30 November 2001

Chemical Physics Letters 349 (2001) 249±256

www.elsevier.com/locate/cplett

The millimeter/sub-millimeter spectrum of the LiS

radical in its 2Pi ground state
M.A. Brewster, L.M. Ziurys *

Department of Chemistry, Department of Astronomy and Steward Observatory, University of Arizona,

933 North Cherry Avenue, Tucson, AZ 85721, USA
Received 12 September 2001

Abstract
The pure rotational spectrum of LiS …X2 Pi † has been recorded in the v ˆ 0 and v ˆ 1 states in the region 130±540
GHz using millimeter/sub-millimeter direct absorption methods. This radical was synthesized from lithium vapor and
CS2 in a DC discharge. Transitions arising from the two orbit components were measured, both which exhibited
lambda-doubling and, for the X ˆ 1=2 ladder, hyper®ne interactions. Rotational, lambda-doubling, and hyper®ne
parameters have subsequently been determined. These data prove unambiguously that the ground state of LiS is 2 Pi
and suggest that the A2 R‡ state lies  4300 cm 1 higher in energy. The bonding in this radical appears to be pre-
dominantly ionic. Ó 2001 Elsevier Science B.V. All rights reserved.

1. Introduction longer and sometimes weaker than their oxide

Metal oxide species play a major role in a
variety of environments, including high tempera-
ture reactions, corrosion processes, catalysis and in
stellar atmospheres [1±3]. Examining the bonding
in these molecules has thus been the topic of much
experimental, e.g., [4±6], and theoretical work,
e.g., [7±9]. Also of interest are the corresponding
metal sul®de species. Although substitution of the
oxygen atom by sulfur produces an isovalent
compound, di€erences in electronegativity and
valence electron con®gurations between these two
elements are thought to generate subtle structural
variations [10,11]. For example, metal mono-
sul®des are predicted to form bonds that are
*
Corresponding author. Fax: +520-621-1532.
E-mail address: lziurys@as.arizona.edu (L.M. Ziurys).
0009-2614/01/$ - see front matter Ó 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 0 9 - 2 6 1 4 ( 0 1 ) 0 1 2 0 2 - 7
counterparts. They also may be more covalent in
certain instances.
One oxide system which has been heavily in-
vestigated in the past is the alkali metal group.
These molecules have attracted particular interest
because the ground state term is predicted to
change from 2 P to 2 R as the periodic table is
descended [12,13], with the cross-over occurring
between NaO and KO. Experimentally, it has been
found that both NaO and LiO have 2 P ground
electronic states [14,15], while those of RbO and
CsO are 2 R [5,6]. There is some evidence that KO
has 2 P symmetry in its ground state as well [16].
This change in electronic term and hence electron
con®guration (r2 p3 vs. p4 r1 ) has been attributed
to the competition between electrostatic and ex-
change interactions [11]. A similar trend is pre-
dicted for the alkali sul®des, except the change in
symmetry is calculated to occur later down the
250 M.A. Brewster, L.M. Ziurys / Chemical Physics Letters 349 (2001) 249±256
column. Computations have suggested that KS
and RbS, for example, have 2 P ground states, in
contrast to their oxide counterparts [11].
Naturally, it is of interest to investigate the
electronic ground states of the alkali sul®de spe-
cies, as well as their bonding properties and other
characteristics, especially in comparison to the
oxides. To achieve this end, we have measured the
pure rotational spectrum of both NaS [17] and KS
[18], using millimeter/sub-millimeter direct ab-
sorption methods. These radicals had not been
studied previously by any spectroscopic technique.
The recorded spectra have clearly shown that the
