Khả Năng Phản Ứng Quang Học của Dioxyt Clo

American Association for the Advancement of Science (AAAS) - Tập 268 Số 5216 - Trang 1443-1448 - 1995
Veronica Vaida1, John D. Simon2
1Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO 80309 USA
2Department of Chemistry and Biochemistry, University of California at San Diego, La Jolla, CA 92093-0341, USA.

Tóm tắt

Việc xác định chi tiết khả năng phản ứng quang học của các gốc tự do quan trọng trong các quá trình khí quyển đòi hỏi thông tin từ cả các phép đo trong phòng thí nghiệm và thực địa cũng như các tính toán lý thuyết. Các thí nghiệm trong phòng và các tính toán lượng tử đã được thực hiện để phát triển sự hiểu biết toàn diện về khả năng phản ứng quang học của dioxyt clo (OCIO). Khả năng phản ứng quang học phụ thuộc mạnh mẽ vào môi trường (pha khí, dung dịch lỏng, hoặc ma trận cryogen). Các dữ liệu này tiết lộ chi tiết về hóa học phức tạp của OCIO. Vai trò tiềm năng của gốc tự do này trong việc làm suy giảm tầng ozon ở tầng bình lưu được thảo luận phù hợp với các phép đo trong phòng thí nghiệm này.

Từ khóa

#phản ứng quang học #gốc tự do #quá trình khí quyển #dioxyt clo #tính toán lượng tử #suy giảm tầng ozon #tầng bình lưu #phòng thí nghiệm #phép đo thực địa #ma trận cryogen

Tài liệu tham khảo

World Meteorlogical Organization Report 20 1 (1990).

ADRIAN, F.J., ELECTRON-SPIN-RESONANCE INVESTIGATION OF THE PHOTOISOMERIZATION OF OCIO TO CIOO IN AN H2SO4 GLASS - MAGNETOPHOTOSELECTION AND KINETICS, JOURNAL OF CHEMICAL PHYSICS 85: 2692 (1986).

ANDERSON, J.G., OZONE DESTRUCTION BY CHLORINE RADICALS WITHIN THE ANTARCTIC VORTEX - THE SPATIAL AND TEMPORAL EVOLUTION OF CLO-O3 ANTICORRELATION BASED ON INSITU ER-2 DATA, JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES 94: 11465 (1989).

ANDERSON, J. G., JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES 94: 11480 (1989).

ARKELL, A, MATRIX INFRARED STUDY OF C100 RADICAL, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 89: 5999 (1967).

BAER, S, THERMODYNAMIC AND KINETIC-PROPERTIES OF THE REACTION CL+O2+M-REVERSIBLE-CLOO+M IN THE RANGE 160-300-K AND 1-1000 BAR, JOURNAL OF CHEMICAL PHYSICS 95: 6463 (1991).

BAUMERT, T, FEMTOSECOND REAL-TIME PROBING OF REACTIONS .11. THE ELEMENTARY OCLO FRAGMENTATION, JOURNAL OF CHEMICAL PHYSICS 99: 4430 (1993).

BISHENDEN, E, MODE-SPECIFIC CHEMICAL BRANCHING RATIOS IN THE PHOTODISSOCIATION OF OCLO, JOURNAL OF CHEMICAL PHYSICS 99: 3129 (1993).

Brasseur G. Aeronomy of the Middle Atmosphere (1986).

BRUNE, W. H., JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES 94: 16649 (1989).

COLUSSI, A.J., LASER FLASH-PHOTOLYSIS OF CHLORINE DIOXIDE - FORMATION AND ULTRAVIOLET-ABSORPTION SPECTRUM OF CL2O3, JOURNAL OF PHYSICAL CHEMISTRY 93: 4783 (1989).

COLUSSI, A.J., FORMATION AND DECAY OF (P-3(J))O ATOMS IN THE LASER FLASH-PHOTOLYSIS OF CHLORINE DIOXIDE (OCLO) AT 308NM, JOURNAL OF PHYSICAL CHEMISTRY 94: 8922 (1990).

COON, J.B., ROTATIONAL STRUCTURE OF SOME ELECTRONIC BANDS OF CHLORINE DIOXIDE, JOURNAL OF CHEMICAL PHYSICS 14: 665 (1946).

DAVIS, H.F., DYNAMICS AND MODE SPECIFICITY IN OCLO PHOTODISSOCIATION, JOURNAL OF PHYSICAL CHEMISTRY 96: 5681 (1992).

Dunn R. C. Journal of Physical Chemistry in press.

DUNN, R.C., EXCITED-STATE PHOTOREACTIONS OF CHLORINE DIOXIDE IN WATER, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 114: 4856 (1992).

DUNN, R.C., SOLUTION PHOTOCHEMISTRY OF CHLORINE DIOXIDE - MECHANISMS FOR THE GENERATION OF ATOMIC CHLORINE, JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 115: 5307 (1993).

DUNN, R.C., THE SPECTROSCOPY OF OCLO IN POLAR LIQUIDS, SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY 48: 1293 (1992).

FARMAN, J.C., LARGE LOSSES OF TOTAL OZONE IN ANTARCTICA REVEAL SEASONAL CLOX/NOX INTERACTION, NATURE 315: 207 (1985).

Glownia, J. H., Supercontinuum Lasers: 1 (1990).

