JOURNAL OF CHEMICAL PHYSICS VOLUME 121, NUMBER 23 15 DECEMBER 2004

The rotational spectrum and dynamical structure of LiOH and LiOD:

A combined laboratory and ab initio study
Kelly J. Higgins, Samuel M. Freund,a) and William Klemperer
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138
Aldo J. Apponi and Lucy M. Ziurys
Departments of Chemistry and Astronomy, The University of Arizona, Tucson, Arizona 85721
共Received 30 June 2004; accepted 20 September 2004兲
Millimeter wave rotational spectroscopy and ab initio calculations are used to explore the potential
energy surface of LiOH and LiOD with particular emphasis on the bending states and bending
potential. New measurements extend the observed rotational lines to J⫽7←6 for LiOH and J
⫽8←7 for LiOD for all bending vibrational states up to (033 0). Rotation-vibration energy levels,
geometric expectation values, and dipole moments are calculated using extensive high-level ab
initio three-dimensional potential energy and dipole moment surfaces. Agreement between
calculation and experiment is superb, with predicted B v values typically within 0.3%, D values
within 0.2%, q l values within 0.7%, and dipole moments within 0.9% of experiment. Shifts in B v
values with vibration and isotopic substitution are also well predicted. A combined theoretical and
experimental structural analysis establishes the linear equilibrium structure with r e (Li–O)
⫽1.5776(4) Å and r e (O–H)⫽0.949(2) Å. Predicted fundamental vibrational frequencies are v 1
⫽923.2, v 2 ⫽318.3, and v 3 ⫽3829.8 cm⫺1 for LiOH and v 1 ⫽912.9, v 2 ⫽245.8, and v 3
⫽2824.2 cm⫺1 for LiOD. The molecule is extremely nonrigid with respect to angular deformation;
the calculated deviation from linearity for the vibrationally averaged structure is 19.0° in the 共000兲
state and 41.9° in the (033 0) state. The calculation not only predicts, in agreement with previous
work 关P. R. Bunker, P. Jensen, A. Karpfen, and H. Lischka, J. Mol. Spectrosc. 135, 89 共1989兲兴, a
change from a linear to a bent minimum energy configuration at elongated Li–O distances, but also
a similar change from linear to bent at elongated O–H distances. © 2004 American Institute of
Physics. 关DOI: 10.1063/1.1814631兴

I. INTRODUCTION XOX ⬘ , with X and X ⬘ arbitrary monovalent ligands, the

Molecular structure plays a fundamental role in chemical
reactions. The understanding of chemical bond lengths is
learned essentially from the potential energy function for a
radial coordinate and thus may be readily obtained from a
variety of diatomic examples. Furthermore, the relatively
small variation in internuclear distance generally encoun-
tered in a particular elemental pair reduces the incentive for
detailed understanding with predictive power. Evaluation of
the angular geometry and with it the potential energy func-
tion for angular coordinates is both more important and prob-
ably much more difficult. Since virtually all molecular ge-
ometries can be summarized by an angle of 135°⫾45°, it is
clear that for a predictive utility, theories of angular potential
functions must be accurate to a few degrees. It is indeed the
angular geometry of stereochemistry that has been the target
of numerous ad hoc models.1
The explanations for the geometry of the water molecule
play an important role in the development of the nature of
directed valence. The H2 O molecule is the simplest stable,
readily studied polyatomic molecule. Since the general ex-
planations of the 104° angle of HOH holds equally for
a兲
Present address: Los Alamos National Laboratory, Los Alamos, New
Mexico 87545.
similarity in angular geometry of a wide variety of molecules
is used to establish the validity and power of the presented
explanation. Clearly, it is equally useful to examine the in-
stances in which the geometry of XOX ⬘ is very different than
that of water. There are many systems in which the angle
around oxygen is linear or near linear. For example, this is
the most common angular geometry of Si–O–Si units in
silicate crystals and Li–O–Li molecules in the gas phase.2
The system just between bent H2 O and linear Li2 O is
LiOH. The LiOH molecule was first studied in the gas phase
by Freund,3 who directly measured the l-type doubling tran-
sitions for v 2 ⫽1, 2, and 3 in the microwave region. Mc-
Naughton et al.4 later studied LiOH and several isotopically
substituted species at millimeter wavelengths by measuring
its rotational spectrum in the ground state and in a number of
the bending modes, but only included data for J⭐5 and v 2
⭐2. These authors found LiOH to be linear at least to a first
approximation. They also showed the difficulty in establish-
ing the linearity of the minimum energy configuration from a
pure rotational spectrum for systems suspected of having
large amplitude oscillations.
Previous computational studies of LiOH range from ge-
ometry optimizations and harmonic frequency calcu-
lations5–10 to more complete potential energy surfaces and
rotation-vibration state calculations.4,11 Early work by Pople

0021-9606/2004/121(23)/11715/16/$22.00 11715 © 2004 American Institute of Physics

