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Core-to-Rydberg band shift and broadening of hydrogen bonded ammonia clusters studied with nitrogen K-edge excitation spectroscopy.
| Content Provider | Semantic Scholar |
|---|---|
| Author | Yamanaka, Takeshi Tabayashi, Kiyohiko Takahashi, Osamu Tanaka, Kenichiro Namatame, Hirofumi Taniguchi, Masaki |
| Copyright Year | 2012 |
| Abstract | Nitrogen 1s (N 1s) core-to-Rydberg excitation spectra of hydrogen-bonded clusters of ammonia (AM) have been studied in the small cluster regime of beam conditions with time-of-flight (TOF) fragment-mass spectroscopy. By monitoring partial-ion-yield spectra of cluster-origin products, "cluster" specific excitation spectra could be recorded. Comparison of the "cluster" band with "monomer" band revealed that the first resonance bands of clusters corresponding to N 1s → 3sa(1)/3pe of AM monomer are considerably broadened. The changes of the experimental core-to-Rydberg transitions ΔFWHM (N 1s → 3sa(1)/3pe) = ~0.20/~0.50 eV compare well with the x ray absorption spectra of the clusters generated by using density functional theory (DFT) calculation. The broadening of the core-to-Rydberg bands in small clusters is interpreted as being primarily due to the splitting of non-equivalent core-hole N 1s states caused by both electrostatic core-hole and hydrogen-bonding (H(3)N···H-NH(2)) interactions upon dimerization. Under Cs dimer configuration, core-electron binding energy of H-N (H-donor) is significantly decreased by the intermolecular core-hole interaction and causes notable redshifts of core-excitation energies, whereas that of lone-pair nitrogen (H-acceptor) is slightly increased and results in appreciable blueshifts in the core-excitation bands. The result of the hydrogen-bonding interaction strongly appears in the n-σ* orbital correlation, destabilizing H-N donor Rydberg states in the direction opposite to the core-hole interaction, when excited N atom with H-N donor configuration strongly possesses the Rydberg component of anti-bonding σ* (N-H) character. Contributions of other cyclic H-bonded clusters (AM)(n) with n ≥ 3 to the spectral changes of the N 1s → 3sa(1)/3pe bands are also examined. |
| Starting Page | 014308 |
| Ending Page | 014308 |
| Page Count | 1 |
| File Format | PDF HTM / HTML |
| Alternate Webpage(s) | http://ir.lib.hiroshima-u.ac.jp/files/public/3/34781/20141016203248109163/JCP_136_014308.pdf |
| PubMed reference number | 22239782v1 |
| Alternate Webpage(s) | https://doi.org/10.1063/1.3673778 |
| DOI | 10.1063/1.3673778 |
| Journal | The Journal of chemical physics |
| Volume Number | 136 |
| Issue Number | 1 |
| Language | English |
| Access Restriction | Open |
| Subject Keyword | Ammonia measurement Bands Blood urea nitrogen measurement Dimerization Energy, Physics Excitation Ions Mass Spectrometry Pyschological Bonding RGLCYRPRFVCVG-NH(2) Roentgen Rays Supernumerary maxillary right third molar monomer newton |
| Content Type | Text |
| Resource Type | Article |
