PRODUCTION OF NCL(A) BY THERMAL-DECOMPOSITION OF CLN3

被引:43
作者
BENARD, DJ [1 ]
CHOWDHURY, MA [1 ]
WINKER, BK [1 ]
SEDER, TA [1 ]
MICHELS, HH [1 ]
机构
[1] UNITED TECHNOL RES CTR,E HARTFORD,CT 06108
关键词
D O I
10.1021/j100382a037
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
Thermal decomposition of ClN3 by pulsed CO2 laser pyrolysis has been investigated by using SF6 as a sensitizer. The electronically excited decomposition products, NCl(a) and NCl(b), were monitored by absolute time-resolved emission spectroscopy while ClN3 was followed by ultraviolet absorption. The results indicate a higher barrier to dissociation of ClN3 than FN3, consistent with ab initio calculations, and an NCl(a) yield of order unity, based on a nominal 0.7/s radiative rate for the NCl(a-X) transition. Studies of simultaneous dissociation of FN3 and ClN3 have also revealed that NCl(a), when coproduced with NF(a), upconverts the latter species to NF(b) efficiently (in the presence of trace I2) and cooperatively pumps the IF(B) state (upon addition of CF3I) by an energy pooling mechanism that does not involve NF(b) as an intermediate. These results indicate a potential for development of chemical lasers that operate on either the NF(b→X) or IF(B→X) transitions at visible wavelength. © 1990 American Chemical Society.
引用
收藏
页码:7507 / 7514
页数:8
相关论文
共 56 条
[1]   CONFIGURATION INTERACTION STUDIES OF NF AND NF+ [J].
ANDERSEN, A ;
OHRN, Y .
JOURNAL OF MOLECULAR SPECTROSCOPY, 1973, 45 (03) :358-365
[2]   MATRIX-ISOLATED NCL - RADIATIVE RATES FOR B1-SIGMA+-]A1-DELTA,B1-SIGMA+-]X3-SIGMA- AND A 1-DELTA-]X3-SIGMA- IN SOLID ARGON [J].
BECKER, AC ;
SCHURATH, U .
CHEMICAL PHYSICS LETTERS, 1989, 160 (5-6) :586-590
[3]   PRODUCTION OF NF(A1-DELTA) BY DISSOCIATION OF FLUORINE AZIDE [J].
BENARD, DJ ;
WINKER, BK ;
SEDER, TA ;
COHN, RH .
JOURNAL OF PHYSICAL CHEMISTRY, 1989, 93 (12) :4790-4796
[4]  
BENARD DJ, 1988, 87071 AIR FORC ASTR
[5]  
BENARD DJ, 1986, J APPL PHYS, V60, P405
[6]   CHEMILUMINESCENCE OF IF IN THE GAS PHASE REACTION OF I2 WITH F2 [J].
BIRKS, JW ;
GABELNICK, SD ;
JOHNSTON, HS .
JOURNAL OF MOLECULAR SPECTROSCOPY, 1975, 57 (01) :23-46
[7]  
BOWER RD, UNPUB
[8]   NF(B1-SIGMA+) QUENCHING RATE CONSTANTS BY HALOGENS AND INTERHALOGENS AND THE EXCITATION RATE-CONSTANT FOR IF(B) FORMATION [J].
CHA, H ;
SETSER, DW .
JOURNAL OF PHYSICAL CHEMISTRY, 1987, 91 (14) :3758-3767
[9]   STRUCTURE OF TRIAZADIENYL FLUORIDE, FN3, BY MICROWAVE, INFRARED, AND ABINITIO METHODS [J].
CHRISTEN, D ;
MACK, HG ;
SCHATTE, G ;
WILLNER, H .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1988, 110 (03) :707-712
[10]   KINETIC MECHANISM IN NITROGEN-CHLORINE RADICAL SYSTEMS .1. - FORMATION AND DETECTION OF NCL2 AND N3 FREE RADICALS USING TIME-RESOLVED ABSORPTION SPECTROPHOTOMETRY [J].
CLARK, TC ;
CLYNE, MAA .
TRANSACTIONS OF THE FARADAY SOCIETY, 1969, 65 (563P) :2994-&