Downloaded 25 Mar 2005 to 128.196.209.95. Redistribution subject to AIP license or copyright, see http://jcp.aip.org/jcp/copyright.jsp
11716 J. Chem. Phys., Vol. 121, No. 23, 15 December 2004
and co-workers6,7 calculated geometries as a means to evalu-
ate theoretical methods and basis sets. Gurvich et al.12 have
summarized computational and experimental work through
1996. Most recently, several groups have separately calcu-
lated various properties of LiOH, including its structure and
heat of formation using high-level methods, large basis sets,
and several levels of core electron correlation.9,10,13,14 Mc-
Naughton et al.4 performed limited ab initio calculations of
the bending potential, determining the optimal bond lengths
for six LiOH bond angles at the MP3/6-311G** level of
theory. The most extensive calculations were performed by
Bunker et al.,11 who calculated the potential energy at 166
geometries using the average coupled pair functional 共ACPF兲
method, fit the results to an analytic expression, and calcu-
lated the rotation-vibration energies using Jensen’s morse
oscillator-rigid bender internal dynamics 共MORBID兲 varia-
tional approach on the full three-dimensional analytic sur-
face. They also discovered that there is a large Li–O stretch-
bend interaction that results in an optimal LiOH structure
that is bent when the Li–O bond is stretched.
The methodology of the present research is to generate
an extensive data set of reliable experimental and fully ab
initio results. In this paper, we present a combined laboratory
and ab initio study of LiOH to further investigate its poten-
tial energy surface, paying particular attention to the bending
potential and excited bending states. The experimental mea-
surements were extended to include v 2 ⫽3 for both LiOH
and LiOD, and J⫽7 for LiOH and J⫽8 for LiOD. The
computational approach utilizes extensive coupled-cluster
electronic structure calculations with core electron correla-
tion and a large basis set to calculate the potential. The
rotation-vibration energy levels of LiOH, LiOD, Li 18 OH,
and 6 LiOH for the generated three-dimensional potential are
calculated using the DVR3D package of Tennyson and
co-workers.15 The resulting energy levels are then compared
to experiment through fitted molecular constants as a means
to assess the accuracy of the potential.
II. EXPERIMENT
A. Experimental method
The rotational spectra of LiOH and LiOD were mea-
sured using one of the millimeter wave spectrometers of the
Ziurys group that has been used to detect more than 70 new
metal containing species. Detailed descriptions of these in-
struments have been given previously.16 Briefly, the absorp-
tion experiment consists of a Gunn oscillator/Schottky diode
multiplier source operating in the range of 65– 650 GHz, a
gas cell incorporating a Broida oven, and an InSb hot elec-
tron bolometer detector. Phase sensitive detection is achieved
by FM modulation of the tunable radiation source followed
by demodulation with a lock-in amplifier.
The LiOH and LiOD species were generated in a dc
discharge reaction of Li vapor and the appropriate precursor:
50% H2 O2 for LiOH and D2 O for LiOD. Lithium vapor was
produced by resistive heating of solid Li in an alumina cru-
cible lined with a steel sleeve. Without the sleeve, the experi-
ment would not have been possible because Li reacts readily
with the alumina crucible at high temperature. Although co-
Downloaded 25 Mar 2005 to 128.196.209.95. Redistribution subject to AIP license or copyright, see http://jcp.aip.org/jcp/copyright.jsp
Higgins et al.
pious amounts of both LiOH and LiOD were produced with-
out the aid of a dc discharge, the signals were even stronger
in the presence of one, where the optimal conditions were
typically 500–1000 mA and 3–20 V. A variable amount of
Ar carrier gas was introduced to further optimize the signals
as required. This production technique is quite different to
those used by either McNaughton et al.4 or Freund,3 where
Li2 O was heated to 1400 K and then reacted with H2 O or
D2 O and resulted in weak signals. In the work presented
here, high signal to noise was achieved for all the modes
observed, and with that, complete spectral coverage was pos-
sible across the entire working band pass of the instrument,
which allowed for the collection of a more complete data set.
B. Experimental results
The rotational transitions measured for LiOH and LiOD
in the X 1 ⌺ ⫹ ground state are listed in Tables I and II. As
these tables show, seven transitions were recorded for LiOH
and eight transitions for LiOD in the frequency range 70–
504 GHz starting from the lowest possible transition (J lower
⫽l) in each case. This approach allowed the unambiguous
assignment of the rotational spectrum in each vibrational
mode because J must be greater than or equal to l. The lines,
for example, associated with the (033 0) mode disappear in
the J⫽3←2 transition. The same effect was observed for the
(022 0) and the (011 0) modes as well. Moreover, this restric-
tion verified the position of the (020 0) mode because its
lines have a similar intensity to those of the (022 0) mode
and they are seen all the way through the J⫽1←0 transition.
Spectra for v 2 ⫽0, 1, 2, and 3 were measured for both LiOH
and LiOD.
Figures 1 and 2 are stick diagrams illustrating the pro-
gression of the vibrational modes as a function of frequency
within the J⫽5←4 rotational transition of LiOH and LiOD
near 352 and 317 GHz, respectively. As these figures illus-
trate, the line intensities drop off considerably with increas-
ing v 2 quantum number. Using the calculated vibrational en-
ergies listed in Table XI, a vibrational temperature of about
400 K is typically found under normal experimental condi-
tions. In LiOH, the v 2 progression occurs towards lower fre-
quency of the ground 共000兲 state, indicating that the rotation-
vibration term ␣ 2 ⬎0, and it is fairly regular for the states
with v 2 ⫽l. The l-type splitting is sufficiently large in the
(011 0) and (031 0) modes that the upper l-type component in
these cases lies to the high frequency side of the 共000兲 line.
The (022 0) mode is split by a much smaller amount, and the
l-type doubling could not be resolved in the (033 0) mode for
any of the measured transitions. The (020 0) mode is shifted
by over 1 GHz higher in frequency from that of the centroid
of the (022 0), indicating some degree of anharmonicity in
the potential. The rotational constant decreases essentially
linearly with v 2 , indicating a strong cross anharmonicity be-
tween v 2 and v 3 . The (022 0) state is bent more than the
(020 0) state. For LiOD, the vibrational progression begins at
the higher frequency of the 共000兲 state, indicating a small
negative value for ␣ 2 , but reverses at the (033 0) mode ow-
ing to high-order terms in the vibration-rotation interaction.
The l-type doubling in the (011 0) state is large enough to
place the lower component of the doublet on the low fre-
J. Chem. Phys., Vol. 121, No. 23, 15 December 2004 Rotational spectrum of LiOH 11717

TABLE I. Observed transition frequencies 共in MHz兲 for LiOH (X̃ 1 ⌺ ⫹ ). TABLE II. Observed transition frequencies 共in MHz兲 for LiOD (X̃ 1 ⌺ ⫹ ).

