| Alternative title | The ultrafast vacuum ultraviolet (VUV) Rydberg state dynamics of cyclic ethers reflects ring strain |
|---|
| DOI | Resolve DOI: https://doi.org/10.1039/D0CP04292G |
|---|
| Author | Search for: Röder, AnjaORCID identifier: https://orcid.org/0000-0001-9291-347X; Search for: Skov, Anders B.; Search for: Boguslavskiy, Andrey E.1; Search for: Lausten, Rune1; Search for: Stolow, AlbertORCID identifier: https://orcid.org/0000-0002-8447-3678 |
|---|
| Affiliation | - National Research Council of Canada. Security and Disruptive Technologies
|
|---|
| Format | Text, Article |
|---|
| Abstract | The vacuum ultraviolet (VUV) absorption spectra of cyclic ethers consist primarily of Rydberg ← n transitions. By studying three cyclic ethers of varying ring size (tetrahydropyran, tetrahydrofuran and trimethylene oxide, n = 6–4), we investigated the influence of ring size on the VUV excited-state dynamics of the 3d Rydberg manifold using time-resolved photoelectron spectroscopy (TRPES), time-resolved mass spectroscopy (TRMS) and ab initio electronic structure calculations. Whereas neither the electronic characters nor the term energies of the excited-states are substantially modified when the ring-size is reduced from n = 6 to 5 to 4, the excited-state lifetimes concomitantly decrease five-fold. TRPES and TRMS allow us to attribute the observed dynamics to a Rydberg cascade from the initially excited d-Rydberg manifold via the p-Rydberg manifold to the s-Rydberg state. Cuts through potential energy surfaces along the C–O bond reveal that a nσ* state crossing brings the s-Rydberg state along a path to the ring-opened ground state. The observed difference in excited-state lifetimes is attributed to an increasing slope along the repulsive C–O bond coordinate as ring size decreases. |
|---|
| Publication date | 2020-10-27 |
|---|
| Publisher | Royal Society of Chemistry |
|---|
| In | |
|---|
| Language | English |
|---|
| Peer reviewed | Yes |
|---|
| Export citation | Export as RIS |
|---|
| Report a correction | Report a correction (opens in a new tab) |
|---|
| Record identifier | 02863ef9-5bfd-443d-9c03-4ad55a3be971 |
|---|
| Record created | 2021-05-11 |
|---|
| Record modified | 2021-05-13 |
|---|
