Photofragmentation of Ammonia 193.3 nm: Bimodal Rotational Distribution and Vibrational Excitation of NH2( )

Published

January 1, 2000

Author(s)

R A. Loomis, J P. Reid, S R. Leone

Abstract

Time-resolved Fourier transform infrared emission spectroscopy is used to measure the nascent rovibrational distribution of low-lying electronically excited NH₂(A²A₁) produced in the 193.3 nm photolysis of room-temperature and jet-cooled ammonia. Emission is observed predominantly from NH₂(A) states with rotational motion about the a-axis and without bending excitation 1/2=0. A bimodal N'=K'_a rotational state population distribution is observed with up to K'/a =7 in 1/2 = 0 and with maxima at K'/a = 5 and K'/a = 1. We suggest that the bimodal rotational distribution may result from the competition between planar and bent geometries during dissociation. Weaker emission from NH₂(A) with bending excitation, Ņ'/2 =1 and 2, is detected; the Ņ'/2=1, N' = K'/a rotational state population distribution spans from K'/a = 0 to the energetic limit of K'/a=4. The vibrational energy partitioning for the formation of NH₂(A,Ņ'/2=1) is 3:1 and 2:1 in the room-temperature and jet-cooled conditions, respectively. An upper limit of the NH₂(A, Ņ'/2=2)population is 10% of the total NH₂(A) photofragments. Emission from rotational states with N'>K'/a (molecules with rotational excitation about the b/c-axes) is also observed. Under jet-cooled conditions the NH₂(A) b/c-axes rotational temperature of 120 K is higher than that expected from the rotationally cold parent species and is attributed to a mapping of the zero-point bending motion in the Ņ6d4^ H-N-H scissors bending coordinate of the NH₃(A) predissociative state onto the NH₂(A, Ņ'/2, N', K'/1) + H photofragments.

Citation

Journal of Chemical Physics

Volume

112

Issue

No. 2

Pub Type

Journals

Keywords

photodissociation, reaction dynamics, zero-point motion

Citation

Loomis, R. , Reid, J. and Leone, S. (2000), Photofragmentation of Ammonia 193.3 nm: Bimodal Rotational Distribution and Vibrational Excitation of NH₂( ), Journal of Chemical Physics (Accessed October 15, 2024)