JOURNAL OF MOLECULAR SPECTROSCOPY 141, 175-203 (1990)

Selenoformaldehyde: Rotational Analysis of the A”’A,-2 ‘A, 735 nm

Band System of H&‘%e, H2CB0Se, and D2Ca0Se from High-
Resolution Laser Fluorescence Excitation Spectra

DENNIS J. CLOUTHIER

Department of Chemistry. University of Kentucky, Le.xington. Kentuck.v 40506-0055

R. H. JUDGE
Department o$Chemistry. University of Wisconsin-Parkside, Kenosha. Wisconsin 53141-2000

AND

D. C. MOULE
Department of Chemistry. Brock University. St. Catharines. Ontario. Canada L2S 3.41

High-resolution laser fluorescence excitation spectra of vibronic bands in the J’&.?A, system
of H#?‘*Se, HzC*‘Se, and D2Cx0Sehave been observed with Doppler-limited resolution. Three
bands have been analyzed, yielding upper state molecular constants and improved ground state
constants. The electronic transition is shown to be singlet-singlet in nature and the band polar-
izations are consistent with previous vibronic assignments. Erratic perturbations are observed in
all three bands. The derived excited state r. structure is similar to that of HzCS. suggesting that
selenoformaldehyde adopts a near-planar equilibrium structure in the excited state. o 1990 Academic
Press. Inc.

I. INTRODUCTION

The series of molecules H2C=X (X = 0, S, Se) provides a key opportunity to

study the spectroscopic consequences of substituting heavier atoms down a group in
the periodic table into a simple and well-characterized chromophore. In recent years
we have developed an interest in such studies, resulting in a recent review of periodic
group relationships in the spectroscopy of the carbonyls, ketenes, and nitriles ( 1). The
general conclusion from the review of the literature was that substitution of progres-
sively heavier atoms into a chromophore can have substantial effects on the spectro-
scopic properties of a molecule. This is particularly true of the excited states. For
example, the UV absorption bands of formaldehyde result in a nonplanar excited
state structure whereas the corresponding transition in H2CS occurs in the visible and
yields a planar excited state geometry. It is these sharp contrasts that have prompted
us to extend our studies to the selenoformaldehyde molecule.
Simple aldehydes and ketones have played an important role in the development
of high-resolution molecular spectroscopy. Formaldehyde has served for many years
as the prototype polyatomic molecule for detailed analysis of transitions in the mi-
crowave, infrared, and ultraviolet regions of the spectrum (2,3). It has also been used

175 0022-2852190 $3.00

Copyright Q 1990 by Academic Press Inc.
All rights of reproduction in any form reserwd
176 CLOUTHIER, JUDGE, AND MOULE

as a proving ground for many new experimental techniques, such as IR-UV double
resonance (4)) stimulated emission pumping (5)) and transient gain spectroscopy (6).
Historically, the analysis of the rotational subband structure of several vibronic tran-
sitions in the ultraviolet absorption spectrum of formaldehyde, in 1934, by Dieke and
Kistiakowsky ( 7), is recognized as the first interpretation of the electronic spectrum
of a polyatomic molecule ( 8). The beautifully sharp rovibronic band system has con-
tinued to inspire new investigations in the areas of spectroscopy, photochemistry, and
photophysics throughout the intervening decades.
In 1970 ( 9)) the existence of thioformaldehyde ( H2CS), the sulfur analog of form-
aldehyde, was firmly established by microwave spectroscopy. Thioformaldehyde is a
transient species, unstable with respect to polymerization, which is usually generated
by pyrolysis of various stable precursors including thiacyclobutane, dimethyl disulfide,
and 1,3-dithietane. Subsequent microwave, laser Stark, and FTIR studies thoroughly
explored the ground state rovibrational manifold of levels (3). In 1975, one of us
(RHJ) reported the first positive identification of the electronic spectrum of thioform-
aldehyde (IO), followed by detailed analyses of the vibrational (11) and rotational
(12, 13) structure. Two very sharp, discrete absorption systems, in the 800-6 10 and
6 lo-400 nm regions, were assigned as E3A2-z ‘Ai and ki AZ-2 ‘Ai, respectively,
analogous to the corresponding UV bands of formaldehyde. Following the observation
that emission could be readily excited from the triplet and the singlet states (14, 15)
in thioformaldehyde vapor, a variety of papers ( 16-28) reported laser-induced fluo-
rescence (LIF) studies which delved deeply into the spectroscopy of both states.
In 1984, both the photoelectron (29) and electronic (30) absorption spectra of
selenoforrnaldehyde were reported, adding a third member to the series. Selenoform-
aldehyde again proved to be a transient species, prone to polymerization. Microwave
studies have been done on a number of isotopomers of H2CSe (31, 32), yielding a
ground state substitution structure. The low-resolution electronic absorption spectrum
(30) revealed a small group of bands in the 825-700 nm region which were assigned
to the c3A2-2 ‘A, electronic transition. A subsequent LIF study of the band system
by Clouthier, Judge, and Moule (33) extended the vibrational analysis and uncovered
a very weak singlet-singlet system at 735 nm. Further work (34) with H2CSe and
DzCSe refined the vibrational analysis, assigned the Si-&, 0: band in the D&Se com-
pound, and established that the molecule is near-planar in the triplet state. A new
method of generating selenoformaldehyde for LIF experiments, based on the pyrolysis
of polymeric H*CSe, was also successfully developed.
In this paper we report detailed rotational analyses of three bands in the k’&
2 ‘A, system of selenoformaldehyde, for the three isotopomers H2C7%e, H2Cg0Se,
and D2Cg0Se. The polarizations of the 08 and 4; bands are established and they are
shown to be consistent with a singlet-singlet electronic transition. In addition, improved
rotational constants are reported for the ground states of the three compounds. A
geometry has been determined for the excited state, indicating that the k’Az structure
of selenoformaldehyde is similar to that of thioformaldehyde. A large variety of excited
state perturbations have been discovered during the analysis.

II. EXPERIMENTAL DETAILS

All of the laser experiments were carried out at the MIT Laser Research Center.
The excitation source was a computer-controlled scanning ring dye laser (Coherent
 SPECTRA OF SELENOFORMALDEHYDE 177

