Abstract
Two new band systems have been observed in absorption following flash photolysis of AsH
3
and AsD
3
, and are assigned to
2
A
1
-
2
B
1
electronic transitions of AsH
2
and AsD
2
. The origins of both systems are at 19905 cm
-1
. The bands have the complex rotational structure associated with an asymmetric rotor. Rotational analyses have been carried out for three bands of the AsH
2
spectrum, leading to the following molecular parameters: ground state,
r"
0
= 1.518 Å valence angle = 90° 44'; excited state,
r'
0
= 1.48 Å, valence angle = 123° 0'. The parameters associated with rotation about the
a
inertial axis increase rapidly with increase in
v'
2
. The spectrum shows doublet splittings of up to 41 cm
-1
, and the excited state furnishes the first example of a doublet state of an asymmetric top molecule which shows substantial departures from Hund’s case (
b
).
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