonances in the Dipole-Bound State

2021

Preprint

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Real-time autodetachment dynamics of the loosely-bound excess electron from the vibrational Feshbach resonances of the dipole-bound states (DBS) of 4-bromophonoxide (4-BrPhO-) and 4-chlorophenoxide (4-ClPhO-) anions have been thoroughly investigated. The state-specific autodetachment rate measurements obtained by the picosecond time-resolved pump-probe method on the cryogenically cooled anions, exhibit the exceptionally long lifetime (τ) of ~ 2.5  0.6 ns (as the upper bound) for the 11’1 vibrational mode of the 4-BrPhO- DBS. Strong mode-dependency in the wide dynamic range has also been found, giving τ ~ 5.3 ps for the 10’1 mode, for instance. Though it is nontrivial to get the state-specific rates for the 4-ClPhO- DBS, the average autodetachment lifetime of the 19’120’1/11’1 mode has been estimated to be ~ 548  108 ps. Observation of these exceptionally slow autodetachment rates of vibrational Feshbach resonances strongly indicates that the ‘correlation effect’ may play a significant role in the DBS photodetachment dynamics. The Fermi’s golden rule has been invoked so that the correlation effect is taken into account in the form of the interaction between the charge and the induced dipole where the latter is given by the polarizable counterparts of the electron-rich halogenated compound and the diffuse non-valence electron. This report suggests that one may measure, from the real-time autodetachment dynamics, the extent of the correlation effect contribution to the stabilization and/or dynamics of the excess non-valence electron among many different types of the long-range interactions of the DBS.