699-29 Autoscan) operated with LD 700, yielding single mode output powers of OS-
0.7 W in the 750-700 nm region when pumped with 5 W of multiline red output
from a Kr + laser. The laser linewidth, as specified by the manufacturer, was < 1 MHz.
The fluorescence apparatus was designed to maximize the production of HzCSe
while minimizing the risk associated with the potential toxicity of selenium compounds.
A 20 cm long dimpled quartz pyrolysis tube was attached vertically to a conventional
Pyrex fluorescence T-cell. The vapor from selenoformaldehyde polymer, contained
in a small heated reservoir at the top of the pyrolysis tube, was pyrolyzed at 750°C to
produce monomeric H*CSe at pressures of a few mTorr, controlled by the reservoir
temperature. A liquid nitrogen cooled trap was fused directly below the cell, so that
the pyrolysis products flowed vertically through the cell and were immediately con-
densed in the trap, without any intervening vacuum conduits. The apparatus was
evacuated with a roughing pump to a background pressure of about 1 mTorr.
The laser beam entered and exited the fluorescence cell horizontally through well-
baffled 30 cm long arms sealed directly to the body of the cell. The resulting emission
was imaged with a short focal length lens onto the photocathode of a cooled RCA
C3 1034A photomultiplier through a 790-nm cutoff filter. The photomultiplier output
was routed to a current-to-voltage converter circuit with a variable output time constant
and full scale voltage of 10 V, suitable for digitization by the Autoscan system. Scattered
laser light was negligible with this apparatus.
Three channels of data were collected simultaneously with the Coherent Autoscan
system. The first channel contained the fluorescence excitation spectrum. The second
channel contained the vernier &talon fringes from the Autoscan wavemeter, recorded
to provide a continuous record of scan status, mode hops, or other difficulties. The
third channel contained the optogalvanic signal from an argon-filled uranium hollow
cathode lamp, to provide a wavelength calibration standard for the wavemeter data.
The optogalvanic measurement consisted of chopping the laser beam after it exited
the fluorescence cell, directing it along the axis of a commercial U-Ar hollow cathode
lamp, and detecting changes in the flow of current through the lamp with a lock-in
amplifier. The optogalvanic signals were very strong and weak uranium lines were
readily detected with this technique. The wavenumbers of the lines were taken from
the emission atlas of Palmer et al. (35).
The spectra were scanned in segments of lo-100 cm-‘, with the longest successful
scan being 200 cm-’ in length. The three channels of data were digitized at 20 MHz
intervals during the scan, corresponding to a resolution of 0.00067 cm-‘. The precision
of the wavemeter was checked in different wavelength regions and found to have a
random error of ca. kO.003 cm-‘, well within the manufacturer’s specification of
to.0067 cm -’ .
In order to enhance the marginal data storage and calibration capabilities of the
Autoscan system, we extensively modified the Autoscan software to allow for host
computer control and data handling. In our implementation, the Autoscan scanning
algorithm is interrupted when the dedicated computer memory is full and the data
are rapidly transferred to memory and subsequent disk storage on a HP Vectra portable
computer. The Autoscan program then resumes scanning (typical transfer time 20-
30 set). When a page of data has accumulated in the host computer, a hard copy of
the three channels of data, along with wavelengths of features detected in the spectra
by a peak finding algorithm, is plotted on an HP Quiet Jet Plus printer, with a user-
178 CLOUTHIER, JUDGE, AND MOULE

selected dispersion per page (typically 5-10 cm-‘). Plotting occurs while the laser is
scanning, so that the data acquisition is only interrupted briefly during data transfer.
These enhancements greatly improved our capability to handle the large numbers of
data accumulated during the experiments.
Samples of isotopically pure selenoformaldehyde polymers were prepared using the
method of Weissflog (36). Enriched (>98%) 78Se and “Se were used to prepare
( H2C78Se),, ( H2CsoSe),, and ( D2Cs0Se),, which precipitated as whitish-yellow powders
from the reaction of dichloromethane with Na$e. The isotopic purity of all the samples
was confirmed by mass spectrometry.

III. RESULTS AND ANALYSIS

A. Vibronic Structure
As in our earlier low-resolution work (34), the high-resolution spectra show two
distinct types of bands in all three isotopes. The majority are strong, red-degraded
bands with multiple heads. These we have assigned as belonging to the E3A2-i ‘A,
system (34). In H2C ‘*Se and H2C 80Se, a weak band with extensive type B (perpen-
dicular) rotational structure was recorded in the 13 800-14 100 cm-’ region. A com-
parison of low-, medium-, and high-resolution spectra of this band is shown in Fig.
1, illustrating the weakness of the perpendicular band and the clearly resolved rotational
structure at Doppler-limited resolution. As argued previously (33)) the vibronic spin-
orbit selection rules which govern the rotational structure of triplet-singlet transitions
lead to parallel (A-type) bands. The perpendicular bands are assignable as the 4;
vibronic transition of the k’A*-,f ‘AI band system, consistent with the results of our
detailed rotational analysis (vide infra) . Unfortunately, the 0: band of the 2-2 system
for both hydrogen isotopomers is completely overlapped by a cluster of triplet-singlet
bands, and cannot be assigned.
The situation is reversed in D$*‘Se. The singlet-singlet 0: band shows up as a
weak, single-headed band at 13 600-l 3 650 cm-‘. The rotational structure differs
substantially from the neighboring triplet-singlet bands, and line-by-line analysis shows
that the band is a singlet-singlet A-type band (vide infra). The 4; band is badly
overlapped by the 2:3; T,-So band making it unsuitable for rotational analysis.

B. Rotational Analysis
1. Selection rules and notation. In the ground state, H&‘?Se, H2Cg0Se, and D2C8’Se
are all near-prolate asymmetric tops ( K = -0.9962, -0.9962, and -0.9878, respectively)
(32). The k ‘AZ + J? ‘A 1transition is orbitally forbidden under electric dipole selection
rules, but presumably gains intensity through Herzberg-Teller vibronic interactions,
analogous to the vibronically induced bands of formaldehyde (2) and thioformaldehyde
(3). The V’ = 0 + D” = 0 origin band is not vibronically induced, but appears in the
spectrum as a magnetic dipole-allowed transition. The bands can be classified as parallel
(type A) with a single red-degraded head or perpendicular (type B or C) with an
extended subband structure. The rotational selection rules are AK, = 0, f2, . . . , AK,
= +1, +3,. . . ) fortypeAbands;aK,=+1.+3 ,..., AK,=+1,+3 ,..., fortypeB
bands; and AK, = f I, *3, . . . , AKc = 0, *2, . . . for type C bands. The general
 SPECTRA OF SELENOFORMALDEHYDE 179

FIG. 1.Comparison of low-, medium-, and high-resolution LIF spectra of H2CSe. The top section gives
an overview of the vibronic structure as reported in Ref. (34). All of the strong bands belong to the r,-&
system. The middle section shows the S,-S, 4; perpendicular band structure. The bottom section illustrates
the well-resolved subband structure observed at high resolution for the H2C7%e species.

