Picocavity-Enhanced Raman Spectroscopy of Physisorbed H$_2$ and D$_2$ Molecules
Fuente:
arXiv
Saved in:
| Main Authors: | , , , , , , |
|---|---|
| Format: | Preprint |
| Published: |
2024
|
| Subjects: | |
| Online Access: | |
| Tags: |
Add Tag
No Tags, Be the first to tag this record!
|
| _version_ | 1866908371647463424 |
|---|---|
| author | Shiotari, Akitoshi Liu, Shuyi Trenins, George Sugimoto, Toshiki Wolf, Martin Rossi, Mariana Kumagai, Takashi |
| author_facet | Shiotari, Akitoshi Liu, Shuyi Trenins, George Sugimoto, Toshiki Wolf, Martin Rossi, Mariana Kumagai, Takashi |
| contents | We report on tip-enhanced Raman spectroscopy of H2 and D2 molecules physisorbed within a plasmonic picocavity at 10 K. The intense Raman peaks resulting from the rotational and vibrational transitions are observed at subnanometer gap distances of the junction formed by an Ag tip and an Ag(111) surface, where a picocavity-enhanced field plays a crucial role. A significant redshift of the H-H stretch frequency is observed as the gap distance decreases, while the D-D stretch frequency is unaffected. Density functional theory, path-integral molecular dynamics, and quantum anharmonic vibrational energy calculations suggest that this unexpected isotope effect is explained by a different molecular density between H2 and D2 on the surface. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2411_10994 |
| institution | arXiv |
| publishDate | 2024 |
| record_format | arxiv |
| spellingShingle | Picocavity-Enhanced Raman Spectroscopy of Physisorbed H$_2$ and D$_2$ Molecules Shiotari, Akitoshi Liu, Shuyi Trenins, George Sugimoto, Toshiki Wolf, Martin Rossi, Mariana Kumagai, Takashi Optics Mesoscale and Nanoscale Physics We report on tip-enhanced Raman spectroscopy of H2 and D2 molecules physisorbed within a plasmonic picocavity at 10 K. The intense Raman peaks resulting from the rotational and vibrational transitions are observed at subnanometer gap distances of the junction formed by an Ag tip and an Ag(111) surface, where a picocavity-enhanced field plays a crucial role. A significant redshift of the H-H stretch frequency is observed as the gap distance decreases, while the D-D stretch frequency is unaffected. Density functional theory, path-integral molecular dynamics, and quantum anharmonic vibrational energy calculations suggest that this unexpected isotope effect is explained by a different molecular density between H2 and D2 on the surface. |
| title | Picocavity-Enhanced Raman Spectroscopy of Physisorbed H$_2$ and D$_2$ Molecules |
| topic | Optics Mesoscale and Nanoscale Physics |
| url | https://arxiv.org/abs/2411.10994 |