ground state of both molecules is 2 P, in agreement
with theory. Moreover, transitions of both radicals
exhibited large lambda-doubling, signifying the
existence of a nearby 2 R state, also predicted by
theoretical calculations [10]. LiS, on the other
hand, has never been investigated by any spec-
troscopic method. This sul®de is particularly im-
portant because it can be compared most directly
to the hydrogen analog, SH. Despite the fact that
hydrogen and lithium both have one valence
electron, their corresponding analogs are often
predicted to have di€erent electronic ground
states, such as CH (X2 Pr ) and LiC …X4 R† [19].
Here we present the ®rst experimental study of
the LiS radical. The pure rotational spectrum of
this species has been recorded using millimeter/
sub-millimeter direct absorption methods. Ob-
servation of both spin±orbit components (X ˆ 1=2
and 3/2) and their lambda-doubling interactions
con®rms that the electronic ground state of this
species is indeed 2 Pi . Hyper®ne splittings, arising
from the 7 Li nucleus, were also observed. In this
Letter we present our spectroscopic measurements
and analysis for this molecule, compare these re-
sults with those obtained previously for NaS and
KS, and discuss the implications for bonding in
alkali sul®de compounds.
2. Experimental
The measurements were conducted with one of
the millimeter/sub-millimeter direct absorption
spectrometers of the Ziurys group. Details can be
found in [20]. Brie¯y, this instrument consists of a
phase-locked Gunn oscillator/varactor multiplier
radiation source, a 0.5 m long double-pass reac-
tion cell containing a Broida-type oven, and an
InSb hot electron bolometer detector. Phase-sen-
sitive detection is carried out using source mod-
ulation.
Lithium sul®de was generated in a DC glow
discharge in a mixture of 5±8 mTorr CS2 , 15±20
mTorr argon, and K 1 mTorr of Li vapor. The
metal vapor was produced by the Broida-type
oven. Carbon disul®de and argon were mixed to-
gether prior to introduction into the reaction
chamber. They were then ¯owed into the cell be-
neath the oven to assist in carrying the metal vapor
into the discharge region, located about 5 cm
above the oven itself. The discharged gas mixture
exhibited a bright magenta color, likely due to
emission of atomic lithium.
An approximate rotational constant of LiS was
initially estimated from theoretical studies [19],
which predicted bond lengths. Based on this value,
extensive regions in frequency space … 5±6 GHz†
were continuously searched to locate the LiS sig-
nals. Once the rotational pattern had been estab-
lished and both spin±orbit components identi®ed,
only scans 100 MHz in frequency coverage were
required to ®nd additional transitions. The LiS
signals were in general suciently intense such that
transition frequencies could be obtained from an
average of one scan taken in increasing frequency
and another in decreasing frequency. However,
below 250 GHz, the presence of hyper®ne split-
tings required as many as 20 such scan averages to
obtain reasonable signal levels. Typical linewidths
varied from 470±1300 kHz.
3. Results and analysis
Table 1 presents the transition frequencies
measured for LiS. Forty-three individual lines
were recorded for this radical in its v ˆ 0 vibra-
tional state, and 18 in the v ˆ 1 level. As is evident
in the table, both spin±orbit components were
observed in each state. In the X ˆ 3=2 ladder, the
lambda-doubling was found to be on the order of
3±35 MHz, with the splitting increasing with in-
creasing J; it was considerably larger … J 5 GHz†
Table 1
Observed transition frequencies for LiS (X2 Pi )a
vˆ0 vˆ1
2 2 2 2
P3=2 P1=2 P3=2 P1=2
J 00 J0 Parity F 00 F0 mobs mo c mobs mo c mobs mo c mobs mo c