selection rule AJ = 0, k 1 places further restrictions on the number of possible rotational

transitions. Individual rotational transitions are designated as *& AJpO(J”), where
AK, and A J denote changes in K, and J. J” and Kb are the values of these quantum
numbers in the lower state. This notation does not distinguish between lines in which
the asymmetry splitting is resolved, so that K’ and KL must be inferred from the band
type and the restrictions that KC = J - K, or KC = J - K, + 1. It is common practice
to use the designations E (even) and 0 (odd) to refer to the parity of J” + KL
+ KS, which then fully characterizes the KC quantum number.
2. Determination of molecular constants. Once detailed rotational assignments were
made, the molecular constants of the ground and upper states were determined by
iterative variation to give a least-squares fit between observed and calculated transition
frequencies. A version of the ASYROT program of Birss and Ramsay (37)) modified
for use on a microcomputer (38), was used for this purpose. The Hamiltonian em-
ployed for the ground and excited states was Watson’s A-reduction (39) in the I’
180 CLOUTHIER, JUDGE, AND MOULE

representation. Although they are not used in the fitting procedure, the program also
calculates the relative line intensities, which were invaluable in refining the assignments.
3. The ground state rotational constants. The available ground state rotational con-
stants for the various isotopomers of selenoformaldehyde come from two papers pub-
lished by Brown and co-workers (31, 32). Unfortunately, the microwave data are
very limited, consisting of only eight AK, = 0 lines, with K, = 0, 1 and J = 1-3, in
each case. The authors derived the constants A, B, C, A,, and AJK from the data,
fixing AKat 0. These constants were found to be inadequate to reproduce ground state
combination differences derived from our assignments of the electronic spectra.
The 4; bands of H2C7’Se and H2CsoSe provided a large number of combination
differences with A& > 0, which can be used to provide precise values for the A and
A, constants. We combined the available microwave data and optical combination
differences in a least-squares fit, weighted according to the precision of measurement,
to obtain refined parameters. The results are shown in Table I. The constants are all
well determined, with values significantly improved over those obtained solely from
microwave data. The A values are substantially different from those published by
Brown et al. (31). The AK constant was of particular concern, because it has a sub-
stantial effect on the optical data at higher K, values. The combined optical and mi-
crowave data reduce the correlation between A and AK, allowing them to be determined
separately with reasonable standard deviations.
Unfortunately, the ground state constants for DpCsOSecould not be refined in the

TABLE I

Ground State Molecular Constants of Selenoformaldehyde (in cm-‘)’

COllStCUlt H,PSe H,PSe DzC8%

A 9.69038,(32) 9.69098,(36) 4.869,(19)

B 0.413828,(25) 0.41541%(32) 0.34432933(40)

C 0.396145,(25) 0.397551Q32) 0.32101736(40)

l(r AK 7.84,(12) 8.02,(14) 1.73O66

IO6 Ax 10.368~(41) 10.402&2) 5.53*(9)

106 A, 0.3728r,(88) 0.380,(12) 0.211,(21)

l@ s, 37.,(12) 50.,(16) 0.W

lob ST 0.014711(38) 0.01265(36) 0.W

#of Comb.
Diffs. FiP 1521 1280 390

Std. Dev.= 0.010 0.01 I 0.021

‘The ermr limits are 3a and are right justitied to the last digit on the line; sufficient additional
digits are quoted below the line to reproduce the original data wilh full accuracy.

bA weigh& least squares fit of the 8 reported microwave lines from Rcfs. 31 and 32 for each
isotopomer and rhe reported number of opdcal combination differences was uxd IO determine
the constams.

%andard deviation of tit for the optical combination differences

%xlstant Iixed In final fir.

 SPECTRA OF SELENOFORMALDEHYDE 181

same manner. The 4; band was severely overlapped by the bands of the triplet-singlet
system, so that only the type A 0: band was amenable to rotational analysis. The AK,
= 0 selection rule imposes the same constraints on determining A and AK as do the
microwave data. The final constants were obtained by fixing AKand varying A, B, C,
A,, and AJK.The inclusion of a5and aKcaused the standard deviations in the parameters
to deteriorate, so they were set to zero. The AKconstant was fixed at a value of 5.1882 1
MHz. which was obtained by multiplying the AKvalue of H2C8’Se by the ratio of the
AK values for D2CS and H$ZS. This compromise seemed reasonable, considering the
close agreement between the AK values of H2CS and H*CSe. This value of AK is also
in close agreement with the value derived from ab initio force constants ( 5.175 MHz)
(32). The resulting ground state constants are summarized in Table I. The constants
are not as precise as one would like for determining combination differences at high
J and K, . More extensive microwave and millimeter-wave spectroscopic studies will
be needed to refine the constants any further.
4. Analysis of the 4; bands of H2C7’Se and HzCsoSe. The starting point for the
rotational analyses was the well-resolved perpendicular band, 4& of H2C8’Se at 7 19
nm. The band has the characteristic appearance of a perpendicular band of a prolate
symmetric rotor. A series of well-defined heads, formed by the RR(J) branches, extend
to the blue of the band center. Subbands with odd KL are three times more intense
than those with even K’Adue to the nuclear statistical weighting, which readily estab-
lishes the K0 numbering. Since the first line in each RR branch must have J = K,, the
J numbering can be established if the branches can be followed back to the weaker
first member. These assignments enabled the band to be analyzed in the symmetric
top limit, establishing a provisional set of constants.
A perpendicular band can be either type B or type C, with slight differences in the
rotational structure near the band origin in the two cases. In order to ascertain the
band type and determine B and C separately, it was necessary to assign the asymmetry
split subbands. These splittings are large for low K,, except for K, = 0 which is not
split, and increase with J within a subband. The magnitude of the splitting decreases
rapidly with K,, so that the asymmetry splitting in H>CSe is not resolvable for KL
> 3 and Kh > 4. The first assignments were made by following the closely spaced
asymmetry doublets in the RR2 branch back to lower J, until the lines merged at J”
= 13. A bootstrap approach was used to arrive at a complete set of assignments and
rotational constants.
In the final fit of the data, the ground state constants were assumed to give the
ground state terms with negligible error and the upper state constants and the band
origin were varied. A total of 1376 lines were assigned and 1248 of these assignments
were included in the final least-squares analysis, yielding an overall standard deviation
of fit of 0.020 cm-‘, somewhat greater than the estimated precision of the measure-
ments. The excited state rotational constants are shown in Table II and the assignments
are listed in Table IX of the Appendix.
The isotope shift on substitution of 78Se for “Se is -0.203 cm-‘. The analysis of
the 4; band of H2C78Se was aided by direct comparison with the corresponding tran-
sitions in the H2Cs0Se spectrum as shown in Fig. 2. A total of 1273 assignments were
made and 1139 of these were fitted to give the rotational constants given in Table II.
The standard deviation of the fit was 0.020 cm -‘, identical to that of the other isotope.
182 CLOUTHIER, JUDGE, AND MOULE

TABLE II

Excited State Molecular Constants of Selenoformaldehyde (in cm-‘)=

4’ Level 00Lmel

COllSt~t H2C”Se H2C7% npse

A 9 01486,(39) 9.01597,(49) 47114(37)

0 ‘X37668,(25) 0.37783&!5) 0.3 16060&(62)

C 0.35987,(27) 0.3617Oo(28) 0.295534,(66)

104 AK 3.707,(58) 3.588,(71) 0 272,(62)

106 Am 4.96(1 1) 9.9,(13) 28.14,(71)

lo6 A, 0.66&(26) 0.7879(35) -0.547,(44)

106 & 360.30(52) 341.4,(69) O.Ob

106 s, 0.19,(14) -0.08,(15) O.Ob

TO 13909.251(S) 13909.048(S) 13631.770(6)

#of
assignments
fined 1248 1139 809

Std. Dev. 0.020 0.020 0.020

The error limits are 30 and are right justified to the last digit on the line; sufficient additional
digits are quoted below the line to reproduce the original data with full accuracy.

bConstant fixed in final fit.