Frequency Observed- Frequency Observed-

( v 1 , v l2 , v 3 ) Transition observed Calculated ( v 1 , v l2 , v 3 ) Transition observed Calculated

共000兲 J⫽1←0 70 684.827 ⫺0.007 共000兲 J⫽1←0 62 954.770 0.009

J⫽2←1 141 364.458 0.007 J⫽2←1 125 905.882 0.001
J⫽3←2 212 033.641 0.008 J⫽3←2 188 849.733 0.015
J⫽4←3 251 782.599 ⫺0.031
J⫽4←3 282 687.165 0.001
J⫽5←4 314 700.981 0.005
J⫽5←4 353 319.812 ⫺0.014 J⫽6←5 377 601.122 0.007
J⫽6←5 423 926.405 0.003 J⫽7←6 440 479.411 0.006
J⫽7←6 494 501.678 0.002 J⫽8←7 503 332.199 ⫺0.005
(011c 0) J⫽2←1 140 187.606 0.024 (011c 0) J⫽2←1 125 412.870 ⫺0.013
J⫽3←2 210 268.260 ⫺0.002 J⫽3←2 188 110.215 0.008
J⫽4←3 280 333.188 ⫺0.018 J⫽4←3 250 796.581 ⫺0.009
J⫽5←4 350 377.172 0.001 J⫽5←4 313 468.386 0.000
J⫽6←5 420 394.917 0.005 J⫽6←5 376 121.958 0.010
J⫽7←6 490 381.183 ⫺0.001 J⫽7←6 438 753.630 0.002
J⫽8←7 501 359.776 ⫺0.005
(011d 0) J⫽2←1 141 370.558 0.000
(011d 0) J⫽2←1 126 607.559 0.019
J⫽3←2 212 042.371 0.006
J⫽3←2 189 901.644 0.004
J⫽4←3 282 698.008 0.001
J⫽4←3 253 184.114 ⫺0.022
J⫽5←4 353 332.096 0.003 J⫽5←4 316 451.142 ⫺0.018
J⫽6←5 423 939.221 ⫺0.015 J⫽6←5 379 698.854 0.010
J⫽7←6 494 514.055 0.008 J⫽7←6 442 923.353 0.032
J⫽8←7 506 120.702 ⫺0.019
(020 0) J⫽1←0 70 331.918 ⫺0.054
J⫽2←1 140 655.765 ⫺0.065 (020 0) J⫽1←0 63 194.510 ⫺0.107
J⫽3←2 210 963.418 ⫺0.043 J⫽2←1 126 378.475 ⫺0.223
J⫽4←3 281 246.754 0.005 J⫽3←2 189 541.556 ⫺0.151
J⫽5←4 351 497.638 0.055 J⫽4←3 252 673.077 ⫺0.033
J⫽6←5 421 707.929 0.081 J⫽5←4 315 762.480 0.111
J⫽6←5 378 799.147 0.198
J⫽7←6 491 869.362 ⫺0.067
J⫽7←6 441 772.409 0.094
(022c 0) J⫽8←7 504 671.774 ⫺0.157
J⫽3←2 210 104.778 0.134
J⫽4←3 280 114.958 0.060 (022c 0) J⫽3←2 189 049.044 0.196
J⫽5←4 350 103.961 ⫺0.058 J⫽4←3 252 047.741 0.119
J⫽6←5 420 066.612 ⫺0.059 J⫽5←4 315 031.378 0.012
J⫽7←6 489 997.487 0.037 J⫽6←5 377 996.187 ⫺0.084
J⫽7←6 440 938.337 ⫺0.118
(022d 0) J⫽3←2 210 114.728 ⫺0.058 J⫽8←7 503 854.004 0.088
J⫽4←3 280 140.236 ⫺0.030
J⫽5←4 350 154.806 ⫺0.005 (022d 0) J⫽3←2 189 074.709 0.041
J⫽6←5 420 155.730 ⫺0.012 J⫽4←3 252 112.145 ⫺0.041
J⫽7←6 490 140.466 0.019 J⫽5←4 315 160.430 ⫺0.121
J⫽6←5 378 222.454 ⫺0.072
(031c 0) J⫽3←2 208 802.505 ⫺0.021 J⫽7←6 441 301.003 0.056
J⫽8←7 504 398.794 0.024
J⫽4←3 278 373.373 0.021
J⫽5←4 347 918.473 0.023 (031c 0) J⫽3←2 188 115.134 0.077
J⫽6←5 417 431.349 ⫺0.039 J⫽4←3 250 789.440 ⫺0.021
J⫽7←6 486 905.749 0.014 J⫽5←4 313 437.571 ⫺0.054
J⫽6←5 376 053.064 ⫺0.033
(031d 0) J⫽3←2 212 463.497 ⫺0.112 J⫽7←6 438 629.728 0.070
J⫽4←3 283 252.183 ⫺0.057 J⫽8←7 501 161.510 ⫺0.021
J⫽5←4 354 013.067 0.114
J⫽6←5 424 738.861 ⫺0.094 (031d 0) J⫽3←2 191 893.843 ⫺0.063
J⫽7←6 495 422.623 ⫺0.081 J⫽4←3 255 824.349 0.004
J⫽5←4 319 725.313 0.052
(033cd 0) J⫽4←3 278 489.120 0.003 J⫽6←5 383 588.945 0.042
J⫽5←4 348 080.687 0.012 J⫽7←6 447 407.040 ⫺0.073
J⫽8←7 511 171.102 0.021
J⫽6←5 417 651.727 ⫺0.024
J⫽7←6 487 198.260 0.010 (033c 0) J⫽4←3 251 938.141 a
J⫽5←4 314 914.894 ⫺0.001
J⫽6←5 377 886.567 0.002
J⫽7←6 440 851.625 ⫺0.002
J⫽8←7 503 808.614 0.000
quency side of the 共000兲 line. The l-type splitting of (022 0)
(033d 0) J⫽4←3 251 938.141 a
is again much smaller, but in this case the (033 0) doublet is J⫽5←4 314 916.569 0.001
resolved in all the observed transitions; these features are J⫽6←5 377 891.090 ⫺0.002
shown in the inset. Like LiOH, the (020 0) line for LiOD is J⫽7←6 440 861.953 0.001
J⫽8←7 503 829.481 0.000
shifted by more than 1 GHz from the centroid of the (022 0)
a
doublet. Unresolved doublet not included in the fit.

