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353 Tb7.

2
T1a7.2

SPECTROSCOPY
SPECTROSCOPY AND
AND FIR
FIR LASER
LASER EMISSION:
EMISSION: PERISCOPE
PERISCOPE TO
TO THE
THE VIBRATIONAL
VIBRATIONAL WORLD
WORLD OF
OF METHANOL
METHANOL AND
AND METHYLAMINE
METHYLAMINE

R.M. Lees
R.M. Lees

Dept.
Dept. of
of Physics,
Physics, University
University of
of New
New Brunswick,
Brunswick, Fredericton,
Fredericton, N.B.,
N.B., Canada
Canada E3B
E3B 5A3
5A3

The
The methyl alcohol and
methyl alcohol and methylamine
methylamine molecules
molecules
both are
both are notable
notable for for their large large-amplitude
-amplitude CH3CH 3 paper, we will review
In this paper, review the
the information
information
torsional motions,
torsional motions, whilewhile methylamine
methylamine has second
has a second on vibrational interactions
on vibrational interactions so
so far
far obtained
obtained from
from
large-amplitude motion in the inversion or perturbations
perturbations and
and FIR laser emission,
FIR laser emission, and
and present
present
"wagging" of the NH NH,2 group. As well, both some recent new
some recent new data
data on
on additional
additional perturbations
perturbations
molecules
molecules are notable in
are notable in having
having strong
strong infrared
infrared observed
observed for several isotopic
for several isotopic species
species of
of methanol
methanol
(IR)
(IR) CC-0 -0 or C-NC -N stretching
stretching bands bands whichwhich overlap
overlap and for methylamine.
well with the CO,
well C0 2 laser
laser bands,
bands, andand thereby
thereby provide
provide
numerous opportunities for
numerous for optical
optical pumping
pumping andand FIR
FIR
laser line emission. Although the ACKNOWLEDGEMENTS
torsion-rotation
torsion -rotation structure of the ground and
excited state energy level manifolds is quite The research
research described
described here
here has
has proceeded
complex, sustained
complex, sustained spectroscopic
spectroscopic effort effort overover the
the with the active
with the active assistance
assistance and
and collaboration
collaboration ofof
last
last decade
decade has has led to to a reasonable
reasonable understanding
understanding Drs. W. Lewis
Drs. W. Lewis-Bevan,
-Bevan, J.W.C.
J.W.C. Johns,
Johns, G.
G. Moruzzi
Moruzzi and
and
and accurate mapping
and accurate mapping of substantial
substantial portions
portions ofof I.
I. Mukhopadhyay, whose help is
is gratefully
these manifolds.
these manifolds. In addition to
In addition to thethe principal
principal acknowledged. Financial support
Financial support was provided by
was provided
species
species of CH3OH CH 3 OH (1
(1-8) CH 3 NH 2 ,(9-11)
-8) and CH3NH2,(9 several
-11) several the Natural
the Natural Sciences
Sciences and
and Engineering
Engineering Council
Council of
of
isotopic
isotopic variants
variants of of the former have been studied, studied, Canada and the University of New Brunswick
including 13 CH 3 OH (12,
including 13CH3OH (12, 13), 13), CH 3 18 OH (14,
CH3180H (14, 15) and
15) and Research Fund.
CD 3 OH (16).
CD3OH (16).
There are,
There are, however,
however, other other vibrational
vibrational modes modes
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excited
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also
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the CO2C0 2 laser
laser region
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very (1) J.P.
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lines (17) or or toto yield
yield laser
laser StarkStark spectra
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(18). F.
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105,
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spectroscopic observations do do notnot generally
generally give give 24-52
24 -52 (1984).
an overall view of the energy energy manifolds,
manifolds, but (8) R.M.
(8) R.M. Lees,
Lees, Far Infrared Science