b
2.5 3.5 f 4 5 132 017.458 )0.160 135 072.592 )0.017 ± ±
2.5 3.5 f 3 4 ± 135 073.530 0.197 ± ±
2.5 3.5 f 2 3 ± 135 073.876c 0.175 ± ±

M.A. Brewster, L.M. Ziurys / Chemical Physics Letters 349 (2001) 249±256
2.5 3.5 f 1 2 ± 135 073.876c 0.164 ± ±
2.5 3.5 e 4 5 132 015.776b 0.192 130 203.366 )0.062 ± ±
2.5 3.5 e 3 4 ± 130 204.165c 0.377 ± ±
2.5 3.5 e 2 3 ± 130 204.165c 0.055 ± ±
2.5 3.5 e 1 2 ± 130 204.165c )0.229 ± ±
3.5 4.5 f 5 6 169 724.380b )0.057 172 954.484 )0.020 ± ±
3.5 4.5 f 4 5 ± 172 954.955 0.056 ± ±
3.5 4.5 f 3 4 ± 172 955.173c 0.062 ± ±
3.5 4.5 f 2 3 ± 172 955.173c 0.033 ± ±
3.5 4.5 e 5 6 169 721.147b 0.098 168 088.874 0.078 ± ±
3.5 4.5 e 4 5 ± 168 089.273c 0.290 ± ±
3.5 4.5 e 3 4 ± 168 089.273c 0.098 ± ±
3.5 4.5 e 2 3 ± 168 089.273c )0.096 ± ±
b
5.5 6.5 f 245 107.485 0.028 248 685.234 0.015 ± ±
b
5.5 6.5 e 245 100.373 0.022 243 828.882 )0.002 ± ±
b
6.5 7.5 f 282 779.366 0.006 286 529.426 )0.025 ± ±
b
6.5 7.5 e 282 769.888 )0.005 281 679.080 )0.023 ± ±
b
7.5 8.5 f 320 435.329 0.001 324 356.743 )0.046 ± ±
b
7.5 8.5 e 320 423.146 )0.022 319 513.274 0.009 ± ±
b
8.5 9.5 f 358 073.178 )0.035 362 164.999 )0.032 ± ±
b
8.5 9.5 e 358 058.025 )0.003 357 329.151 )0.021 ± ±
b
9.5 10.5 f 395 690.866 0.000 399 951.941 )0.040 391 439.150 0.038 ±
b
9.5 10.5 e 395 672.283 )0.046 395 124.590 )0.035 391 420.950 0.013 390 820.585 0.006
b
10.5 11.5 f ± 437 715.408 )0.032 428 630.017 0.006 ±
b
10.5 11.5 e ± ± 428 608.196 )0.027 428 185.187 )0.004
b
11.5 12.5 f 470 856.876 )0.007 475 453.219 0.007 465 796.520 )0.014 470 354.374 0.003
b
11.5 12.5 e 470 830.649 )0.015 470 645.365 )0.010 465 770.796 )0.019 465 525.114 )0.013
b
12.5 13.5 f 508 400.979 0.029 513 163.161 0.059 502 936.521 )0.027 507 656.253 )0.004
b
12.5 13.5 e 508 370.429 0.022 508 366.301 0.024 502 906.573 )0.007 502 838.220 0.016
b
13.5 14.5 f ± ± 540 047.926 0.010 544 928.253 0.002
b
13.5 14.5 e ± ± 540 013.414 0.030 540 122.233 )0.065
a
In MHz.
b
Blend of all hf components.
c
Blended lines.

251
252 M.A. Brewster, L.M. Ziurys / Chemical Physics Letters 349 (2001) 249±256

in the X ˆ 1=2 sub-level, and in this case the

splitting decreased with increasing J. The X ˆ 3=2
lines were also found to be stronger in intensity
than the other ladder, verifying the inverted nature
of the P term. In addition, in the lower rotational
transitions of the X ˆ 1=2 ladder, hyper®ne
structure was partially resolved, which arises from
the lithium 7 nuclear spin of I ˆ 3=2. The hy-
per®ne interactions in principle should split each
lambda-doublet into four strong components, but
in the case of LiS, only two features were typically
observed. One such feature appeared to be the
strongest hf component, for example, the
F ˆ 5 ! 6 line in the J ˆ 7=2 ! 9=2 transition
(see Table 1), and the second was composed of the
other three components (F ˆ 4 ! 5, 3 ! 4, and
2 ! 3). Usually, these three hf transitions were
totally collapsed, but in certain cases, one com-
ponent appeared as a shoulder on the line com-
prising the other two, and its frequency could be
measured separately. Hyper®ne interactions were
not observed in the X ˆ 3=2 ladder, and at higher
J, the hf splitting in the X ˆ 1=2 sub-level was
completely collapsed as well. Hence, in these cases

Fig. 2. Spectra of the J ˆ 5=2 ! 7=2 transition of LiS (X2 Pi :

Fig. 1. A section of the 25=2 ! 27=2 rotational transition of
LiS (X2 Pi : v ˆ 0) near 508.4 GHz, showing the lambda-doub-
lets of the X ˆ 3=2 sub-level (labeled e and f) and the e parity
component in the X ˆ 1=2 ladder. The X ˆ 3=2 doublets are
split by  30 MHz, while those of the X ˆ 1=2 sub-level are
separated by almost 5 GHz. The stronger intensities of the
X ˆ 3=2 lines indicate that the P state is inverted. This spec-
trum was obtained as a single, 100 MHz scan, lasting ap-
proximately 1 min.
v ˆ 0), showing both the X ˆ 3=2 spin±orbit ladder near 132
GHz (top panel) and the X ˆ 1=2 sub-level near 130±135 GHz
(bottom panel). The X ˆ 3=2 transition consists of two lines
which are lambda-doublets, indicated by parity designations e
and f. The X ˆ 1=2 transition, on the other hand, is split by
both lambda-doubling (see e and f labeling) and hyper®ne in-
teractions. Each lambda-doublet therefore appears as two fea-
tures which result from four hf components, indicated by
quantum number F . The approximate positions and relative
intensities of these hyper®ne components are shown under each
spectrum. The top spectrum is an average of 20, 5 MHz scans,
each lasting 10 s in duration; the bottom spectra are 16 scan
averages, also 5 MHz in frequency coverage and with 10 s scan
time.
there is only a single feature observed for each
lambda-doubling component.
Representative spectra illustrating these e€ects
are presented in Figs. 1 and 2. Fig. 1 shows the
lambda-doublets in the X ˆ 3=2 sub-level of the
J ˆ 25=2 ! 27=2 transition of LiS (v ˆ 0) near
 M.A. Brewster, L.M. Ziurys / Chemical Physics Letters 349 (2001) 249±256 253

