PHOTODISSOCIATION DYNAMICS OF STATE-SELECTED RESONANCES OF HCO (X))OVER-TILDE(2)A' PREPARED BY STIMULATED-EMISSION PUMPING

被引:60
作者
NEYER, DW
LUO, X
BURAK, I
HOUSTON, PL
机构
[1] CORNELL UNIV,DEPT CHEM,ITHACA,NY 14853
[2] TEL AVIV UNIV,SCH CHEM,IL-69978 TEL AVIV,ISRAEL
关键词
D O I
10.1063/1.468896
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
Metastable resonances on the ground electronic state of the HCO radical have been prepared by stimulated emission pumping. The resonances have energies 5000 to 10 000 cm-1 above the dissociation limit of HCO and can be assigned by their vibrational and asymmetric-top rotational character. The transition linewidths of the resonances and the rotational and vibrational distributions of the CO dissociation products have been measured. The linewidths show a strong dependence on the vibrational character of the resonance rather than a monotonic dependence on energy, and thus provide an important example of nonstatistical behavior. CO(v=2) was produced in the decay of all six resonances studied, while only the three highest energy resonances produced measurable amounts of CO(v=3). CO rotational distributions with population in low-J states, which often showed nonstatistical structure, were characteristic of the products from all the resonances studied. The rotational distributions depend both on the vibrational character of the parent state and on the rotational state prepared in the HCO. The experimental results are compared and contrasted with previous quantum mechanical calculations and analyzed in the context of a modified Franck-Condon model for the dissociation. © 1995 American Institute of Physics.
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页码:1645 / 1657
页数:13
相关论文
共 91 条
[1]   THE HCO (B)TILDE(2)A'[--](X)TILDE(2)A' SYSTEM - FLUORESCENCE EXCITATION AND STIMULATED-EMISSION PUMPING SPECTRA [J].
ADAMSON, GW ;
ZHAO, XS ;
FIELD, RW .
JOURNAL OF MOLECULAR SPECTROSCOPY, 1993, 160 (01) :11-38
[2]  
ADAMSON GW, 15TH P COMB RES C BR
[3]   STRONG PROPENSITY RULES IN THE PHOTODISSOCIATION OF A SINGLE ROTATIONAL QUANTUM STATE OF VIBRATIONALLY EXCITED H2O [J].
ANDRESEN, P ;
BEUSHAUSEN, V ;
HAUSLER, D ;
LULF, HW ;
ROTHE, EW .
JOURNAL OF CHEMICAL PHYSICS, 1985, 83 (03) :1429-1430
[4]   BENDING CONTRIBUTION TO ROTATIONAL DISTRIBUTIONS IN THE PHOTO-DISSOCIATION OF POLYATOMIC-MOLECULES [J].
BESWICK, JA ;
GELBART, WM .
JOURNAL OF PHYSICAL CHEMISTRY, 1980, 84 (24) :3148-3151
[5]   ABINITIO CALCULATIONS OF ELECTRONIC AND VIBRATIONAL ENERGIES OF HCO AND HOC [J].
BOWMAN, JM ;
BITTMAN, JS ;
HARDING, LB .
JOURNAL OF CHEMICAL PHYSICS, 1986, 85 (02) :911-921
[6]   VARIATIONAL CALCULATIONS OF BOUND AND QUASI-BOUND STATES OF HCO (J=0 AND 1) AND COMPARISON WITH EXPERIMENT [J].
BOWMAN, JM ;
GAZDY, B .
CHEMICAL PHYSICS LETTERS, 1992, 200 (03) :311-317
[7]   A SIMPLE METHOD TO ADJUST POTENTIAL-ENERGY SURFACES - APPLICATION TO HCO [J].
BOWMAN, JM ;
GAZDY, B .
JOURNAL OF CHEMICAL PHYSICS, 1991, 94 (01) :816-817
[8]   AXIS SWITCHING IN A2A''-X2A' TRANSITION OF HCO - DETERMINATION OF MOLECULAR GEOMETRY [J].
BROWN, JM ;
RAMSAY, DA .
CANADIAN JOURNAL OF PHYSICS, 1975, 53 (19) :2232-2241
[9]   STATE-RESOLVED DIFFERENTIAL CROSS-SECTIONS FOR THE REACTION D+H2-]HD+H [J].
BUNTIN, SA ;
GIESE, CF ;
GENTRY, WR .
JOURNAL OF CHEMICAL PHYSICS, 1987, 87 (02) :1443-1445
[10]   STATE-TO-STATE PHOTODISSOCIATION DYNAMICS OF TRANS-GLYOXAL [J].
BURAK, I ;
HEPBURN, JW ;
SIVAKUMAR, N ;
HALL, GE ;
CHAWLA, G ;
HOUSTON, PL .
JOURNAL OF CHEMICAL PHYSICS, 1987, 86 (03) :1258-1268