The rotational constants are very similar for the two isotopes, with comparable standard
deviations. The assignments for this isotope are given in Table X of the Appendix.
5. Perturbations in the 4h bands, All of the observable LIF bands in the Sl-S, system
of selenoformaldehyde are buried in a set of much more intense T,-So bands. A
variety of perturbations were found in the 4; bands which are due to either mixing
with triplet levels or high levels of the ground state. Both types of perturbations have
been shown to occur in the thioformaldehyde case ( 19, 25). The only possible per-
turbing Sl level would be O”, which lies 300-400 cm -’ lower in energy and is therefore
not a viable candidate.
Kb = 8 (‘%e) : A small resonance-type perturbation occurs at J’ = 15, shifting
the level down 0.14 cm-‘. It is seen in the R and & branches and only appreciably
affects the one level. The perturbation is not observed in the “Se species.
KL = 7 ( 78Se): A few weak lines, which fit reasonably well, were found for this
isotope. The corresponding lines in the *‘Se spectrum were too weak to be assigned.
KL = 6: The Kh = 6 levels of both isotopes are strongly perturbed, with all the
levels shifted to higher energy. A plot of the perturbation is shown in Fig. 3 for the
*‘Se case. The behavior is very similar in 78Se, with the maximum occurring at the
same value of J’ = 25. The perturbation was readily assigned in all 3 branches of the
Kh = 6- K6 = 5 subband in both isotopes. The form of the perturbation is quite com-
plex, with a series of resonances superimposed on a rising positive deviation. The fact
that it starts off at approximately 0.2 cm-’ is disturbing, since it may indicate that the
higher K; levels are also perturbed. This would lead to a substantial error in AK, which
 SPECTRA OF SELENOFORMALDEHYDE

i ‘A,

Ir I I I I I
13032.00 13D3400 1381000 13B3L.w 13940.00

Vacuum Wavenumber (cm -1)

FIG. 2. A comParisonof the RRI branch rotational structure of the 46 bands of H2Cs0Se and HzC78Se.

might manifest itself as this type of offset in one or more K stacks. However, the value
of A;, is within the expected range, so that the most likely explanation is that K:,
= 6 is perturbed.
KL = 5: There appears to be a weak resonance at J’ = 11 and 12 in the *‘Se case.
Kh = 4: This is the first K stack where combination differences with the AK,
= -1 progressions can be formed. In the *‘Se case, a weak resonance is seen at J
= 10 and 11, which can be observed in all six branches. A similar but stronger break

,^ 0.6 Ka = 6
I .i
E
22
i 0.4

s
I
m 0.2

0”

0.0
25 30

FIG. 3. Plot of the residuals (observed - calculated) for transitions terminating on the Kh = 6 levels of
the 4; band of H2C *‘Se.
184 CLOUTHIER, JUDGE, AND MOULE

occurs at J’ = 4 in the 78Secase. The intensities of the AK, = - 1 subbands in the ‘%e
spectrum are anomalous. The ‘R(J) branch is stronger than the Q and P branches.
This is not the case in the *‘Se spectrum, where the relative intensities of the branches
appear normal. It is unclear whether the intensity anomalies are due to a transient
experimental problem or a change in the fluorescence efficiency in this region of the
spectrum.
Kb = 2: The 80Se spectrum shows a small perturbation in both asymmetry com-
ponents at J’ = 4. The progression breaks sharply at J’ = 32 in the upper component
(Kc = J - Ka) and at J’ = 34 in the lower. We were unable to find the progression
on the other side of the break. The assignments in the high J’ region are somewhat
questionable, since we could not find the corresponding lines in the AKa = - 1 region
for the upper asymmetry component. The ‘%e spectrum shows a small resonance at
J’ = 21 in the lower asymmetry component (Kc = J - K, + 1). It appears to be
absent in the other component, or at least much weaker. The progression again has a
major break at J’ = 34, which could not be resumed at higher J.
Kh = 1: Nuclear statistics dictate that transitions terminating on these levels will
be weak, but calculations predict that some of the branches, particularly RQo, should
have appreciable intensity. We are unable to assign any progressions terminating on
K:, = 1 levels in either isotope. The AK, = + 1 subband lines are too weak and irregular
to be found. To complicate matters, the AK, = - 1 progressions are strongly overlapped
by a triplet-singlet band. This was proven by assigning an 0 or S branch progression,
which showed characteristic first differences greater than those of the singlet-sin-
glet bands.
Kh = 0: A variety of interesting resonance-type perturbations were found. The
“Se spectrum shows a strong break at J’ = 30 with the largest deviation being -0.37
cm-‘. In the 78Se case the corresponding break occurs on the positive side (+OSO
cm-i), as shown in Fig. 4. It appears that the slight shift in the term values for the
two isotopes may account for the different J’ values and reversal of sign of the maximum
deviation. Both bands abruptly break at J’ = 34 and we were unable to extend the
progressions past this point.

0.6
K. = 0 .
‘;
E
2% 0.3

E
I 0.0

ui

-.3
0 5 10 15 20 25 30 35

J'
FIG. 4. Plot of the residuals (observed - calculated) for transitions terminating on the Kb = 0 levels of
the 46 band of H2C7*Se.
 SPECTRA OF SELENOFORMALDEHYDE 185

D 2CBoSe i’A 2c ii ‘A 1
Origin Band

FIG. 5. The high-frequency end of the high-resolution St-S, 08 band of D2CSoSe,showing the prominent
QR heads and the strong QP branches.

6. Analysis of the O$ band qf D2Ca0Se. This band is very weak and was difficult to
assign. However, enough assignments were made to clearly show that it is a type A
singlet-singlet band. For D2CSe, nuclear statistics dictate that subbands with even
KL should be twice as intense as those with odd K;. The starting point for the analysis
was the identification of the stronger QP4, QP2, and QPOprogressions extending to the
red of the single strong head as shown in Fig. 5. The K, numbering was established
from these progressions. The asymmetry splitting was then found in the K, = 2 lines
by following one set to lower J’ until it merged with another set of lines, which occurs
at .J’ = 9. The progression was followed back to the first member to establish the J
numbering, which was confirmed by calculating combination differences to the QR
lines. In this fashion the P and R branches of the stronger subbands were readily
identified. A preliminary set of constants derived from these lines was used to predict
the positions of the remaining subbands. In most cases, only P and R lines could be
used to confirm the assignments, since the Q branches are strongest at J = K, and
lose intensity rapidly at higher J values. A total of 957 assignments were made, of
which 809 were fitted with an overall standard deviation of 0.020 cm-‘. The excited
state rotational constants are shown in Table II. Table XI in the Appendix lists all the
assigned lines.
The rotational constants for the 0: band are not nearly as precise as those for the
44 bands, due to the AK, = 0 restriction and our inability to refine the ground state
constants satisfactorily. A variety of perturbations in the excited state levels, as outlined
below, also limited the range of data that could be satisfactorily fitted.
7. Perturbations in the O$ band of D2CsoSe. K:, = 8: The subband starts with a
negative deviation (-0.08 cm-‘) at J’ = 8 which slowly decreases. Beyond J’ = 26
the assignments were only possible for the R branch, but do not appear to be signifi-
cantly perturbed.
186 CLOUTHIER, JUDGE, AND MOULE

A 0.6
I
E
23 0.4
ci
;5
0
0.2

ci

6
0.0
1

5 10 15 20 25 30

FIG. 6. Plot of the residuals (observed-calculated) for transitions terminating on the Kh = 4 levels of the
0: band of DzC8’Se.