508.4 GHz. The doublets, labeled by the parity
designation e and f, are separated in this transition
by about 30 MHz. Also present in the spectrum is
the e component of the X ˆ 1=2 sub-level; its
matching doublets lies  5 GHz higher in fre-
quency. The X ˆ 3=2 lines are clearly stronger in
intensity than the X ˆ 1=2 feature, evidence for a
2
Pi ground state.
In Fig. 2, a low frequency transition
…J ˆ 5=2 ! 7=2† in both X ladders is shown at 132
GHz …X ˆ 3=2† and at 130±135 GHz …X ˆ 1=2†.
Both lambda-doublets in the X ˆ 1=2 sub-level
(lower panel) are additionally split into two fea-
tures because of lithium hyper®ne interactions.
One feature is attributable to the F ˆ 4 ! 5
transition, and the other is a blend of the
F ˆ 3 ! 4, 2 ! 3, and 1 ! 2 lines. One of these
components …F ˆ 3 ! 4† appears as a shoulder on
the left side of the f parity line, making it broader
by about 300 kHz than the expected linewidth. The
positions and relative intensities of the four hf
components that compose the e and f transitions
are indicated beneath the respective spectrum. At
higher frequencies, these two features merge to-
gether and eventually form a single line. In the
X ˆ 3=2 spectrum (top panel) there is little evi-
dence of hf splittings in the closely spaced lambda-
doublets.
The data were analyzed using a standard
Hund's case (a) Hamiltonian consisting of mole-
cular frame rotation, spin±orbit interaction,
lambda-doubling, and hyper®ne coupling, includ-
ing centrifugal distortion corrections [21]:
H^eff ˆ H^rot ‡ H^so ‡ H^LD ‡ H^hf : …
The v ˆ 0 and v ˆ 1 data sets were ®t sepa-
rately. Because there had been no previous spec-
troscopic studies of LiS, an estimate of the
spin±orbit constant A was not available for the
data ®t. Consequently, that of NaS was used as an
initial value ()8000 GHz [17]). The spin±orbit
constant was allowed to vary in the ®t and a rea-
sonably de®ned value was obtained.
Analysis of the hyper®ne interaction in the
v ˆ 0 state proved somewhat problematic because
it was observed only in one X ladder, and, even in
this sub-level, it was not completely resolved. (No
hf splittings were recorded for the v ˆ 1 state.)
Hence, all four hf parameters (a, b, c, and d) could
not be independently determined. Because there
was a noticeable di€erence between the hyper®ne
splittings in the e and f parity components in the
X ˆ 1=2 ladder, the d constant could be estab-
lished. Also, the a parameter appeared necessary
for a reasonable ®t. A signi®cant correlation, on
the other hand, was found between b and c, and
consequently in the ®nal ®t, only the value …b ‡ c†
could be determined. The v ˆ 0 transition fre-
quencies were ®t as one data set, even though the
hf splittings were collapsed for levels with
J > 11=2, and for all X ˆ 3=2 transitions. Parity
was chosen to match that of KS [18], which con-
sequently made the hf constant d positive.
The spectroscopic constants resulting from this
analysis are presented in Table 2 for both the v ˆ 0
and v ˆ 1 vibrational states of LiS …X2 Pi †, as well
as the individual rms of the data ®ts. As shown in
the table, all constants are well determined and the
rms of the ®ts are well below the estimated ex-
perimental uncertainty of 100 kHz. The residuals
are given in Table 1. (Those listed for the transi-
tions where the hyper®ne splitting was totally
collapsed are an average over the four individual
residuals given for each hf component.) As is evi-
dent in the table, centrifugal distortion corrections
were found necessary for the spin±orbit constant
and lambda-doubling parameter p.
Because two vibrational states were in-
vestigated, equilibrium rotational constants could
be derived. These values are presented in Table 3.
1†
Table 2
Spectroscopic constants for LiS (X2 Pi )a
Parameter vˆ0 vˆ1
A )8 222 000 (90 000) )8 185 000 (81 000)
AD )2.69 (94) )2.17 (83)
BV 18 906.2805 (31) 18 702.7044 (37)
DV 0.090507 (12) 0.089923 (10)
p 4 860.84 (27) 4 883.68 (35)
q )6.73 (20) )6.58 (17)
pD )0.08569 (52) )0.08910 (57)
a 3.92 (69) ±
b‡c )7.7 (1.4) ±
d 3.6 (2.1) ±
rms of ®t 0.086 0.016
a
In MHz; errors are 3r.
254 M.A. Brewster, L.M. Ziurys / Chemical Physics Letters 349 (2001) 249±256