Downloaded 25 Mar 2005 to 128.196.209.95. Redistribution subject to AIP license or copyright, see http://jcp.aip.org/jcp/copyright.jsp
11718 J. Chem. Phys., Vol. 121, No. 23, 15 December 2004
FIG. 1. A stick figure showing the progression of the vibrational modes in
the J⫽5←4 rotational transition of LiOH. The heights of the sticks indicate
the observed relative intensity as compared to the ground vibrational mode.
Figures 3 and 4 show typical spectra obtained for LiOH
and LiOD. Figure 3 shows a portion of the spectrum of the
J⫽5←4 transition of LiOH near 353.3 GHz. The ground
vibrational state and the upper l component of the (011 0)
mode are shown. The scan width is 100 MHz and the acqui-
sition time is ⬇1 min. The signal to noise ratio in this spec-
trum is greater than 200:1 for the strongest feature present.
Figure 4 shows sections of the spectrum of the J⫽8←7
transition of LiOD near 503 GHz. The panel on the left
shows the ground vibrational mode while that on the right
shows the lower l component of the (022 0) state and the
l-type doublet of the (033 0) mode. The intensity of the lines
decreases exponentially with increasing v 2 . This is consis-
tent with a Boltzmann distribution, as expected under the
conditions of this experiment.
C. Experimental analysis
The rotational data in all of the observed vibrational
states for LiOH and LiOD were analyzed using a standard
linear molecule Hamiltonian consisting of rotation, centrifu-
gal distortion, and l-type interactions 共see Ref. 17兲. The re-
FIG. 2. A stick figure showing the progression of the vibrational modes in
the J⫽5←4 rotational transition for LiOD. The vibrational modes shown
are 共000兲, (011 0), and (022 0). The heights of the sticks indicate the ob-
served relative intensity as compared to the ground vibrational mode.
Downloaded 25 Mar 2005 to 128.196.209.95. Redistribution subject to AIP license or copyright, see http://jcp.aip.org/jcp/copyright.jsp
Higgins et al.
FIG. 3. Spectrum of the J⫽5←4 transition of LiOH in its ground vibra-
tional and first excited modes near 353 GHz. The scan width is 100 MHz
and the acquisition time is ⬇1 min. The signal to noise ratio of this spectrum
is ⬎200:1, illustrating the improvement of this method over those used in
the past.
sulting spectroscopic constants are given in Table III. The
data for both molecules in their respective 共000兲 and (020 0)
modes were fit with only two parameters, B and D, while the
remaining vibrational modes also required two l-type dou-
bling parameters, q and q D . In addition, several high-order
centrifugal distortion terms were necessary to obtain an ac-
ceptable fit for LiOD.
Using the rotational constants determined for each bend-
ing vibration, the vibrational progression was modeled with
the following expression:
B 共 0,v 2 ,0兲 ⫽B̃ e ⫺ ␣ 2 共 v 2 ⫹1 兲 ⫹ ␥ 22共 v 2 ⫹1 兲 2 ⫹ ␥ ll l 2 , 共1兲
where B (0,v 2 ,0) is the rotational constant per v 2 state, B̃ e
⫽B e ⫺ 12 ( ␣ 1 ⫹ ␣ 3 ) is the effective equilibrium rotational con-
stant, ␣ 2 and ␥ 22 are the vibration-rotation interaction con-
stants, and ␥ ll is the l-dependent vibration-rotation interac-
tion constant. The ␣ 2 , ␥ 22 , and ␥ ll parameters determined
from Eq. 共1兲 are given in Table IV, as well as theoretical
FIG. 4. The spectrum of the J⫽8←7 transition of LiOD near 503 GHz; a
baseline has been removed. The panel on the left shows the ground vibra-
tional mode while the panel on the right shows the lower l component of the
(022 0) mode and both l components of the (033 0) mode. The y scale for the
left panel is ten times larger than that on the right. Each spectrum is a 100
MHz scan with an acquisition time of ⬇1 min.
J. Chem. Phys., Vol. 121, No. 23, 15 December 2004 Rotational spectrum of LiOH 11719

TABLE III. Experimental and theoretical values of molecular constants 共in MHz兲 for LiOH and LiOD.

LiOH LiOD

Theoretical Theoretical

( v 1 , v l2 , v 3) Constant Experimental Current PES Ref. 11 PES a

Experimental Current PES Ref. 11 PESa

共000兲 B 35 342.852共5兲 35 237.568 35 016.604 31 477.684共4兲 31 391.313 31 211.351

D 0.217 38共7兲 0.216 96 0.214 18 0.151 73共5兲 0.151 46 0.150 11

(011 0) B 35 196.097共4兲 35 088.089 34 868.876 31 503.492共3兲 31 414.508 31 242.106

D 0.221 53共5兲 0.221 05 0.217 63 0.156 56共3兲 0.156 24 0.154 72
q ⫺295.792共8兲 ⫺293.804 ⫺308.271 ⫺298.738共6兲 ⫺296.890 ⫺315.481
qD 0.0060共1兲 0.005 927 0.006 332 0.009 21共7兲 0.009 05 0.010 346
⌬B ⫺146.755 ⫺149.479 ⫺147.727 25.808 23.193 30.756

(020 0) B 35 166.662共5兲 35 055.707 34 850.049 31 598.186共4兲 31 506.259 31 342.270

D 0.338 08共7兲 0.335 85 0.370 51 0.438 99共5兲 0.436 94 0.583 64
⌬B ⫺176.190 ⫺181.861 ⫺166.554 120.502 114.946 130.919

(022 0) B 35 019.956共4兲 34 909.869 34 692.885 31 510.511共3兲 31 419.126 31 249.947

D 0.167 01共6兲 0.167 33 0.143 84 0.021 79共4兲 0.022 19 ⫺0.054 12
qef f 0.1056共1兲 0.1043 0.1418 0.268 94共8兲 0.267 48 0.414 12
q Def f 1.6(3)⫻10⫺7 1.2⫻10⫺7 2.4⫻10⫺7 1.6(1)⫻10⫺7 1.6⫻10⫺7 2.4⫻10⫺7
⌬B ⫺322.896 ⫺327.699 ⫺323.718 32.827 27.813 38.597

