Dissociative detachment of the fluoroformate anion

Eugene Shirman; Abhishek Shahi; Robert E. Continetti; Daniel Strasser

doi:10.1039/d0cp04283h

Dissociative detachment of the fluoroformate anion

Physical Chemistry Chemical Physics ◽

10.1039/d0cp04283h ◽

2020 ◽

Vol 22 (47) ◽

pp. 27666-27672

Author(s):

Eugene Shirman ◽

Abhishek Shahi ◽

Robert E. Continetti ◽

Daniel Strasser

Keyword(s):

Dissociative Photodetachment

3D fragment imaging of the fluoroformate anion (FCO2−) dissociative photodetachment products shows reductive fragmentation, forming FCO + O, as well as a dominant cleavage of the CF bond.

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Dissociative Photodetachment Dynamics of the OH–(C2H4) Anion Complex

The Journal of Physical Chemistry A ◽

10.1021/acs.jpca.1c01835 ◽

2021 ◽

Author(s):

Yanice Benitez ◽

Austin J. Parsons ◽

Katharine G. Lunny ◽

Robert E. Continetti

Keyword(s):

Anion Complex ◽

Dissociative Photodetachment

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On-the-Fly Ring-Polymer Molecular Dynamics Calculations of the Dissociative Photodetachment Process of the Oxalate Anion

Molecules ◽

10.3390/molecules26237250 ◽

2021 ◽

Vol 26 (23) ◽

pp. 7250

Author(s):

Yukinobu Takahashi ◽

Yu Hashimoto ◽

Kohei Saito ◽

Toshiyuki Takayanagi

Keyword(s):

Molecular Dynamics ◽

Potential Energy ◽

Quantum Effects ◽

Experimental Spectrum ◽

Computational Time ◽

Oxalate Anion ◽

Dissociative Photodetachment ◽

Ring Polymer ◽

Ring Polymer Molecular Dynamics ◽

Nuclear Quantum Effects

The dissociative photodetachment dynamics of the oxalate anion, C2O4H− + hν → CO2 + HOCO + e−, were theoretically studied using the on-the-fly path-integral and ring-polymer molecular dynamics methods, which can account for nuclear quantum effects at the density-functional theory level in order to compare with the recent experimental study using photoelectron–photofragment coincidence spectroscopy. To reduce computational time, the force acting on each bead of ring-polymer was approximately calculated from the first and second derivatives of the potential energy at the centroid position of the nuclei beads. We find that the calculated photoelectron spectrum qualitatively reproduces the experimental spectrum and that nuclear quantum effects are playing a role in determining spectral widths. The calculated coincidence spectrum is found to reasonably reproduce the experimental spectrum, indicating that a relatively large energy is partitioned into the relative kinetic energy between the CO2 and HOCO fragments. This is because photodetachment of the parent anion leads to Franck–Condon transition to the repulsive region of the neutral potential energy surface. We also find that the dissociation dynamics are slightly different between the two isomers of the C2O4H− anion with closed- and open-form structures.

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