KL = 7, 6, and 6: No substantial perturbations.

KL = 4: A strong positive deviation starts at J’ = 23 and gets rapidly larger to
the limit of our recorded spectra. This perturbation is illustrated in Fig. 6.
K:, = .3: A positive deviation starts at J’ = 22 which increases rapidly and then
falls off to the red with a change in sign.
K:, = 2: A strong perturbation affects levels at higher J. Both asymmetry com-
ponents are affected. Although the perturbation appears to be a resonance type, the
change in sign is not well-established.
Kb = 1: A weak perturbation affects the higher J levels, but was difficult to assign
beyond J’ = 25. Both asymmetry components appear perturbed.
Kb = 0: A strong, positive deviation sets in at J’ = 17 which could be followed
out to a maximum deviation of 0.76 cm-r at J’ = 25. The perturbation is illustrated
in the residual plot in Fig. 7.

0.8 . K,’
= 0
.
I
0.6 /

0.4 - i

0.2 . /
0..

A
0 5 10 15 20 25 30

J'
FIG. 7. Plot of the residuals (observed - calculated) for transitions terminating on the & = 0 levels of
the 08 band of D2C80Se.
 SPECTRA OF SELENOFORMALDEHYDE 187

C. Determination of the Excited State Structure

The determination of the excited state geometry was frustrated by the lack of suf-
ficient isotopic data for the levels of interest. In particular, the only data attainable
for the vibrationless excited state level (0’) are those from D2Cg0Se. By fixing two of
the four structural parameters, we were able to calculate an r. geometry. We chose to
fix the C-D bond length and DCD angle at the values obtained for the 0’ level of
DzCS, since we were most interested in those structural parameters that change on
excitation. Franck-Condon considerations suggest that these would be the out-of-
plane angle and the C = Se bond length. The resulting parameters are shown in Ta-
ble Ill.
For the H2CSe species, data are only available for the 4 ’ level. Unfortunately, the
effect of the out-of-plane bending vibration, v4, on the A rotational constant is expected
to be severe, so that the 0’ geometry cannot be approximated by that obtained from
4 ’ . As expected, isotopic substitution along the A rotational axis does not help in
determining the structure. Although the six rotational constants obtained from the
H2Cg0Se and HzC 78Sebands were used, the least-squares equations are ill-conditioned
unless two of the four parameters are fixed. As in the DzCSe case, we chose to fix the
HCH angle and C-H bond length at the appropriate HzCS values and vary the other
parameters. The results are shown in Table Ill.

IV. DISCUSSION

Although the bands reported in this work are very weak and overlapped by the
much stronger T,-So band system, they proved to be experimentally observable and
amenable to detailed analysis. All three bands clearly originate in the 2)”= 0 level of
the electronic ground state of the appropriate isotopomer and terminate in an excited
singlet state. The refined ground state constants are compared in Table IV with those
of formaldehyde and thioformaldehyde. In most cases, a smooth trend in the constants
is observed, indicating that there is nothing unusual about the ground state constants
of selenoformaldehyde and that it fits well into the series. The inertial defects (A)
shown in Table IV are slightly larger than zero, as expected for planar molecules with

TABLE III

Excited State Effective Geometric Parameters for Selenoformaldehyde

r(C=Sc) A) 1.856(4Y 1.857(9)

OOP angk (“)d 12.215) 29 2(2)

HCH angle (“) 121.6 116.8

r(C-H) (d) 1.075 1093

‘From the excited stare rotational constants of D#?Se.

%om a combined tit of rhe excned state mrauonal consots of H,C”Se and H,C”Se.

Clhe error limits are 30.

dOut-of-plane angle; defined as the angle between the HCH plane and the C-Se bond.

‘Paramctcr fIXcd 1” the tinal fir.

188 CLOUTHIER, JUDGE, AND MOULE

TABLE IV

Comparison of the Ground State Molecular Constants of Formaldehyde, Thioformaldehyde,

and Selenoformaldehyde (in cm -I)=

CCilStant H,COb H,CSb H,PW D2COb D2CSb D,PSe’

-

A 9.4055 9.727 I 9.6904 4.7250 4.8821 4.8694

B 1.2954 0.5904 0.4138 1.0769 0.4972 0.3443

C 1.1342 0.5554 0.3961 0.8734 0.4502 0.3210

IO’ AK 6.48 1.62 7.84 1.47 1.68 1.73

l@ AK 43.05 17.43 10.37 20.78 11.93 5.54

106 A, 2.512 0.649 0.373 1.771 0.436 0.211

106 SK 34.22 12.40 37.3 17.35 8.67 O.od

106 8, 0.349 0.040 0.015 0.381 0.066 O.od

A(Expt)’ 0.058 0.064 0.079 0.078 0.088 0.093

A(CaIc)’ 0.054 0.068 0.077 0.072 0.089 ----

‘The number of significant figures in the constants reported in this Table do not reflect the
precision of the determination.

bFrom Ref. 3

Qxls1ant fixed in final fit.

‘Inertial defect in amu AZ.

‘Inertial defect calculated from A = 67.452/v where Y is the frequency of the lowest in-plane
vibrational mode in cm-’ (Ref. 41).

a small zero point vibrational contribution to A. Herschbach and Laurie (41) have
shown the inertial defects of planar tetraatomic molecules can be approximated by A
= 4Kf u with K = h /8r2 = 16.863 amu A* cm-’ and v the frequency of the lowest
in-plane vibrational mode in cm -’ . The good agreement between calculated and ex-
perimentally derived values (Table IV) shows that the inertial defect in the series of
H2C = X molecules is dominated by the in-plane vibrational contribution.

TABLE V

Comparison of Experimental” and ab initiob Centrifugal Distortion Constants of Ground State

Selenoformaldehyde (in MHz)

AK Alx 4

Expt Calc Expt talc Expr MC

npse 23.518 20.984 0.3108 0.3113 0.01 A2 0.0122

D#?Se 5.188 5.175 0.1660 0.1641 0.0063 O.CC68

*This work

bRef. 32.
 SPECTRA OF SELENOFORMALDEHYDE 189

TABLE VI

Comparison of the Excited State Molecular Constants of Formaldehyde, Thioformaldehyde,

and Selenoformaldehyde (in cm-‘)”

4’ Level 00 Level

COlIStMlt H,COb H,W H,C%e’ D,COb D,W D2Cn0Se~

8.7519 9.0572 9.0149 4.5134 4 7357 4.7110

1.1250 0 5378 0.3767 0.9558 0 4578 0.3160

1.0114 05102 0.3599 0.7964 0.4173 0.2955

500 3.70 3.71 I 28 3.13 0.27

65.6 21.3 4.9 41. 70 28.1

2.59 0.83 0.66 1.5 0.78 -0.55

20.7 13.0 360.3 O.ff O.Od O.Od

2.05 0.044 0.19 O.ff o.o* o.o*

28313 16766 13909 28302 16484 13632

“Ihe number of signiticant figures m the consfants reportedin this Table do not reflect the
preasion of the determination.

bFrom Ref. 3.