(031 0) B 35 109.982共4兲 34 996.234 34 791.941 31 672.034共6兲 31 577.333 31 412.579

D 0.279 41共6兲 0.277 81 0.287 57 0.2885共2兲 0.2869 0.3481
H ⫺2.4(2)⫻10⫺5 ⫺2.4⫻10⫺5 ⫺6.5⫻10⫺5
q ⫺610.591共8兲 ⫺606.044 ⫺611.923 ⫺630.37共1兲 ⫺625.85 ⫺641.197
qD 0.0228共1兲 0.0225 0.0235 0.031共2兲 0.031 0.038
qH 7.3(2)⫻10⫺7 7.2⫻10⫺7 1.8⫻10⫺6
⌬B ⫺232.870 ⫺241.334 ⫺224.663 194.350 186.020 201.228

(033 0) B 34 813.529共4兲 34 701.940 34 491.611 31 492.82共1兲 31 399.367 31 231.924

D 0.170 68共7兲 0.171 16 0.152 68 0.0405共4兲 0.0409 ⫺0.0249
H 2.6(3)⫻10⫺5 2.4⫻10⫺5 6.6⫻10⫺5
qef f Unresolved ⫺0.126 ⫺0.022 0.003共9兲 0.002 0.008
q Def f Unresolved 4.5⫻10⫺4 7.8⫻10⫺4 ⫺3(2)⫻10⫺4 ⫺3⫻10⫺4 ⫺7⫻10⫺4
qH 3.4(2)⫻10⫺5 3.4⫻10⫺5 8.3⫻10⫺5
⌬B ⫺529.323 ⫺535.628 ⫺524.993 15.135 8.054 20.573
rms 0.045 0.034 0.067 0.071 0.076 0.137
a
From DVR3D calculations using the PES of Ref. 11.

values obtained from computations described below. The
terms ␥ 22 and ␥ ll are exceptionally high, suggesting that
LiOH and LiOD exhibit large amplitude oscillations. The
nature of the large amplitude motions become clear after the
comparison of the spectroscopic constants obtained from
electronic structure theory is made.
III. COMPUTATIONAL
A. Computational methods
The three-dimensional potential energy surface 共PES兲
for LiOH was calculated at the coupled-cluster level with
single and double excitations and perturbative contributions
of connected triple excitations 关CCSD共T兲兴. Preliminary
CCSD共T兲 geometry optimization calculations were per-
formed to determine the optimal basis set to use, the effect of
core electron correlation, and the effect of basis set superpo-
sition error 共BSSE兲 on the computed geometries and energies
of LiOH. A three-dimensional dipole moment surface was
also calculated using second-order Møller-Plesset perturba-
tion theory 共MP2兲. Electronic structure calculations were
performed using MOLPRO2000.18,19 To gauge the quality of the
PES by making comparisons to the current and previous ex-

TABLE IV. Vibrational dependence of B v 共values quoted are in MHz兲 from states in the current study.

LiOH LiOD

Constant Experimental Theoretical Experimental Theoretical

B̃ e a 35 497.50共1兲 35 395.28共3兲 31 451.28共1兲 31 368.07共3兲

␣2 176.86共1兲 179.98共2兲 ⫺14.467共8兲 ⫺11.43共2兲
␥ 22 22.291共2兲 22.332共4兲 11.543共2兲 11.591共4兲
␥ ll ⫺36.9937共6兲 ⫺36.7183共16兲 ⫺22.2339共8兲 ⫺22.1639共16兲
1
a
B̃ e ⫽B e ⫺ 2 ( ␣ 1 ⫹ ␣ 3 ).

Downloaded 25 Mar 2005 to 128.196.209.95. Redistribution subject to AIP license or copyright, see http://jcp.aip.org/jcp/copyright.jsp
11720 J. Chem. Phys., Vol. 121, No. 23, 15 December 2004 Higgins et al.

TABLE V. Geometry optimization results 共in Å and cm⫺1 unless noted兲 and a sampling of previous results.

Method Basis r(LiO) r(OH) E tot (hartree) De D e (CPC) a CPC%

CCSD共T兲 avqz 1.5954 0.9490 ⫺83.262 878 ⫺73 546 ⫺73 276 0.37
Frozen core av5z 1.5945 0.9486 ⫺83.269 810 ⫺73 849 ⫺73 726 0.17
acvqz 1.5947 0.9491 ⫺83.264 447 ⫺73 548 ⫺73 328 0.30

CCSD共T兲 cvqz 1.5759 0.9477 ⫺83.365 913 ⫺73 634 ⫺73 196 0.59
Full electron acvqz 1.5805 0.9483 ⫺83.369 319 ⫺74 014 ⫺73 781 0.31
correlation

Hartree-Fock acvqz 1.5743 0.9300 ⫺82.959 498 ⫺47 350 ⫺47 318 0.07

ACPFb b 1.5857 0.9499 ⫺83.266 532

MP3c 6-311G** 1.5732 0.9446 ⫺82.938 316
CCSD共T兲d 6-311⫹⫹G(2d f ,2pd) 1.587 0.948 ⫺83.268 74
CCSD共T兲e e 1.5802 0.9510 ⫺83.284 58
a
Counterpoise correction 共CPC兲 applied to noncounterpoise corrected optimized geometry.
b
Reference 11. See reference for details of the basis set.
c
Reference 4.
d
Reference 14.
e
Reference 9. See reference for details of the basis set.

