Reactions of laser-ablated chromium atoms with dioxygen. Infrared spectra of CrO, OCrO, CrOO, CrO3, Cr(OO)(2), Cr2O2, Cr2O3 and Cr2O4 in solid argon

被引:95
作者
Chertihin, GV
Bare, WD
Andrews, L
机构
[1] Department of Chemistry, University of Virginia, Charlottesville
关键词
D O I
10.1063/1.474637
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
Reactions of laser-ablated Cr atoms with O-2 gave a very strong, sharp 965.4 cm(-1) band and weak, sharp 1869.7, 984.3, 914.4, 846.3, 716.2, and 643.1 cm(-1) bands. The 1869.7, 965.4, and 914.4 cm(-1) bands track together on annealing, show Cr-52, Cr-53, Cr-54 isotopic splittings appropriate for a single Cr atom and triplets with statistical O-16,18(2) for two equivalent O atoms, and are assigned to the upsilon(1) + upsilon(3), upsilon(3) and upsilon(1) modes of the bent (128 degrees+/-4 degrees) chromium dioxide OCrO molecule. The 984.3 cm(-1) band shows chromium isotopic splittings for two Cr atoms and O-16,18(2) components for two O atoms, and is attributed to the bent CrOCrO molecule. The weak 846.3 cm(-1) band exhibits proper oxygen isotopic behavior for CrO and is redshifted 39 cm(-1) from the gas-phase value, the maximum shift observed for a first row transition metal monoxide. The sharp 716.2 and 643.1 cm(-1) bands crack together; the former reveals Cr isotopic splittings for two Cr atoms and the latter O-16,18(2) splittings for two sets of dioxygen subunits; the branched-puckered-ring dimer O(Cr2O2)O is identified. Annealing produces new bands due to CrOO, CrO3, Cr(OO)(2) and the ring dimers (Cr2O2) and (Cr2O2)O, which are identified from isotopic shifts and splitting patterns. (C) 1997 American Institute of Physics.
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页码:2798 / 2806
页数:9
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共 32 条
[1]   MATRIX PHOTOOXIDATION OF THE METAL-CARBONYLS CR(CO)6,W(CO)6 BY THE ISOELECTRONIC MOLECULES CARBON-DIOXIDE AND NITROUS-OXIDE [J].
ALMOND, MJ ;
DOWNS, AJ ;
PERUTZ, RN .
INORGANIC CHEMISTRY, 1985, 24 (03) :275-281
[2]   FORMATION OF MOLECULAR CHROMIUM(IV) OXIDE (CRO2) BY PHOTOLYSIS OF CR(CO)6 IN O-2-DOPED ARGON MATRICES [J].
ALMOND, MJ ;
HAHNE, M .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1988, (09) :2255-2260
[3]   REACTIONS OF PULSED-LASER EVAPORATED ALUMINUM ATOMS WITH OXYGEN - INFRARED-SPECTRA OF THE REACTION-PRODUCTS IN SOLID ARGON [J].
ANDREWS, L ;
BURKHOLDER, TR ;
YUSTEIN, JT .
JOURNAL OF PHYSICAL CHEMISTRY, 1992, 96 (25) :10182-10189
[4]   REACTIONS OF PULSED-LASER EVAPORATED CA, SR, AND BA ATOMS WITH O-2 - INFRARED-SPECTRA OF THE METAL-OXIDES, OXIDE DIMERS, DIOXIDES, AND PEROXIDES IN SOLID ARGON [J].
ANDREWS, L ;
YUSTEIN, JT ;
THOMPSON, CA ;
HUNT, RD .
JOURNAL OF PHYSICAL CHEMISTRY, 1994, 98 (26) :6514-6521
[5]   Reactions of laser-ablated iron atoms with oxygen molecules: Matrix infrared spectra and density functional calculations of OFeO, FeOO, and Fe(O-2) [J].
Andrews, L ;
Chertihin, GV ;
Ricca, A ;
Bauschlicher, CW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (02) :467-470
[6]   ROTATIONAL ANALYSIS OF THE A'(5)DELTA-X(5)PI TRANSITION OF CRO [J].
BARNES, M ;
HAJIGEORGIOU, PG ;
MERER, AJ .
JOURNAL OF MOLECULAR SPECTROSCOPY, 1993, 160 (01) :289-310
[7]   TRANSITION-METAL OXIDES - CRO, MOO, NIO, PDO, AGO [J].
BAUSCHLICHER, CW ;
NELIN, CJ ;
BAGUS, PS .
JOURNAL OF CHEMICAL PHYSICS, 1985, 82 (07) :3265-3276
[8]   THEORETICAL-STUDY OF THE FIRST TRANSITION ROW OXIDES AND SULFIDES [J].
BAUSCHLICHER, CW ;
MAITRE, P .
THEORETICA CHIMICA ACTA, 1995, 90 (2-3) :189-203
[9]   REACTIONS OF LASER-ABLATED TITANIUM, ZIRCONIUM, AND HAFNIUM ATOMS WITH OXYGEN MOLECULES IN CONDENSING ARGON [J].
CHERTIHIN, GV ;
ANDREWS, L .
JOURNAL OF PHYSICAL CHEMISTRY, 1995, 99 (17) :6356-6366
[10]   Reactions of laser-ablated iron atoms with oxygen molecules in condensing argon. Infrared spectra and density functional calculations of iron oxide product molecules [J].
Chertihin, GV ;
Saffel, W ;
Yustein, JT ;
Andrews, L ;
Neurock, M ;
Ricca, A ;
Bauschlicher, CW .
JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (13) :5261-5273