Qmstanr fixed in final fit.

Attempts were made to further refine the ground state r. geometry using our new
constants and the other isotopic data of Brown et al. (32) with no success. It appears
that the microwave data with AK = 0 are incompatible with our data, for which AK
has a nonzero value which affects the A rotational constant. Brown et al. (32) have
calculated ab initio force constants and derived centrifugal distortion constants for

TABLE VII

Comparison of the Excited State Effective Geometries of Formaldehyde. a Thiofonnaldehyde, b

and Selenoformaldehyde’

00 Level 4’ Level

H2a H,CS H,CSe H&O H,CS H,CSe

r(C=X) (A) 1.321 1.707 1.856 1.321 1 706 1.857

LOOP (“1 20.5 8.9 122 31.1 27.x 29.2

MCH (“) 121.5 121.6 121.66 118.6 116.8 116.S6

r(C-H) <A, 1.392 1.075 I.0756 1.096 I.093 1.0936

‘Ref. 43.

bRef. 12.

‘This work.

*Parameter fxd at H&S value

190 CLOUTHIER, JUDGE, AND MOULE

TABLE VIII

Ground and Excited State Vibrational Frequencies of Selenoformaldehyde (in cm-‘)”

H,CSe D,CSe

~,(a,) C-H a-. 2988 .. ..

v,(q) CHI bend 1397 1312 996

V&) c=se SIT’. 874 704 662 667 619

v,@,) OOP bend 942 29? 355b 20Sb

v,(bJ C-H str. 3059 ..

v&z) CHz rock 914 812 563 ._

‘Ground state frequencies are scaled ab iniao values from Ref. 32. Excited state frequencies
from Ref. 34.

b41 - 4O inversion splittingcalculated

fromthetriplet state double minimum potential function,
Ref. 34.

H2Cg0Se and D2C8’Se in the ground state. Our experimental results are in excellent
agreement with their calculated values as shown in Table V.
The excited state molecular constants of formaldehyde, thioformaldehyde, and se-
lenoformaldehyde are compared in Table VI. Smooth trends are again observed for
most of the constants, with the exception of those with large uncertainties (see Table
II). The To values show that the &-So transition in HzCSe is only slightly lower in
energy than that of H,CS, in contrast to the much larger excitation energy for HKO.
Collins et al. (42) have estimated the singlet (n, ?r* ) state to be a 14 400 cm-’ above
the ground state, in reasonable agreement with our experimental results.
A detailed comparison of excited state geometric parameters for the 0’ and 4 ’ levels
of formaldehyde, thioformaldehyde and selenoformaldehyde is shown in Table VII.
In all cases, the reported values are effective parameters determined directly from
experimental moments of inertia, so that comparisons with the selenoformaldehyde
data are valid. The excited state structure of selenofonnaldehyde shows an elongation
of the C=Se bond consistent with promotion of an electron out of an n orbital into
a P* orbital. The change in bond length on excitation for the series H,CO, H?CS,
H2CSe is 0.12, 0.10, and 0.10 A, respectively. The out-of-plane angle is of particular
interest, since the equilibrium excited state structure of H&Se may or may not be
planar. In formaldehyde, the molecule definitely has a nonplanar excited state structure
with a 0’ level out-of-plane angle of 20.5”. In thioformaldehyde, the angle is 8.9”,
reflecting the fact that the equilibrium geometry is in fact planar (40). In both mol-
ecules, addition of one quantum of the out-of-plane bending mode (vi) increases the
out-of-plane angle in the effective 4 ’ structure. Comparison of these trends with the
data for selenoformaldehyde suggess that the excited state geometry is closer to that
of thioformaldehyde. Collins et al. (42) also suggest, on the basis of their ab initio
results, that the Si state is pyramidal with a very low inversion barrier, reminiscent of
the ab initio results for H2CS (44, 45). Similarly, analysis of the vibrational structure
 SPECTRA OF SELENOFORMALDEHYDE 191

in the Ti-So band system of selenoformaldehyde (34) gave an inversion barrier of

less than 20 cm-‘, very close to that of thioformaldehyde. Although the limited number
of observed Sr-& vibronic bands precludes a definitive determination of the equilib-
rium excited state structure, all the evidence suggests a planar geometry.
The large number of excited state perturbations in levels of such low vibrational
energy in Sr is surprising. These perturbations must come from interactions with
nearby levels of the first excited triplet state, high vibrational levels of the ground state,
or some other excited state in the vicinity. Consideration of the relevant vibrational
intervals shows that there are a variety of nearby triplet levels. The vibrational fre-
quencies in the ground and excited states are shown in Table VIII. For HZCSe, the
Sr(4’)-T,(O’)energygapis 1738cm- ’ . The only triplet state vibrational combinations
that approximate this energy are 45 N 1775, 3 ‘43 = 1778, and 3*4’ x 1705 cm-‘.
The first two levels are likely too high in energy for a close resonance to occur, assuming
AK, = 0 or ? 1 selection rules (46). In D*CSe, the energy difference between the
vibrationless levels in the two states is 1369 cm -‘, which corresponds to the vibrational
combinations 3* N 1314, 436’ N 1356, and 4’6’ N 1334 cm-‘. A second triplet
state ( 3AI ) is calculated (42) to actually lie slightly lower in energy than the 3A2 state
we have labelled T, , although there is no experimental evidence to support the theo-
retical prediction. If the state is in the vicinity, it could also be coupled to levels in
S, , further complicating the situation. Studies of the magnetic rotation spectrum or
the effects of magnetic fields on the LIF spectrum would be invaluable in further
attempts to understand the complex pattern of perturbations observed in this work.
Sub-Doppler perturbations involving high vibrational levels of the ground state
have been identified in the S, state of thioformaldehyde ( 19). It is not unlikely that
similar effects are to be found in selenoformaldehyde. The inflated standard deviations
of fit (0.02 cm-‘) for the three bands analyzed in this work are larger than expected.
Comparisons of wavemeter measurements to optogalvanic line standards suggest a
precision of at least 0.005 cm-‘. It appears that a number of small, persistent pertur-
bations in the bands are responsible for the discrepancy.
A variety of triplet-singlet bands in the 700-800 nm region were also observed at
high resolution during these experiments. Now that the ground state constants are
well established, and the upper singlet state constants can be used as guidelines, the
analysis of the more complex T1-So bands is being attempted. Since bands for the
same upper vibronic state of H2CSe and DzCSe were resolvable, we anticipate being
able to obtain a much more precise excited triplet state geometry than the constrained
S, geometric data reported in this work.

APPENDIX

Tables IX, X, and XI list all the assigned transitions of the rotationally analyzed
bands of the k ‘AZ-J? ‘A, system of selenoformaldehyde. The lines are presented in
subband tables organized by upper state J, in order to clearly show the excited state
perturbations evident in the spectra. An asterisk indicates an assignment that was not
included in the least-squares determination of the excited state rotational constants.
 192 CLOUTHIER, JUDGE, AND MOULE

TABLE IX

Selenofomaldehyde H2Cs0Se 4;

Observed Ohs.._ Observed ObS._ Observed Ohs. -

J’ Wavenumber Calc. Wa”*“wnber oak. Wavenumber Calc.