perimental results, the energy levels, transition frequencies,
and various expectation values for LiOH, LiOD, Li 18OH,
and 6 LiOH were calculated using the DVR3D package of Ten-
nyson and co-workers.15
The atomic basis sets used for the preliminary calcula-
tions were the correlation-consistent polarized valence,
cc-pVnZ共vnz) and correlation-consistent polarized core-
valence, cc-pCVnZ共cvnz), 20 basis sets of Dunning and
co-workers,21,22 and these sets augmented with diffuse func-
tions for O and H, aug-cc-pVnZ共avnz) or aug-cc-
pCVnZ共acvnz). For the core-valence basis sets cvnz and
acvnz, calculations were performed using sets of double-,
triple-, and quadruple-zeta 共the highest available兲 quality,
while for the vnz and avnz basis sets the quality ranged from
double to quintuple zeta. Because there are no diffuse func-
tions available for the Dunning basis sets for Li and no core-
valence sets for H the total basis used for LiOH in each case
is labeled by the set used for the O atom with the understand-
ing that Li and H used the closest available basis set.
CCSD共T兲 calculations were performed at the frozen-core
approximation and with all electrons correlated. In addition,
a single geometry optimization at the Hartree–Fock/acvqz
level was performed to determine the effect of completely
ignoring electron correlation has on the geometry and bind-
ing energy of LiOH. Binding energies for the optimized ge-
ometries were calculated relative to the ground state atoms
by subtracting the atomic energies calculated in the atomic
basis from the molecular energy. The energetic effect of
BSSE was calculated by using the counterpoise 共CP兲
method23 with the non-CP optimized geometry.
Selected geometry optimization results are listed in
Table V along with results from previous studies for com-
parison. Frozen-core results using the avnz basis sets illus-
trate the convergence of the geometry and binding energy as
a function of basis set size, with the avqz results differing
from the av5z results by just 0.0009 Å for the Li–O bond
length, 0.0004 Å for the O–H bond length, and 0.41% in the
binding energy. The effect of core-electron correlation can be
seen by comparing the results for the acvqz basis sets using
full electron correlation to those using the frozen-core ap-
proximation. There is very little difference for the binding
energy and the O–H distance 共0.63% and 0.0008 Å, respec-
tively兲, but the Li–O bond distance shrinks considerably
共0.0142 Å兲. This shrinkage proved vital to getting the correct
rotational constants in the rovibrational calculations pre-
sented below. Comparing the acvqz results with the cvqz
results shows that the inclusion of diffuse functions on the O
and H result in a lengthening of the Li–O bond by 0.0046 Å
and of the O–H bond by 0.0006 Å, and an increase in the
binding energy of 0.51%. Also note in Table V the effect of
BSSE as estimated using the CP correction, which for the
acvqz basis set amounts to just 0.31% of the total binding
energy. The best calculations using the acvqz basis yield an
equilibrium Li–O bond length of 1.5805 Å and an equilib-
rium O–H bond length of 0.9483 Å. These results are in
good agreement with the most recent reported LiOH
calculations.9,10 Included in Table V are results for Hartree–
Fock level calculations using the acvqz basis set. These cal-
culations result in a binding energy that is 64% of the
CCSD共T兲 binding energy as well as Li–O and O–H bond
lengths that are somewhat shorter.
Based on the results of the preliminary calculations, the
full three-dimensional CCSD共T兲 potential energy surface
was calculated with the acvqz basis set utilizing full electron
correlation with no counterpoise correction. The potential
was calculated in a Jacobi coordinate system with R the dis-
tance from Li to the center of mass of OH, r the OH bond
length, and ␪ the angle between R and r with ␪⫽0 defined as
the linear Li–OH arrangement. Calculations were performed
on a grid of points with ten values of r ranging from 0.6 to
1.8 Å, eight values of R from 1.1 to 3.0 Å, and ␪ ranging
from 0° to 180° in increments of 15° for a total of 1040
geometries.24 As with the optimized geometry binding ener-
gies, the potential at each point is taken as the difference
between the LiOH energy and the ground state energies of
the individual atoms calculated with the atom’s basis set.
Interpolation of the potential was performed using a
three-dimensional cubic spline routine.25 To ensure a smooth

