METAL OXIDATION-STATE EFFECT IN PHOTOIONIZATION OF GAS-PHASE METAL-HALIDES

被引:2
作者
STRANGES, S
ADAM, MY
DESIMONE, M
DECLEVA, P
LISINI, A
CAULETTI, C
PIANCASTELLI, MN
FURLANI, C
机构
[1] UNIV PARIS 11,LURE,F-91405 ORSAY,FRANCE
[2] UNIV TRIESTE,DIPARTIMENTO SCI CHIM,I-34127 TRIESTE,ITALY
[3] UNIV ROMA TOR VERGATA,DIPARTIMENTO SCI & TECNOL CHIM,I-00173 ROME,ITALY
[4] UNIV ROME 3,I-00154 ROME,ITALY
关键词
D O I
10.1063/1.468579
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The full-valence photoelectron (PE) spectrum of SnCl4 excited by synchrotron radiation in the ultraviolet (UV) region is reported here for the first time, and compared with the analogous spectrum of SnCl2 previously published. Electron correlation effects in the different valence spectral regions are experimentally and theoretically analyzed for both tin chlorides. The theoretical results are obtained at ab initio 2h-1p CI level. Total-ion-yield (TIY) spectra excited by synchrotron radiation are obtained for both molecules in the Sn 4d-1 thresholds region for the first time. Sn 4d excited states in the two chlorides are hence identified through the resonant features displayed by the TIY spectra. The assignment is in good qualitative agreement with the excitation energies and oscillator strengths calculated at ab initio CI level. Clear differences exhibited by both PE and TIY spectra reported in this work originate from the different metal oxidation state in the two apparently similar chlorides, or equivalently, from the different involvement of the valence atomic orbitals of tin to form the chemical bonds of the molecule. Inner-valence ionizations in the investigated molecules are shown to be a sensitive probe of the halogen chemical environment, being related to the Sn-Cl bond polarization. © 1995 American Institute of Physics.
引用
收藏
页码:3555 / 3565
页数:11
相关论文
共 50 条
[41]   GAS-PHASE EMBRITTLEMENT BY METAL VAPORS [J].
BECKMAN, JP ;
WOODFORD, DA .
METALLURGICAL TRANSACTIONS A-PHYSICAL METALLURGY AND MATERIALS SCIENCE, 1989, 20 (01) :184-188
[42]   PHOTOIONIZATION OF PROPYNAL IN THE GAS-PHASE [J].
OPITZ, J .
INTERNATIONAL JOURNAL OF MASS SPECTROMETRY, 1991, 107 (03) :503-513
[43]   MODEL CALCULATIONS OF THE THERMOCHEMICAL PROPERTIES OF GASEOUS METAL-HALIDES [J].
HILDENBRAND, DL .
JOURNAL OF THE ELECTROCHEMICAL SOCIETY, 1979, 126 (08) :1396-1400
[44]   EFFECT OF METAL-HALIDES ON THERMAL, MECHANICAL, AND ELECTRICAL-PROPERTIES OF POLYPYROMELLITIMIDE FILMS [J].
VARMA, IK ;
SAXENA, S ;
TRIPATHI, A ;
GOEL, TC ;
VARMA, DS .
JOURNAL OF APPLIED POLYMER SCIENCE, 1986, 32 (03) :3987-4000
[45]   REACTION OF HALOGENS WITH METAL-HALIDES OF THE I-GROUP [J].
BATSANOV, SS ;
LAZAREVA, EV ;
KOPANEVA, LI .
ZHURNAL NEORGANICHESKOI KHIMII, 1979, 24 (08) :2258-2261
[46]   REACTIONS OF SOME PHENYLTELLURIUM(IV) COMPOUNDS WITH METAL-HALIDES [J].
KHANDELWAL, BL ;
JAIN, SK ;
BERRY, FJ .
INORGANICA CHIMICA ACTA-ARTICLES, 1982, 59 (02) :193-196
[47]   A NEW SUBCLASS OF INTERCALATION HOST MATERIALS - METAL-METAL BONDED BINARY METAL-HALIDES [J].
KENNEDY, JR .
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 1994, 208 :313-INOR
[48]   RHEOLOGY OF NYLON-6 CONTAINING METAL-HALIDES [J].
SHENOY, AV ;
SAINI, DR ;
NADKARNI, VM .
JOURNAL OF MATERIALS SCIENCE, 1983, 18 (07) :2149-2155
[49]   EFFECT OF METAL-HALIDES ON THE GLASS-TRANSITION TEMPERATURE OF NYLON-6 [J].
SIEGMANN, A ;
BARAAM, Z .
MAKROMOLEKULARE CHEMIE-RAPID COMMUNICATIONS, 1980, 1 (02) :113-117
[50]   Incommensurate structures in organic-inorganic metal-halides [J].
Gagor, A. ;
Drozdowski, D. .
ACTA CRYSTALLOGRAPHICA A-FOUNDATION AND ADVANCES, 2024, 80