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

Molecules

Yu Hashimoto¹  Toshiyuki Takayanagi¹  Yukinobu Takahashi¹  Kohei Saito¹ 

[1] Department of Chemistry, Saitama University, Shimo-Okubo 255, Sakura-ku, Saitama 338-8570, Japan;

关键词: dissociative photodetachment;    oxalate anion;    reaction dynamics;    ring-polymer molecular dynamics;    path-integral molecular dynamics;    nuclear quantum effect;   

DOI  :  10.3390/molecules26237250

来源: DOAJ

【 摘 要 】

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.

【 授权许可】

Unknown