Downloaded 25 Mar 2005 to 128.196.209.95. Redistribution subject to AIP license or copyright, see http://jcp.aip.org/jcp/copyright.jsp
J. Chem. Phys., Vol. 121, No. 23, 15 December 2004
TABLE VI. Morse oscillator parameters 共in bohr and hartree兲 for the basis sets used in DVR3DRJZ.
LiOH
r 1⫽ re 2.064 197 3
r(OH) De 0.169
␻e 3.245 356 1⫻10⫺2
r 2 ⫽R re 3.919 755 3
De 0.168
␻e 2.696 256 8⫻10⫺3
and accurate interpolation in the R coordinate additional
points were generated by fitting the ab initio points for each
r and ␪ combination to an analytical potential function in R,
6 pure vibrational (J⫽0) or Coriolis-decoupled vibrational
V 共 R, 关 r, ␪ 兴 兲 ⫽A exp共 ⫺ ␤ R 兲 ⫺ 兺
n⫽1
C n R ⫺n ⫺V OH共 r 兲 , 共2兲
where V OH(r) is the potential energy of OH calculated in the
same manner as the LiOH potential energy, and then using
this function to produce points on a finer spacing over the
range R⫽0.9– 3.0 Å. 26 Additional points at r⫽0.5 Å were
generated by fitting the r dependence of V(R,r, ␪ ) for each
关 R, ␪ 兴 combination to a simple quadratic expression using
the r⫽0.6, 0.7, and 0.8 Å points as input. The spline routine
uses a natural spline at both ends of the r range and the outer
end of the R range, a constraint that the slope of the potential
be zero in the ␪ direction for ␪⫽0° and 180°, and a constraint
that the slope in the R direction at the inner end of the R
range be determined by fitting the inner two points to an
exponential expression in R, A exp(⫺␤R), and taking its
slope at R⫽0.9 Å. Because a square grid of potential points
was used, some of the input geometries were in areas of
tremendous atomic repulsion with correspondingly high po-
tential energies, and these points caused problems with the
cubic spline interpolation, therefore any potential energy
greater than 5⫻105 cm⫺1 was scaled on input to lie between
5 and 10⫻105 cm⫺1 using the formula V scaled⫽5
⫻105 (1 – 5⫻105 /V unscaled)⫹5⫻105 . The potential subrou-
tine also shifts the center of mass used for OD or 18OH in
their respective calculations.
The dipole moment surface was calculated at the MP2
level using the acvqz basis set on the same grid of points as
the ab initio potential calculation with all electrons
correlated.24 A fixed orientation with the z axis directed along
the OH bond was used in the MP2 calculations, although for
the dipole expectation value calculations described later the
calculated dipole components were rotated into the inertial
frame by diagonalizing the moment of inertia tensor for each
geometry calculated. The dipole surface was interpolated us-
ing the same cubic spline routine as the potential, but this
time a natural spline was used for both ends of the r and R
range while the same constraint of zero slope at ␪⫽0° and
180° was used. No extra points were necessary because the
dipole surface is smooth enough for a cubic spline to inter-
polate accurately on the calculated grid.
Rovibrational energy levels of LiOH, LiOD, Li 18OH,
and 6 LiOH for the CCSD共T兲 potential surface were calcu-
lated using the DVR3D program suite.15 This package uses a
discrete variable representation 共DVR兲 method in all three
Downloaded 25 Mar 2005 to 128.196.209.95. Redistribution subject to AIP license or copyright, see http://jcp.aip.org/jcp/copyright.jsp
Rotational spectrum of LiOH 11721
LiOD Li 18 OH 6
LiOH
2.046 788 6 2.062 770 5 2.064 197 3
0.169 0.169 0.169
1.992 938 8⫻10⫺2 3.234 628 2⫻10⫺2 3.245 356 1⫻10⫺2
4.014 451 2 3.917 075 7 3.920 488 9
0.168 0.168 0.168
2.654 322 3⫻10⫺3 2.620 228 5⫻10⫺3 2.994 541 7⫻10⫺3
coordinates to calculate the energy levels, wave functions,
and expectation values of triatomic molecules. It employs a
two-step process in which the program DVR3DRJZ solves the
(J⭓0) problem and then the program ROTLEV3 uses the re-
sults of DVR3DRJZ as a basis to solve the full rovibrational
problem. The basis functions for DVR3DRJZ consist of Morse-
oscillator-like functions for the radial coordinates and Leg-
endre polynomials or associated Legendre polynomials for
the angular coordinate.
By default DVR3D takes as input the number of DVR
points and the Morse parameters r e , D e , and ␻ e describing
the basis for each radial coordinate and determines the points
to use for that coordinate. To test convergence in terms of
range and/or number of DVR points, D e was held fixed
while r e and ␻ e were chosen so that the inner and outer
radial limits for a given number of DVR points matched the
values desired. Convergence characteristics were determined
by performing extensive calculations in which the number of
DVR points in each coordinate and the inner and outer limits
for the radial coordinates were varied. In addition, the num-
ber of basis functions in the final Hamiltonian for DVR3DRJZ
and the number of energy levels to be kept and used as input
to ROTLEV3 were varied. Results for J⫽0, 1, and 2 were used
to determine B and D for the 共000兲 and (020 0) states to
gauge the convergence of predicted spectroscopic constants
in addition to the convergence of absolute energy levels.
Convergence to 0.0003 cm⫺1 in absolute energy, 10 kHz in
B, and 0.3 kHz in D was achieved using a DVR grid of 50
points in R between 1.1 and 3.0 Å, 40 points in r between 0.6
and 1.5 Å, and 40 points in ␪ between 0° and 180°. Because
the center of mass of OD is shifted ⬇0.05 Å away from the
O atom the DVR grid in R for LiOD is between 1.15 and
3.05 Å. Parameters for the Morse-oscillator-like basis func-
tions for the four isotopomers are listed in Table VI. For
DVR3DRJZ the z axis was embedded along the R coordinate,
the intermediate one-dimensional solutions were truncated at
0 cm⫺1, the final basis size was 2000 functions, and the
resulting lowest 200 states were used as input to ROTLEV3.
Expectation values of various geometric coordinates and the
dipole moment function were calculated with the program
XPECT3 using the wave function output from DVR3DRJZ for
J⫽0 and from ROTLEV3 for J⭓0. The dipole moment com-
ponent along the a inertial axis, ␮ a , is calculated by taking
the expectation value of the instantaneous projection of the
dipole moment along the a axis. For comparison purposes,
rovibrational energy levels for LiOH and LiOD were calcu-
11722 J. Chem. Phys., Vol. 121, No. 23, 15 December 2004 Higgins et al.

FIG. 5. Contour plot of the LiOH CCSD共T兲 potential energy surface for
r(OH) held fixed at 0.9489 Å. The origin is at the OH center of mass and
contours are labeled in 104 cm⫺1 .

lated using the PES from Bunker et al.11 in exactly the same
manner described above for the current PES.

