Laboratory of Millimetre-wave Spectroscopy of Bologna The
ROTATIONAL SPECTRUM of HDO : ACCURATE SPECTROSCOPIC and HYPERFINE
PARAMETERS G. Cazzoli*, V. Lattanzi*, C. Puzzarini*, J. Gauss #
*Dip. Chimica Giacomo Ciamician Universit di Bologna # # Institut
fr Physikalische Chemie, Universitt Mainz 69th Meeting - June
16-20, 2014 Champaign-Urbana, Illinois 69th Meeting - June 16-20,
2014 Champaign-Urbana, Illinois 69th Meeting - June 16-20, 2014
Champaign-Urbana, Illinois Submitted ABSTRACT Laboratory of
Millimetre-wave Spectroscopy of Bologna Working frequency range: 65
GHz 1.6 THz Laboratory of Millimetre-wave Spectroscopy of Bologna
Measurements: Lamb-dip technique using free-space cell G. Cazzoli
& L. Dore, J. Mol. Spectrosc. 143, 231 (1990) Laboratory of
Millimetre-wave Spectroscopy of Bologna H 2 S: J = 8 6,3 8 5,4 >
4 MHz Lamb-dip in the THz Laboratory of Millimetre-wave
Spectroscopy of Bologna H 2 S: J = 8 6,3 8 5,4 ~100 kHz Cazzoli
& Puzzarini, J. Phys. Chem. A 117, (2013) Laboratory of
Millimetre-wave Spectroscopy of Bologna D 2 O: J = 3 2,2 3 1,3 50
kHz F = F = F = 5 - 5 69th Meeting - June 16-20, 2014
Champaign-Urbana, Illinois NO hyperfine structure Hyperfine
structure due to D Hyperfine structure: effect of H Hyperfine
structure: inclusion of spin-spin coupling Experiment Calc: full
HFS ? ? Experiment Calc: real + ghost Results ParameterEXPAB INITIO
aa (D) / MHz0.2772(12)0.281 bb (D) / MHz (38) cc (D) / MHz (38) C
aa (D) / kHz -1.19(18) C bb (D) / kHz-4.63(20) C cc (D) /
kHz-3.78(16)-3.48 C aa (H) / kHz-57.95( 40) C bb (H) /
kHz-9.59(37)-8.52 C cc (H) / kHz ( 57) S aa (H-D) /
kHz-8.33(59)-8.40 Level of Theory Geometry Geometry: semi-exp r e
Equilibrium Equilibrium: all-CCSD(T)/aug-cc-pCV6Z Vibrational
Correction Vibrational Correction: all-CCSD(T)/aug-cc-pCV5Z Results
ParameterEXPAB INITIO aa (D) / MHz0.2772(12)0.281 bb (D) / MHz (38)
cc (D) / MHz (38) C aa (D) / kHz -1.19(18) C bb (D) / kHz-4.63(20)
C cc (D) / kHz-3.78(16)-3.48 C aa (H) / kHz-57.95( 40) C bb (H) /
kHz-9.59(37)-8.52 C cc (H) / kHz ( 57) S aa (H-D) /
kHz-8.33(59)-8.40 Hyperfine structure only due to D with SR of D
without SR of D Hyperfine structure only due to D ~ 4 kHz Other
Results Spectroscopic Parameters Rotational Constants Rotational
Constants: Uncert. = 4-10 kHz Centrifugal Distortion Const.
Centrifugal Distortion Const.: up to octics (a few decics) Future
Work 500 1600 GHz Lamb-dip Measurements up to 1.2 THz (strong
lines) Improved Doppler-limited Measurements: up to 1.6 THz (weak
lines) Laboratory of Millimetre-wave Spectroscopy of Bologna THANK
YOU For YOUR ATTENTION THANKS $$$$$$: MIUR & University of
Bologna