Table 3 di€erent rotational spectrum from what has been

Equilibrium constants for LiS (X2 Pi )a observed. As discussed in various theoretical
Parameter This work Theoryb works [11,19], there is competition between elec-
Be 19 008.0681 (39) ± trostatic and exchange forces, the former favoring
ae 203.5761 (48) ± the r2 p3 con®guration, and the latter p4 r1 . For
De 0.090799 (14) ± most of the lighter alkali oxides and sul®des, it has
be )0.000584 (16) ±
been found that the electrostatic forces dominate,
xe 580 cm 1 597 cm 1
re 
2.1497 A 
2.147 A as in the case of LiS.
a
Although, the 2 P term is the ground state for
In MHz, unless indicated otherwise.
b
From [19].
the lighter alkali species, the nearest excited state is
predicted to be 2 R, and results from promotion of
From Be and De , the harmonic vibrational fre- a r electron into a p orbital. As the periodic table
quency was also estimated using the relationship is descended, this A2 R state is calculated theoreti-
 3 1=2
4Be cally to move closer in energy to the X2 Pi state,
xe ˆ : …2† until the P state is overtaken, and the energy or-
De
dering reverses. These theoretical energies are gi-
The frequency obtained is xe  580 cm 1 , close ven in Table 4 for the alkali sul®des and oxides.
to that predicted from ab initio calculations Many of the alkali oxides and sul®des have only
(xe ˆ 597 cm 1 [19]. Furthermore, an equilibrium been studied by pure rotational spectroscopy.
bond length for LiS of re ˆ 2:1497 A  was de-
Hence, measurements of the A2 R‡ excited state
termined from Be , also similar in value to that energies are generally not available. However,
 [19]).
derived theoretically (re ˆ 2:147 A these energies can be estimated from rotational
data using the lambda-doubling constant p, as-
suming pure precession [22]:
4. Discussion
4AB
pˆ : …3†
This work is the ®rst spectroscopic observation EP ER
of LiS, and analysis of its pure rotational spectrum Using the p constant derived in this work, the
has veri®ed that the electronic ground state of this A2 R‡ state is estimated to lie  4268 cm 1 above
radical is 2 Pi . The electron con®guration of this the ground state ± close to that predicted by ab
molecule in this state is therefore 1r2 2r2 1p3 . An- initio calculations ( 5000 cm 1 ; see Table 4).
other possible con®guration for LiS is 1r2 1p4 2r1 , Using data from [18,19], the 2 R energies have also
which would have resulted in a 2 R state, and a been estimated for NaS and KS. These values are

