DC Field | Value | Language |
---|---|---|
dc.contributor.author | Bae, C | ko |
dc.contributor.author | Han, YK | ko |
dc.contributor.author | Lee, Yoon Sup | ko |
dc.date.accessioned | 2013-03-04T17:22:46Z | - |
dc.date.available | 2013-03-04T17:22:46Z | - |
dc.date.created | 2012-02-06 | - |
dc.date.created | 2012-02-06 | - |
dc.date.issued | 2003-02 | - |
dc.identifier.citation | JOURNAL OF PHYSICAL CHEMISTRY A, v.107, no.6, pp.852 - 858 | - |
dc.identifier.issn | 1089-5639 | - |
dc.identifier.uri | http://hdl.handle.net/10203/83443 | - |
dc.description.abstract | Spin-orbit and scalar relativistic effects on geometries, vibrational frequencies, and energies for group 17 fluorides EF3 (E = 1, At, and element 117) are evaluated with two-component methods using relativistic pseudopotentials and effective one-electron spin-orbit operators. The inclusion of relativistic effects makes the D-3h structure of (I 17)F-3 a stable local minimum, whereas IF3 and AtF3 retain C-2nu local minima even with relativistic effects. The valence shell electron pair repulsion model is not appropriate to explain the molecular structure of (I 17)F-3. The geometries of EF3 (E = 1, At, and element 117) molecules are optimized at the HF level with and without spin-orbit effects. Spin-orbit interactions elongate the bond lengths and decrease the harmonic vibrational frequencies. In the case of AtF3, spin-orbit interactions increase the bond lengths by 0.044 and 0.023 Angstrom for r(e)(eq) and r(e)(ax), respectively. Spin-orbit effects widen the bond angle of C-2nu structures of re re IF3 and AtF3, i.e., spin-orbit effects diminish the second-order Jahn-Teller term. The bond angle alpha(e) of AtF3 increases by 3.9degrees due to spin-orbit interactions in addition to the increase of 4.8degrees by scalar relativistic effects. For (I 17)F-3, spin-orbit effects increase the bond length by 0.109 Angstrom. The spin-orbit interactions stabilize (I 17)F-3 by a significant margin (similar to1.2 eV). This stabilization of the molecule compared with open p-shell atoms is quite unusual. Enhanced ionic bonding may be responsible for this stabilization because the electronegative F atom can effectively polarize or attract electrons from the destabilized 7(P3/2) spinors of element 117 due to huge spin-orbit splitting of 7p. | - |
dc.language | English | - |
dc.publisher | AMER CHEMICAL SOC | - |
dc.subject | EFFECTIVE CORE POTENTIALS | - |
dc.subject | SUPERHEAVY HYDROGEN HALIDES | - |
dc.subject | HARTREE-FOCK METHOD | - |
dc.subject | INTERMOLECULAR INTERACTIONS | - |
dc.subject | POLYATOMIC-MOLECULES | - |
dc.subject | HEAVY | - |
dc.subject | OPERATORS | - |
dc.subject | BOND | - |
dc.subject | RN | - |
dc.subject | (118)F-4 | - |
dc.title | Spin-orbit and relativistic effects on structures and stabilities of group 17 fluorides EF3 (E = I, At, and element 117): Relativity induced stability for the D-3h structure of (117)F-3 | - |
dc.type | Article | - |
dc.identifier.wosid | 000182533500014 | - |
dc.identifier.scopusid | 2-s2.0-0037434676 | - |
dc.type.rims | ART | - |
dc.citation.volume | 107 | - |
dc.citation.issue | 6 | - |
dc.citation.beginningpage | 852 | - |
dc.citation.endingpage | 858 | - |
dc.citation.publicationname | JOURNAL OF PHYSICAL CHEMISTRY A | - |
dc.contributor.localauthor | Lee, Yoon Sup | - |
dc.contributor.nonIdAuthor | Bae, C | - |
dc.contributor.nonIdAuthor | Han, YK | - |
dc.type.journalArticle | Article | - |
dc.subject.keywordPlus | EFFECTIVE CORE POTENTIALS | - |
dc.subject.keywordPlus | SUPERHEAVY HYDROGEN HALIDES | - |
dc.subject.keywordPlus | HARTREE-FOCK METHOD | - |
dc.subject.keywordPlus | INTERMOLECULAR INTERACTIONS | - |
dc.subject.keywordPlus | POLYATOMIC-MOLECULES | - |
dc.subject.keywordPlus | HEAVY | - |
dc.subject.keywordPlus | OPERATORS | - |
dc.subject.keywordPlus | BOND | - |
dc.subject.keywordPlus | RN | - |
dc.subject.keywordPlus | (118)F-4 | - |
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