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Microwave spectroscopy of the heavy-atom carbene analog
HSiI and DSiI
Lu KangSouthern Polytechnic State University
Marietta, GA
Mohammed A. Gharaibeh and Dennis J. ClouthierUniversity of Kentucky, Lexington, KY
Stewart E. NovickWesleyan University, Middletown, CT
Dennis Clouthier (pronounced Clue-chay)
Pete Pringle (pronounced Pringle) & Lu Kang
Jim Cederberg, St. Olaf College
Lu is at St. Olaf learning to use Jim’sMBER (originally Norman Ramsey’s)
H3SiI in a methanol/dry ice bath held between -40 and -50 C, P ~ 5 torr
5 torr H3SiI in 2 atm of Ne, discharge of -1000 V immediately followingsupersonic expansion to produce HSiI (or DSiI if we start with D3SiI)
2/3
Spectroscopic constants of HSiI as measured by FTMW spectroscopy
The r0 structure of HSiI
1.5405 A
92.68 o
2.4614 A
This work Clouthier et al a
r0(H – Si) 1.5405(16) Å 1.534(1) Å
r0(Si – I) 2.46143(9) Å 2.463(1) Å
θ0(HSiI) 92.68(6)° 92.4(1)°
a. D.J. Clouthier, W.W. Harper, C.M. Klusek, T.C. Smith, J. Chem. Phys. 109, 7827 (1998), jet-cooled pulsed-discharge
HSiCl a HGeCl b HGeBr c HSiI d
Bond angle
95o 95.3o 94.1o 92.7 o
(Xbb-Xcc) Xaa
-1.185e -1.025e -0.965 -0.914
a. W. Lin, S. E. Novick, M. Fukushima, W. Jäger, J. Phys. Chem. A 106, 7703 (2002), D.A. Hostutler, N. Ndiege, D.J. Clouthier, S.W. Pauls, J. Chem. Phys. 115, 5485 (2001)b. W. Lin, L. Kang, S.E. Novick, J. Mol. Spectrosc. 230, 93 (2005)c. L. Kang, F. Sunahori, A.J. Minei, D.J. Clouthier, S.E. Novick, J. Chem. Phys. 130, 24317 (2009)d. This worke. B3LYP/aug-cc-pvqz
b
a
c
χaa=-795.744 MHz
χbb=+833.330 MHz
χcc=-37.586 MHz
Extended Townes-Dailey analysis of the quadrupole tensor
χ0 = +2292.712 MHz, 127I, 5p electron. Gordy & Cooke has +292.71 MHz, a typo.
Xaa
0
0
0
Xbb
0
0
0
Xcc
na
X0
0
0
0
.5 X0
0
0
0
.5 X0
nb
.5 X0
0
0
0
X0
0
0
0
.5 X0
nc
.5 X0
0
0
0
.5 X0
0
0
0
X0
HSiI: na = 1.53, nb = 2.00, nc =1.75
{HGeBr: na = 1.58, nb = 2.00, nc = 1.80}
