dorsal/arxiv
View SchemaA high-resolution infrared spectroscopic investigation of the halogen atom-HCN entrance channel complexes solvated in superfluid helium droplets
| Authors | Jeremy M. Merritt, Jochen Küpper, Roger E. Miller |
|---|---|
| Categories | |
| ArXiv ID | physics/0610041 |
| URL | https://arxiv.org/abs/physics/0610041 |
| DOI | 10.1039/B611340K |
| Journal | Phys. Chem. Chem. Phys. 9, 401-416 (2007) |
Abstract
Rotationally resolved infrared spectra are reported for the X-HCN (X = Cl, Br, I) binary complexes solvated in helium nanodroplets. These results are directly compared with that obtained previously for the corresponding X-HF complexes [J. M. Merritt, J. K\"upper, and R. E. Miller, PCCP, 7, 67 (2005)]. For bromine and iodine atoms complexed with HCN, two linear structures are observed and assigned to the $^{2}\Sigma_{1/2}$ and $^{2}\Pi_{3/2}$ ground electronic states of the nitrogen and hydrogen bound geometries, respectively. Experiments for HCN + chlorine atoms give rise to only a single band which is attributed to the nitrogen bound isomer. That the hydrogen bound isomer is not stabilized is rationalized in terms of a lowering of the isomerization barrier by spin-orbit coupling. Theoretical calculations with and without spin-orbit coupling have also been performed and are compared with our experimental results. The possibility of stabilizing high-energy structures containing multiple radicals is discussed, motivated by preliminary spectroscopic evidence for the di-radical Br-HCCCN-Br complex. Spectra for the corresponding molecular halogen HCN-X$_{2}$ complexes are also presented.
{
"annotation_id": "39995544-0369-4b58-9492-83bc3496b757",
"date_created": "2026-03-02T18:01:14.473000Z",
"date_modified": "2026-03-02T18:01:14.473000Z",
"file_hash": "6ca7e5edfd5ba02e977204e971d0b2b9325082fcdd939cc9a3891aff5996207d",
"private": false,
"record": {
"abstract": "Rotationally resolved infrared spectra are reported for the X-HCN (X = Cl,\nBr, I) binary complexes solvated in helium nanodroplets. These results are\ndirectly compared with that obtained previously for the corresponding X-HF\ncomplexes [J. M. Merritt, J. K\\\"upper, and R. E. Miller, PCCP, 7, 67 (2005)].\nFor bromine and iodine atoms complexed with HCN, two linear structures are\nobserved and assigned to the $^{2}\\Sigma_{1/2}$ and $^{2}\\Pi_{3/2}$ ground\nelectronic states of the nitrogen and hydrogen bound geometries, respectively.\nExperiments for HCN + chlorine atoms give rise to only a single band which is\nattributed to the nitrogen bound isomer. That the hydrogen bound isomer is not\nstabilized is rationalized in terms of a lowering of the isomerization barrier\nby spin-orbit coupling. Theoretical calculations with and without spin-orbit\ncoupling have also been performed and are compared with our experimental\nresults. The possibility of stabilizing high-energy structures containing\nmultiple radicals is discussed, motivated by preliminary spectroscopic evidence\nfor the di-radical Br-HCCCN-Br complex. Spectra for the corresponding molecular\nhalogen HCN-X$_{2}$ complexes are also presented.",
"arxiv_id": "physics/0610041",
"authors": [
"Jeremy M. Merritt",
"Jochen K\u00fcpper",
"Roger E. Miller"
],
"categories": [
"physics.atm-clus",
"physics.chem-ph"
],
"doi": "10.1039/B611340K",
"journal_ref": "Phys. Chem. Chem. Phys. 9, 401-416 (2007)",
"title": "A high-resolution infrared spectroscopic investigation of the halogen atom-HCN entrance channel complexes solvated in superfluid helium droplets",
"url": "https://arxiv.org/abs/physics/0610041"
},
"schema_id": "dorsal/arxiv",
"source": {
"execution_id": "23182346-8112-42ef-84c6-15659c571b4f",
"id": "arXiv Dataset IDs",
"type": "Model",
"variant": "snapshot-2026-03-01",
"version": "0.1.0"
},
"user_id": 1000002
}