Synchrotron-based infrared spectroscopy of formic acid: Confirmation of the reassignment of Fermi-coupled 8 μm states
The empirically derived assignment of the strongly interacting 51 and 92 vibrational states of trans-HCOOH has recently been reassigned on the basis of anharmonic frequency calculations, and this, in turn, affects the assignment of many higher energy states. Here, we investigate the high-resolution...
| Main Authors: | , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
AIP Publishing LLC
2019-01-01
|
| Series: | AIP Advances |
| Online Access: | http://dx.doi.org/10.1063/1.5063010 |
| _version_ | 1818940768225591296 |
|---|---|
| author | Killian Hull Tyler Wells Brant E. Billinghurst Hayley Bunn Paul L. Raston |
| author_facet | Killian Hull Tyler Wells Brant E. Billinghurst Hayley Bunn Paul L. Raston |
| author_sort | Killian Hull |
| collection | DOAJ |
| description | The empirically derived assignment of the strongly interacting 51 and 92 vibrational states of trans-HCOOH has recently been reassigned on the basis of anharmonic frequency calculations, and this, in turn, affects the assignment of many higher energy states. Here, we investigate the high-resolution synchrotron-based torsional spectrum of trans-HCOOH, and find experimental confirmation that the proposed reassignment is indeed correct, i.e., that 92 is in fact lower in energy than 51. This is largely based on examining the intensity ratio of transitions with the same rotational quantum numbers between the 92-91 and 51-91 hot bands, which indicates that the 51 [92] state has ∼31% 92 [51] character. We also examined the torsional spectrum of trans-HCOOD, and find that the intensity ratios are consistent with 92 instead being higher in energy than 61 (which is analogous to 51 in trans-HCOOD), as previously determined from higher energy spectra. |
| first_indexed | 2024-12-20T06:44:53Z |
| format | Article |
| id | doaj.art-2d192b817cda40a3bf2341665ec4d29e |
| institution | Directory Open Access Journal |
| issn | 2158-3226 |
| language | English |
| last_indexed | 2024-12-20T06:44:53Z |
| publishDate | 2019-01-01 |
| publisher | AIP Publishing LLC |
| record_format | Article |
| series | AIP Advances |
| spelling | doaj.art-2d192b817cda40a3bf2341665ec4d29e2022-12-21T19:49:44ZengAIP Publishing LLCAIP Advances2158-32262019-01-0191015021015021-710.1063/1.5063010064901ADVSynchrotron-based infrared spectroscopy of formic acid: Confirmation of the reassignment of Fermi-coupled 8 μm statesKillian Hull0Tyler Wells1Brant E. Billinghurst2Hayley Bunn3Paul L. Raston4Department of Chemistry and Biochemistry, James Madison University, Harrisonburg, Virginia 22807, USADepartment of Chemistry and Biochemistry, James Madison University, Harrisonburg, Virginia 22807, USACanadian Light Source Inc., 44 Innovation Boulevard, Saskatoon, Saskatchewan S7N 2V3, CanadaDepartment of Chemistry, University of Adelaide, South Australia, 5005, AustraliaDepartment of Chemistry and Biochemistry, James Madison University, Harrisonburg, Virginia 22807, USAThe empirically derived assignment of the strongly interacting 51 and 92 vibrational states of trans-HCOOH has recently been reassigned on the basis of anharmonic frequency calculations, and this, in turn, affects the assignment of many higher energy states. Here, we investigate the high-resolution synchrotron-based torsional spectrum of trans-HCOOH, and find experimental confirmation that the proposed reassignment is indeed correct, i.e., that 92 is in fact lower in energy than 51. This is largely based on examining the intensity ratio of transitions with the same rotational quantum numbers between the 92-91 and 51-91 hot bands, which indicates that the 51 [92] state has ∼31% 92 [51] character. We also examined the torsional spectrum of trans-HCOOD, and find that the intensity ratios are consistent with 92 instead being higher in energy than 61 (which is analogous to 51 in trans-HCOOD), as previously determined from higher energy spectra.http://dx.doi.org/10.1063/1.5063010 |
| spellingShingle | Killian Hull Tyler Wells Brant E. Billinghurst Hayley Bunn Paul L. Raston Synchrotron-based infrared spectroscopy of formic acid: Confirmation of the reassignment of Fermi-coupled 8 μm states AIP Advances |
| title | Synchrotron-based infrared spectroscopy of formic acid: Confirmation of the reassignment of Fermi-coupled 8 μm states |
| title_full | Synchrotron-based infrared spectroscopy of formic acid: Confirmation of the reassignment of Fermi-coupled 8 μm states |
| title_fullStr | Synchrotron-based infrared spectroscopy of formic acid: Confirmation of the reassignment of Fermi-coupled 8 μm states |
| title_full_unstemmed | Synchrotron-based infrared spectroscopy of formic acid: Confirmation of the reassignment of Fermi-coupled 8 μm states |
| title_short | Synchrotron-based infrared spectroscopy of formic acid: Confirmation of the reassignment of Fermi-coupled 8 μm states |
| title_sort | synchrotron based infrared spectroscopy of formic acid confirmation of the reassignment of fermi coupled 8 μm states |
| url | http://dx.doi.org/10.1063/1.5063010 |
| work_keys_str_mv | AT killianhull synchrotronbasedinfraredspectroscopyofformicacidconfirmationofthereassignmentoffermicoupled8mmstates AT tylerwells synchrotronbasedinfraredspectroscopyofformicacidconfirmationofthereassignmentoffermicoupled8mmstates AT brantebillinghurst synchrotronbasedinfraredspectroscopyofformicacidconfirmationofthereassignmentoffermicoupled8mmstates AT hayleybunn synchrotronbasedinfraredspectroscopyofformicacidconfirmationofthereassignmentoffermicoupled8mmstates AT paullraston synchrotronbasedinfraredspectroscopyofformicacidconfirmationofthereassignmentoffermicoupled8mmstates |