Table 4
Lowest-lying 2 R energies for alkali sul®des and oxidesa
Molecule ER EP (experimental)b ER EP (theory) Reference
LiS 4268 4970c , 5088d [11,19]
NaS 3342 4046d [17,11]
KS 1900 1834d [18,11]
LiO 2565 2400e [14,12]
NaO 2050 1902e [15,12]
KO  200 )46e [16,12]
a
In cm 1 .
b
Derived assuming pure precession hypothesis (see text).
c
QCISD (T)/6-311+G (2df) calculation.
d
SDCI calculation.
e
MRCI calculation.
 M.A. Brewster, L.M. Ziurys / Chemical Physics Letters 349 (2001) 249±256
ER EP  3342 and 1900 cm 1 , respectively, also
reasonably close to ab initio predictions (see Table
4). In contrast, the energies of the R state for LiO
and NaO are 2565 and 2050 cm 1 , based on pure
precession [14,15], and that of KO is  200 cm 1
[16]. Again, these values are close to those calcu-
lated theoretically, though there is disagreement in
the case of KO concerning which state actually lies
lowest [12]. (Theory predicts the 2 R state to be
lower by 46 cm 1 .) In general, the R±P separation
is about a factor of two larger in the sul®des than
in the oxides.
Another isovalent molecule that presumably
could have either a 2 Pi or 2 R‡ ground state, de-
pending on its electron con®guration, is the SH
radical. Like the lighter alkali halides, SH has been
found to have a 2 Pi ground state, but its ®rst ex-
cited state …A2 R‡ † lies  31 000 cm 1 higher in
energy [19]. This energy is considerably larger than
for any of the alkali sul®des or oxides. SH is cer-
tainly a very covalent molecule, and therefore, the
R±P separation may indirectly indicate the degree
of covalent character. Covalent bonding is favored
in the 2 Pi : 1r2 p3 con®guration as opposed to the
2 ‡
R : p4 r1 con®guration because an electron pair in
a sigma orbital can be shared between the two
atoms in the P case, but only a single electron in
the R case [7]. This property is also apparent in the
alkali species. Based on electronegativity argu-
ments, the alkali oxides must be fairly ionic and
hence their R±P energy separation is relatively
small. Because sulfur is less electronegative, the
sul®des have more covalent character than the
oxides, and the R±P energy separation is sig-
ni®cantly larger.
Despite having more covalent character than
lithium oxide, LiS is still partly an ionic
molecule. Evidence for ionicity lies in the spin±
orbit constant for LiS, which is
A ˆ 8222 GHz. This constant is fairly close in
value to that of S (3p5 ): f ˆ 9773 GHz [23].
Therefore, the resonance structure Li‡ S must
contribute substantially to the bonding in this
molecule.
A further comparison of ionic vs. covalent
character can be made by examining the hy-
per®ne constants derived for LiS. This interaction
arises from the unpaired electron spin coupling
255
with the 7 Li nuclear spin …I ˆ 3=2† and hence is a
measure of the electron density near the lithium
nucleus. The Fermi contact term in fact traces the
electron density at the nucleus. Consequently, the
magnitude of hyper®ne constants will indicate
the degree of deviation from the Li‡ S structure,
where the unpaired electron lies exclusively on the
sulfur atom. The hyper®ne constants established
for LiS in fact are quite small in value, with the
Fermi contact term near zero. (The parameter
…b ‡ c† ˆ 7:7 (1.4) MHz.) In contrast, the
atomic Fermi contact term for 7 Li is 409 MHz, a
considerably larger number [24]. Hence, there is
little electron density at the lithium nucleus.
Furthermore, the Fermi contact term has been
measured in SH to be (bF ˆ 73:5 MHz [25]. In
this molecule, the nuclear spin arises from the
hydrogen atom (I ˆ 1=2). The electron density is
clearly greater on the hydrogen nucleus in SH
than on lithium in SLi. (Both hydrogen and li-
thium have comparable magnetic moments so a
direct comparison can be made.) The unpaired
electron is thus shared more evenly in SH than
LiS, and thus the bonding is more covalent in the
hydride.
5. Conclusion
Measurements of the pure rotational spectrum
of LiS have demonstrated that this species has a
2
Pi ground state, as do NaS, KS, and SH. Analysis
of the lambda-doubling interactions suggests that
the A2 R‡ state in this radical lies  4300 cm 1
above ground state. Although this energy separa-
tion suggests that the bonding in LiS is more
covalent in character than in LiO, this molecule is
still very ionic. Evidence for this ionicity is found
in the spin±orbit constant, which is similar to that
of S , and in the small values of the lithium hy-
per®ne parameters. Observation of the v ˆ 0 and
v ˆ 1 states of LiS has allowed for calculation of
equilibrium constants re and xe , which are in good
agreement with ab initio calculations. These mea-
surements have demonstrated that, though alkali
sul®des and oxides are isovalent, there are notice-
able di€erences in their bonding and electronic
structure.
256 M.A. Brewster, L.M. Ziurys / Chemical Physics Letters 349 (2001) 249±256

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