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into thethe excited
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156 -171 (1986).
(1986).
level
level structure. (9) M.S.
(9) M.S. Malghani, R.M. Lees,
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and J.W.C.
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MM Waves
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-825 (1987).
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The presence of of apparent
apparent perturbations
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(10) N. Ohashi, K. Takagi, J.T.
Ohashi, K. J.T. Hougen,
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W.B.
first observed
first observed for for the the (nTK)
(niK) _= (010)(010) levels
levels of of AA Olson, W.J. Lafferty,
Olson, and W.J. Lafferty, J.J. Mol.
Mol. Spectrosc.
Spectrosc.
torsional
torsional symmetry
symmetry in in the
the diode laser spectrum
diode laser spectrum of of 126, 443-459
126, 443 -459 (1987).
the
the C C-0-0 stretch
stretch band band of of CH 3 OH by
CH3OH Sattler et al.
by Sattler al. Lees, W.
(11) R.M. Lees, W. Lewis-
Lewis-Bovan, R.R.J. Goulding,
Bevan, R.R.J. Goulding,
(1).
(1). Subsequently, Henningsen observed and C. Young,
and C. Young, Proc.
Proc. Fourth
Fourth Int.
Int. Conf.
Conf. IR
IR
characterized other strong perturbation perturbation-induced
- induced Zurich, 1988,
Phys., Zurich, 1988, pp.
pp. 587
587-589.
-589.
shifts and
shifts aridmixings
mixings in in this
this band
band from assignments
from assignments (12) I.
(12) I. Mukhopadhyay, Ph.D. Thesis,
Mukhopadhyay, Ph.D. Thesis, University
University of of
and analysis of FIR laser lines (2, (2, 4). The New Brunswick,
Brunswick, 1986.
1986.
analogous C C-0-0 stretch
stretch band band ofof CD 3 OH was
CD3OH was studied
studied by I. Mukhopadhyay,
(13) I. Mukhopadhyay, R.M.
R.M. Lees,
Lees, andandW.W.Lewis
Lewis-
-
Weber and and- Maker (16), who pointed out the Bevan, Proc. 4th
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Int. Conf.
Conf. IR IR Physics,
Physics,
possibility
possibility of Fermi resonance
of Fermi resonance between between the the CC-0 -0 Zurich, 1988,
1988, pp.
pp. 721
721-723.
-723.
stretch state and
stretch and high
high-lying
-lying torsional
torsional levelslevels of of (14) R.R.J.
(14) Goulding, Ph.D.
R.R.J. Goulding, Ph.D. Thesis,
Thesis, University
University of of
the ground
the ground state
state andand werewere thereby
thereby able able to to account
account New Brunswick, 1987.
1987.
for observed shifts in in both CD3OH CD 3 OH and CH3OH.CH 3 OH. (15) R.R.J.
(15) Goulding, C.
R.R.J. Goulding, C. Young,
Young, R.M.
R.M. Lees,
Lees,
Henningsen
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made further significant progress
progress W. Lewis-
W. Lewis-Bevan,
Bevan, and
and J.W.C.
J.W.C. Johns,
Johns, Infrared
in
in accounting
accounting for the the anomalous
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barrier Phys., in press.
Phys., in press.
height in the nn=l =1 torsional state of the CC-0 -0
(16) W.D.
(16) W.D. Weber and P.D.
P.D. Maker, J. J. Mol.
Mol. Spectrosc.
Spectrosc.
stretch as as the
the result
result of of interaction
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-H 72, 298
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-309 (1982).
bending mode,mode, (5) (5) and
and particularly in in identifying
identifying (17) J.O.
(17) J.O. Henningsen, Int. J.
Henningsen, Int. J. IR
IR && MM
MM Waves
Waves 7,
]_,
the
the strong
strong mixing
mixing and shift of
and shift of (nTK)
(ntK) _= (025)
(025) and and 1605-1629
1605 -1629 (1986).
(016)
(016) levels
levels as due to Coriolis
as due Coriolis interaction
interaction with with (18) S.
(18) J.O. Henningsen,
S. Petersen and J.O. Henningsen, Infrared
Infrared
the
the CH3CH 3 rocking
rocking mode,mode, the mysterious "X-
the mysterious "X-state"
state" Phys. 26, 55
Phys. 26, 55-71 (1986).
-71 (1986).
(3).

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