0.011 14003.1ss 0.013

-0.016 14002.260 -0.027
-O.OSB” 14001.314 -0.001
-0.052 14000.2s5 -0.033
-0.013 13sss.212 -0.015
0.003 13998.053 0.001
0.003 139S6..$12 0.008 13862.252 0.003
0.012 13SS5.483 0.004 l3seO.120 0.002

13954.689 -0.004
13951.743 0.005
13946.699 -0.006

K’4 - K”=4 Sub-Band

R(J) P(J) P(J)

Observed Ob.T.- Observed 0br.- Observed Obs.-

Wavenumber Cak. Wa”e”wnber Calc. Wa”e”umber Cal.c.

1s 13878.230 13946.659 0.002

20 13$77.55$ 13944.368 0.011
21 13S76.622 13942.030 0.015
22 13876.007 13!33$.600 0.018
23 13875.112 13937.078 0.003
24 13874.160 13931.527 0.035
25 13873.OS7 13931.845 0.009
26 13972.006 13929.136 0.031
27 13970 801 13926.330 0.031
28 13969.536 13946.666 13923.440 0.022
29 13958.1$6 13941.732 13920.481 0.018
30 13966.778
13965.576 0.009 31 13965.273
13964.254 0.022

K’=4 - v-3 Sub-Band

R(J) Q(J) P(J)

Observed Obr: Obrrrvsd Obn.- Observed 0ba.- Observed Ohs.- Observed obs.- Observed Ohs:
J’ Wavenumber Calc. wavenumber Calc. Wavenumber Calc. J’ w.venumbsr Calc. W.venumher Calc. Wa”e”umber Cak.
SPECTRA OF SELENOFORMALDEHYDE 193

TABLE IX-Continued

K’=J K-4 Sub-Band

R(J) Q(J) P(J)

Obrsrved ax.- Observed oh. - Observed Oil.-

J’ Wavenumber Calc. Wavenumber CSlC. Wa”*“umber Cal=.

3
CLOUTHIER, JUDGE, AND MOULE

TABLE IX-Continued

13663.966 E 13652.65, 13640.491

13663.96, 0 13652.636 13840.506
13663.669 E 13651.555 13636.562
13663.702 0 13651.530 13636.610
13663.283 E 13650.361 13636.563
13663.315 0 13850.324 13636.606
13662.845 E 13648.151 13634.514
13662.816 0 13648.063 13634.581
13662.34L E 13647.84, 13632.393
13662.417 0 13647.773 13832.466
13861.75, E 13646.461 13630.16l
13861.642 0 13846.376 13830.2,D 0.013
l3661.0,‘ E 138U.865 13827.691 0.017
13861.173 0 13844.694 13627.96, -0.005
13860.313 E 13643.462 13625.513 -0.000
13860.166 0 13643.322 13625.659 0.001
13659.509 E 136‘1.690 13823.090 0.013
13859.695 0 13641.696 13823.273 0.023
13658.621 E 13610.186 13820.553 -0.014
13658.,!33 0 13638.879 13820.761 -0.011
13657.633 E 13636.454 13817.97, -0.004
13857.873 0 13638.222 13816.231 0.009
13656.631 E 13636.639 13815.346 0.026
13856.662 0 13636.394 13615.604 0.002
13655.463 E 13634.756 13612.574 -0.010
 SPECTRA OF SELENOFORMALDEHYDE

TABLE IX-Continued

33 E

34 E

35

E
E
E

E
E
E
E E
E
E
 196 CLOUTHIER, JUDGE, AND MOULE

TABLE X

Selenofomaldehyde H2C7*Se4;

K’-8 - K-7 Sub-Band K’-7 - r-6 Sub-Band

Q(J) P(J) R(J) Q(J) P(J)

obs.rved Qbs.- Observed ms.- Observed Qbs.-

J’ Wa”.“udl.r Calc. wavenunb*r c*1c. Wa”*“urhr CSlC.

K’-5 - r-4 Sub-Band

R(J) Q(J) PC.71

5 13979.621
13986.840 0.252 6 13979.989
13985.441 0.269. 7 13980.287
13985.859 0.27,* 13978.549 0.278” 8 13980.533
13985.189 0.2,1* 13977.063 0.269’ 8 13980.673
13984.481 0.301* 13975.541 0.296. 10 13980.729
13983.632 0.254* 13973.883 9.262* 11 13980.729
13982.758 0.27w 139,2.196 0.273* 12 13980.649
13981.806 o.zm* 13970.434 0.283' 13 1398cl.505
13980.729 0.242* 13968.553 0.248* 14 13980.287
13979.620 0.24w 13966.62, 0.2,3' 15 13979.999 13957.781 13954.825
13978.491 0.29w 13964.683 0.294* 16 13979.631 13966.627 13952.810
13977.23.90.301* 13962.620 0.390* 1, 13979.194 13965.383 13950.766
13975.921 0.31,. 13960.486 0.320' 18 13978.642 13964.024 13948.600
13974.526 9.328* 13958.289 0.330* 139,8.033 13962.603 13946.371
13973.065 0.350" 13956.018 0.352* :i 13977.372 13961.139 13944.085
13971.525 0.36,* 13953.666 0.36,' 21 13976.531 13859.575 13941.71,
13964.903 0.376* 13951.229 0.372* 22 13975.816 1395,.9*1 13939.265
13958.236 0.4lW 13946.73l 0.392. 23 13Q74.913 13956.240 13936.753
13966.520 0.4%3* 13946.226 0.47P 24 13973.951 13954.*68 13934.159
13964.777 0.593* 13943.ma 0.56P 25 13972.900 13952.609 13931.194
13962.460 0.20,* 13940.551 0.208* 26 13971.799 1395ll.670 13928.753
13960.557 0.310* 13937.808 0.281' 27 13879.586 13948.685 13925.952
13958.575 0.40.5* 13935.043 0.405* 28 13969.319 13946.589 13923.053
13956.294 0.2tl1* 29 13967.990 13944.412 13920.080
13953.982 0.19** 30 13966.575 13942.209 13Ql7.025
31 13965.035 13939.901
32 13963.413 13937.489

K'=b - P-3 Sub-Band

R(J) Q(J) P(J)

Observed ems:
J’ Wavenumber C.lC

: 13814.683 -0.102* 13*1D.910 *.o?_*

13809.605 -o.los*

6 13818.956 -o.om* 1381&.0,, -o.Lmw 13808.391 -D.DS,*

7 13819.295 -0.024 13.313.582-0.050 13807.090 -D.013

," 13967.782
13967.638 -0.018
-0.012 13961.139 -0.046
13960.439 -0.009 13953.825 -0.009
13952.310 -0.048 g" 13819.684
13819.545 -0.012
-0.000 13812.363
13813.030 -9.023
-0.015 13804.274
13805.720 -0.015
0.012
10 13967.854 -0.021 13859.733 -0.015 13950.790 -0.018 10 13819.751 -0.025 13811.633 -0.019 13802.692 -0.025
11 13967.854 -0.022 13958.910 -0.02, 1394Q.160 -0.025 11 13819.,51
~~ -0.029 13810.817 -0.028
I* 13967.782 -0.021 13958.031 -0.020 l3917.458 -0.019 IZ 13819.684 -0.02, 13809.940 -o.ozl
 SPECTRA OF SELENOFORMALDEHYDE

