Eighth Condensed Phase and Interfacial Molecular Science (CPIMS)

2. Optical Stark study of PtF (Accepted JCP)
Figure 1. The pure rotational spectrum of
195 12 1
Pt C ( X �
� ,v=0) recorded using the
PPMODR technique and associated energy
1
levels. The rotational transitions in the X �
�
state(“a-c”) are detected as an increase in the
laser induced fluorescence (LIF) signal of the
R(2) line of A 1 � � X 1 � + (0,0) band near 540
1
nm. The small splittings in the X �
� state are
due to the nuclear spin-rotation interaction.
� and the 19 F(I=1/2) and 195 Pt(I=1/2) magnetic hyperfine
We have determined el
2
interactions in the [11.9]�=3/2 and X � states of PtF. PtF has been the subject of two electronic
3/2
structure predictions; Liu and Franke [J. Comp. Chem. 23, 564 (2002)] and Zou, Liu and J.E.
Boggs, [Dalton Trans., 39, 2023 (2010)]. Both calculations predict that when spin-orbit coupling is
taken into account the 2
� , 2
2 �
� , and � states expected for a Pt + (5d 9 )F - (2p 6 ) configuration regroup
i i
into two sets of states separated by approximately 10,000 cm -1 : a low energy group having � = 5
2 ,
3 1 , and 2 2
from the
arising from the
4 5 2
d3/2d5/2� 1/2 superconfiguration and the high energy � = 3
2
and 1
2 set
3 6 2
d3/2d5/2� 1/2 superconfiguration. The two theoretical predictions are inconsistent the
observed hyperfine interaction (Figure 2)
2
Electric dipole moments of 2.47(11)D and 3.42(6)D for the [11.9]�=3/2 and X � states,
respectively, were determined. The observed trend in � el for the PtX (X= C,N,O,S and F) series
strongly correlates with electronegativities (Figure 3) .
172
3/2
Figure 2. The observed and predicted
spectra for the R(2.5) (v=11933.4 cm -1 )
branch feature of the for the Ω=3/2 ←
X 2 Π 3/2 (1,0) band of 195 PtF. The
splitting is due to 195 Pt(I=1/2) and
19 F(I=1/2) hyperfine interaction. The
determined hyperfine parameters
h3/2( 195 Pt)(=706 MHz) and h3/2( 195
Pt)(=304MHz) are inconsistent with
current theoretical prediction of 1820
MHz and 0 MHz.