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Citation: Huang Yuhui, Cao Jianru, Wen Ye, Zhong Xian, Zhang Jianming, Fang Wanquan, Wu Xiaojun, Zhu Qihe. PHOTOFRAGMENTATION OF n-C₃H₇I AND i-C₃H₇I[J]. Acta Physico-Chimica Sinica, ;1987, 3(04): 337-340. doi: 10.3866/PKU.WHXB19870401 shu

PHOTOFRAGMENTATION OF n-C₃H₇I AND i-C₃H₇I

1.
Institute of Chemistry; Academia Sinica; Beijing

Received Date: 2 March 1987
Available Online: 15 August 1987

Studies on the photofragmentation of n-C_3H_7I and i-C_3H_7I have been carried out by a photofragment spectrometer with rotatable pulsed molecular beam crossed with KrF excimer laser beam. TOF spectra of the iodine atom fragments (Fig.1, 2) which show the separation of the primary photodissociation channels
n-C_3H_7I→n-C_3H_7+I~*(~2P_(1/2))
n-C_3H_7+I(~2p_(3/2))
i-C_3H_7I→i-C_3H_7+I~*(~2P_(1/2))
i-C_3H_7+I(~2P_(3/2))
are obtatned at 12 different angles. The distribution of total translational energy E_(CM) of recoiling photofragments are then determined. The ratios I~*/I of the photodissociation channels of n-C_3H_7I and i-C_3H_7I are measured to be 1.61 and 0.96 respectively (Table 1). The ratios I~*/I obtained by photofragment translational energy measurement in this Lab~[3]. are od in agreement with most of results abtained by IR emission~[5] and LIF~[4] measurement except the data of i-C_3H_7I, which is much different from I~*/I=0.35 reported by Bershon~[4] using LIF method.
The extent of internal alkyl fragment excitation E_(int)~R is also determined (Table 2) by energy balance. The fraction of the available energy (E_(av1)=E_(CM)+E_(int)~R) which es into internal exciatation of the alkyl fragment increases from 12.5% for I~* channe of CH_3I to 64% for both channels of i-C_3H_7I. The results are consistent with direct impulsive dynamic model of unimolecular decomposition based on “soft” alkyl radicals.
The facts that the ratio I~*/I decreases with increasing carbon atoms and that the difference of the internal excitation of alkyl radicals between the I~* (~2P_(1/2)) and I (~2P_(3/2)) channelsincreases with increasing carbon atoms should be related and important for better understanding the origin of the I(~2P_(3/2)) channel caused by the potential energy surface crossing~[3]. The results of the internal excitation of the alkyl radicals in the photodissociation are also valuable for prediction of secondary products during the UV photolysis of those alkyl iodides in the gas cell.
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PHOTOFRAGMENTATION OF n-C3H7I AND i-C3H7I

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PHOTOFRAGMENTATION OF n-C₃H₇I AND i-C₃H₇I