TABLE X-Continued

23
24

E
0
33 E E
0 0
3‘ E E
0
E
0

K’=3 - r-4 Sub-Band

R(J) Q(J) P(J)

14 E
198 CLOUTHIER, JUDGE, AND MOULE

TABLE X-Continued

0.011
0.002
0.014

-0.001
0.004
0.007
0.010
0.001
0.003

13936.940
13932.6l”JS
13935.401
13931.577
13935.904
13930.465
13935.113
13929.328
13934.407
 SPECTRA OF SELENOFORMALDEHYDE

TABLE X-Continued

K’-2 - P-1 Sub-Band K’4 - K-3 Sub-Band

R(J) Q(J) P(J) R(J) ac.7, P(J)

Observrd ms: Ob**w*d 0k.s: Obser”*d ma.- Obssrv*d oh.- obrerv*d Obs.- 0Lxsrved ok,-
J, Wavsnunber Calc. wav*number oak. W.wnumber ca1c. .,’ !J*o*numb.r ca1c. wav*ntier oak. wIlvenumber Calc.

26 E 138X.296 0.019 13834.494 0.008 E 13612.233

0 13655.621 0.011 13634.171 O.OOl 13612.576
27 E 13654.066 -0.008 13832.347 0.025 13609.400
0 13634.465 0.025 13632.156 -0.004 13609.619
26 6 13852.619 0.022 13630.463 -0.003 e 13606.530
0 13653.234 -0.003 13830.089 0.026 0 13606.952
136W.013 2s E 13651.419 -0.025 13626.592 0.015 13603.515
13906.136 0 13651.856 0.013 13627.693 -0.016 : 13604.053
13696.603 30 E ~3650.004 -0.010 13626.202 0.006
13904.224 0 13650.365 0.010 13625.66Q -0.007
136%. 173 31 E 136‘6.697 -0.012 13623.996 0.055*
13902.201 0 1364S.170 0.035 13623.357 -0.006
13891.569 3.2 E 13646.906 -0.022 13621.619 0.007
13900.166 0 13617.619 -0.002 13620.951 -0.029
13666.981 33 E 13845.276 0.004 13619.179 -0.023
13898.032 0 13846.013 -0.019 13616.522 0.002
13886.279 3 E 13616.6,3 -0.051"
0 13895.827 0 138“.325 -0.011
35 35

K’=O K”=l Sub-Band K’4 - K-1 Sub-sand

Q(J) P(J) I-l(J) Q(J) P(J)

Observed okrs.- Observed Oh- Obrsrved cdl*.-

J’ Hav*number Calc Wa”~number Cdc wavsnumbsr Calc.

0 13896.691 -0.069 16 0 m303.062 -0.022 13665.594 -0.011 0 13673.350 -0.013

E ~3SSS.5SO 0 138S7.S69 -0.103 19 0 13902.642 0.007 13664.031 0.006 0 13671.320 0.010
E x3699.468 0 13697.103 -0.033 20 0 13902.161 0.023 13862.361 0.030 13669.217 0.027
13699.250 0 13696.136 -0.025 21 0 13901.47, -0.059 13680.549 -0.045 13666.953 -0.01,
13896.950 0 13895 060 -0.016 22 0 13900.673 0.000 13676.746 -0.001 13664.73, -0.005
13698.530 0 13893.964 -0.007 23 0 13900.166 0.020 X36,6.640 0.022 13662.432 0.017
138S6.032 0 13692,lll -0.006 24 0 13699.365 0.036 13674.63, 0.038 13660.050 0.033
13697.450 0 13691.515 -0.00, 25 0 13696.530 0.046 13672.748 0.055 13657.602 0.052
13696.791 0 13690.192 -0.009 26 0 13697.59, (1.054' 13670.55, 0.058’ 13855.062 0.049
13896.053 0 13666.604 -0.009 27 0 13696.641 0.10,* 13866.332 0.113' 13652.514 0.109”
138S5.223 0 13667.356 -0.005 26 0 13695.620 O.l66* 13666.022 0.17,' 136C9.666 0.160”
13894.320 0 13665.837 -0.006 29 0 13664.,99 0.496* 13663.696 0.502 13647.176 0.495”
13693.317 0 13664.247 -0.012 30 0 13693.142 0.659' 13660.920 0.066. 13604.220 0.055*
310 13691.916 o.m?* 13656.359 0.131. 13641.COO 0.119"
32 0 13690.192 -0.245' 13655.294 -0.222* 13636.111 -0.219’
13 0 13903.981 -0.041 E 13669.605 -6.046 0 13619.072 -0.011 33 0 1366!3.130 0.11,' 13652.662 0.139* 13635.436 0.126*
16 0 13903.753 -0.024 E 13686.502 -O.OZO 0 13677.243 -0.020 34 0 19667.650 0.127" 13649.974 0.126* 13632.352 0,122”
I7 0 13903.448 -0.017 E 13667.091 -0.016 0 13675.337 -0.009
 CLOUTHIER, JUDGE, AND MOULE

TABLE XI

Selenoformaldehyde D2C 80Se0:

K’-* - K-8 Sub-Band

Q(J) P(J)

i
8
9
SPECTRA OF SELENOFORMALDEHYDE 201

TABLE XI-Continued
 202 CLOUTHIER, JUDGE, AND MOULE

TABLE XI-Continued

K’-Z - r-2 Sub-sand

R(J) Q(J) P(J)

Ob*eev.d ohs: Oba.rved ObEz.- obs*rved ObS -

J’ Wa”e”umb*r Calc. wa”e”umb.r Calc. Wavenumber Calc.

K’-0 - I?-0 Sub-Band

R(J) Q(J) PC.71

Observed 0bS.F Observed Ohs: Observed obr:

J’ Wa”enumber CSlC. wavenumber oak. Wa”enumber CdC.

ACKNOWLEDGMENTS

The experimental part of this work was performed while the authors were Visiting Scientists at the MIT
Laser Research Center, which is a National Science Foundation Regional Instrumentation Facility. We
thank Joe Ma&in, Mike Otteson, and Ramachandra Dasari for their help and hospitality during our stay
at MIT. We also thank Prof. G. W. King for the gift of the pure isotopes of selenium and B. G. Winsborrow
for assistance with the snythesis.
DJC and RHJ acknowledge the Donors of The Petroleum Research Fund, administered by the American
Chemical Society, for support of this work. RHJ also thanks Research Corporation for funding in support
of this work. DCM acknowledges the support of the National Sciences and Engineering Research Council
of Canada.

RECEIVED: January 26, 1990

 SPECTRA OF SELENOFORMALDEHYDE 203

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