GOLE, J.L., PHOTOCHEMICAL ISOMERIZATION OF CIO2 AND THE LOW-LYING ELECTRONIC STATE OF THE ASYMMETRIC ISOMER - POSSIBLE IMPLICATIONS FOR MATRIX-ISOLATION SPECTROSCOPY, JOURNAL OF PHYSICAL CHEMISTRY 84: 1333 (1980).

HANSON, D. R., JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES 96: 5081 (1991).

JAFRI, J.A., THE LOWER ELECTRONIC STATES OF CLOO - A COMPUTATIONAL INVESTIGATION, JOURNAL OF CHEMICAL PHYSICS 83: 1693 (1985).

JOHNSSON, K, A MATRIX-ISOLATION STUDY OF THE WATER COMPLEXES OF CL2, CLOCL, OCLO AND HOCL AND THEIR PHOTOCHEMISTRY, JOURNAL OF MOLECULAR STRUCTURE 293: 137 (1993).

JOHNSSON, K, A MATRIX-ISOLATION STUDY OF THE WATER COMPLEXES OF CL2, CLOCL, OCLO, AND HOCL AND THEIR PHOTOCHEMISTRY, JOURNAL OF PHYSICAL CHEMISTRY 96: 5778 (1992).

JONES, R. L., JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES 94: 11529 (1989).

LAWRENCE, W. G., JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES 95: 18591 (1990).

MCELROY, M.B., REDUCTIONS OF ANTARCTIC OZONE DUE TO SYNERGISTIC INTERACTIONS OF CHLORINE AND BROMINE, NATURE 321: 759 (1986).

MICHIELSEN, S, A STUDY OF THE ROTATIONAL STATE DEPENDENCE OF PREDISSOCIATION OF A POLYATOMIC MOLECULE - THE CASE OF CIO2, JOURNAL OF CHEMICAL PHYSICS 74: 3089 (1981).

MIYAZAKI, K, MICROWAVE-SPECTRUM OF CHLORINE DIOXIDE IN EXCITED VIBRATIONAL-STATES, JOURNAL OF MOLECULAR SPECTROSCOPY 116: 435 (1986).

MOLINA, L.T., PRODUCTION OF CL2O2 FROM THE SELF-REACTION OF THE CIO RADICAL, JOURNAL OF PHYSICAL CHEMISTRY 91: 433 (1987).

10.1126/science.238.4831.1253

MULLER, HSP, SYNTHESIS AND PROPERTIES OF CHLORYL CHLORIDE, CLCLO2, INORGANIC CHEMISTRY 31: 2527 (1992).

PAILLARD, C, INFLUENCE OF CHEMICAL-KINETICS ON DETONATION STRUCTURE - THE CASE OF CHLORINE DIOXIDE, ANNALES DE PHYSIQUE 14: 641 (1989).

PETERSON, K.A., MULTIREFERENCE CONFIGURATION-INTERACTION CALCULATIONS OF THE LOW-LYING ELECTRONIC STATES OF CLO2, JOURNAL OF CHEMICAL PHYSICS 96: 8948 (1992).

Purcell C. J. Journal of Physical Chemistry in press.

Reichardt C. Solvents and Solvent Effects in Organic Chemistry (1988).

RICHARD, E.C., THE DIRECT NEAR ULTRAVIOLET-ABSORPTION SPECTRUM OF THE A2A2[-X2B1 TRANSITION OF JET-COOLED CHLORINE DIOXIDE, JOURNAL OF CHEMICAL PHYSICS 94: 153 (1991).

RICHARD, E. C., JOURNAL OF CHEMICAL PHYSICS 94: 153 (1991).

RICHARDSON, A.W., J MOL SPECTROSC 29: 93 (1973).

ROBERTS J.T. unpublished data.

RUHL, E, PHOTODISSOCIATION OF OCLO - REMPI STUDY OF PRIMARY PHOTOFRAGMENTS, JOURNAL OF PHYSICAL CHEMISTRY 94: 2990 (1990).

10.1126/science.245.4922.1095

SCHILLER, C, NEAR UV ATMOSPHERIC ABSORPTION-MEASUREMENTS OF COLUMN ABUNDANCES DURING AIRBORNE ARCTIC STRATOSPHERIC EXPEDITION, JANUARY - FEBRUARY 1989 .2. OCLO OBSERVATIONS, GEOPHYSICAL RESEARCH LETTERS 17: 501 (1990).

SOLOMON, S, JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES 94: 11393 (1989).

SOLOMON, S, ON THE DEPLETION OF ANTARCTIC OZONE, NATURE 321: 755 (1986).

SOLOMON, S, PROGRESS TOWARDS A QUANTITATIVE UNDERSTANDING OF ANTARCTIC OZONE DEPLETION, NATURE 347: 347 (1990).

10.1126/science.264.5158.527

TUCK, A. F., JOURNAL OF GEOPHYSICAL RESEARCH-ATMOSPHERES 94: 11181 (1989).

TURNIPSEED, A.A., KINETICS AND TEMPERATURE-DEPENDENCE OF THE BRO + CLO REACTION, JOURNAL OF PHYSICAL CHEMISTRY 95: 4356 (1991).

VAIDA, V, COMPARISONS BETWEEN THE REACTIVITY OF CHLORINE DIOXIDE IN THE GAS-PHASE AND WATER SOLUTION, JOURNAL OF MOLECULAR LIQUIDS 61: 133 (1994).

VAIDA, V, PHOTOISOMERIZATION OF OCLO - A POSSIBLE MECHANISM FOR POLAR OZONE DEPLETION, NATURE 342: 405 (1989).

10.1126/science.261.5125.1130