B. Computational results
Although the PES and rotation-vibration calculations use
a Jacobi coordinate system, for discussion of the results it is
physically clearer to use the LiOH valence coordinates
r(LiO), r(OH), and ¯␳ , the deviation from linearity for the
Li–O–H bond angle.27 The global minimum on the spline
interpolated surface is ⫺74 014 cm⫺1 and occurs at r(LiO)
⫽1.5805 Å, r(OH)⫽0.9489 Å, and ¯␳ ⫽0°. This is an OH
bond length 0.0006 Å longer than the optimized structure
listed in Table V. This slight structural difference amounts to
only a 3 MHz difference in rotational constant for a static
structure. A contour diagram of the CCSD共T兲 PES as a func-
tion of Li position relative to the center of mass of OH for
r(OH) held fixed at its equilibrium distance of 0.9489 Å is
shown in Fig. 5. The minimum in the potential occurs in the
linear Li–O–H configuration and there is a wide, flat trough
in the bending potential about this linear configuration.
Details of the minimum energy path as a function of ¯␳
are presented in Fig. 6. Figure 6共a兲 shows the energy along
the minimum energy path and illustrates the monotonic in-
crease in the potential from ¯␳ ⫽0° to 180° as well as the
flatness of the potential from ¯␳ ⫽0° to 90°. The value of
r(LiO) stays roughly the same from ¯␳ ⫽0° to 120° but
r(OH) lengthens dramatically over this same range and then
decreases dramatically as ¯␳ approaches 180°. Note the mini-
mum energy configuration for ¯␳ ⫽180° is O–H–Li, which
calculations show is 44 994 cm⫺1 lower in energy than the
configuration O–Li–H. Figure 7 shows a comparison with
the calculations of Refs. 4 and 11 over the range ¯␳
⫽0° – 90° and it can be seen that the current PES falls be-
tween the previous two in terms of the bending potential and
structure over this range. The analytic PES of Ref. 11 was
derived from ab initio calculations over the range 1.41
⭐r(LiO)⭐1.81 Å, 0.78⭐r(OH)⭐1.18 Å, and 0°⭐¯␳
⭐90°, which is a smaller range than the current calculations
but the analytic form allows for extrapolation. Extrapolating
beyond ¯␳ ⫽90° results in good agreement in terms of energy,
which at ¯␳ ⫽180° is 3.5% higher relative to equilibrium than
the current PES; however, it results in disagreement in terms
FIG. 6. Values of the 共a兲 potential energy, 共b兲 Li–O bond distance, and 共c兲
O–H bond distance along the minimum energy path of the CCSD共T兲 poten-
tial energy surface as functions of ¯␳ , the deviation from linearity for the
Li–O–H angle.
of the optimal bond lengths, with r(LiO) decreasing to
1.5540 Å and r(OH) increasing to 0.9930 Å at ¯␳ ⫽180°.
The interesting effects of stretching r(LiO) or r(OH) are
shown in Figs. 8 and 9, respectively, where it is shown that
the minimum energy structure of LiOH becomes bent as ei-
ther r(LiO) or r(OH) is stretched. The effect for r(LiO) was
first reported by Bunker et al.11 but this is the first report of
a similar effect for r(OH). The molecule stays linear until
r(LiO)⫽1.7259 Å and then approaches a tetrahedral angle
as r(LiO) approaches 3.0 Å. The difference in energy be-
tween the linear configuration and the bent configuration is
shown in Fig. 8共b兲. By r(LiO)⫽3.0 Å the bent form is 2636
cm⫺1 more stable than the linear form. Figure 8共c兲 shows
that the optimal value of r(OH) changes as well, rising from
0.9489 Å at equilibrium to 0.9643 Å at r(LiO)⫽3.0 Å. The
latter value is quite close to the r e value of 0.9644 Å calcu-
lated for OH⫺ using the same basis and method as LiOH.
The analytic PES of Ref. 11 is in good agreement in all
aspects with the current PES, even in the extrapolated region
with r(LiO)⬎1.8 Å, with the change from linearity occur-
ring 0.0177 Å earlier and the bent structure being 2660 cm⫺1
lower in energy than the linear structure at r(LiO)⫽3.0 Å.
The effect of stretching r(OH), shown in Fig. 9, differs

Downloaded 25 Mar 2005 to 128.196.209.95. Redistribution subject to AIP license or copyright, see http://jcp.aip.org/jcp/copyright.jsp
J. Chem. Phys., Vol. 121, No. 23, 15 December 2004
FIG. 7. Comparison with previous LiOH potentials of 共a兲 potential energy
relative to equilibrium value, 共b兲 Li–O bond distance, and 共c兲 O–H bond
distance along the minimum energy path as a function of ¯␳ . Dashed line is
PES of Ref. 11 and filled circles are from Ref. 4.
from that of r(LiO). A local minimum on the PES develops
in the bent configuration at r(OH)⫽1.2900 Å while the lin-
ear minimum persists until r(OH)⫽1.3939 Å, so for a short
distance there are two minimums. The change from linearity
occurs at r(OH)⫽1.3095 Å, when the bent minimum be-
comes lower in energy than the linear minimum and it is
seen as a discontinuous jump in Fig. 9. By r(OH)⫽1.8 Å the
optimal ¯␳ value is 103°, the optimal r(LiO) is 1.6894 Å, and
the bent configuration is 2940 cm⫺1 lower in energy than the
linear configuration. The PES of Ref. 11 predicts qualita-
tively similar behavior even though the change from linearity
begins well beyond their calculated r(OH) region.
To gauge the quality of the PES a comparison is made to
the experimentally determined molecular constants by deter-
mining theoretical constants using the same program and
same transitions used to determine the experimental con-
stants. This approach is favored over a direct comparison of
transition frequencies because even a slight difference in ro-
tational constant can lead to a systematic disagreement be-
tween experiment and computation that masks the true qual-
ity of the PES. In addition, the fitted constants each probe a
different aspect of the PES, with the rotational constant prob-
ing structural agreement and the distortion constants probing
the stiffness of the PES. Table III lists the experimentally and
Downloaded 25 Mar 2005 to 128.196.209.95. Redistribution subject to AIP license or copyright, see http://jcp.aip.org/jcp/copyright.jsp
Rotational spectrum of LiOH 11723
FIG. 8. Effects of stretching the Li–O bond in terms of 共a兲 ¯␳ for the mini-
mum energy configuration, 共b兲 potential energy difference between the mini-
mum energy configuration and the linear configuration, and 共c兲 the variation
of the optimal O–H bond distance. CCSD共T兲 values are represented by the
solid lines and Hartree–Fock values are represented by dashed lines.
computationally determined rotational, distortion, and effec-
tive l-doubling constants for the current experiment. The
agreement is excellent, with the computed rotational con-
stants typically 0.3% too low and the computed distortion
constants typically 0.2% too low. Also listed is the shift in B
with vibrational level, ⌬B. The computed values are within
8.5 MHz of the experimental values. The l-doubling con-
stants are also well predicted, with the computed values typi-
cally within 0.75% of the experimental values. Larger rela-
tive discrepancies start to appear for the higher-order
constants that have values in the kHz range, which is pushing
the limits of the current calculations’ numerical convergence.
The l doubling in the (033 0) state of LiOH is unresolved in
the current experiment but was measured directly by Freund
for J⫽6 – 12.3 Table VII lists the observed and predicted
transition frequencies of this state as an illustration of how
well the current calculation can predict these small splittings.
Also listed in Table III are constants derived from DVR3D
calculations using the PES of Ref. 11. The B values are typi-
cally 0.9% too low and the ⌬B values are within 10.4 MHz
of experiment, but agreement for the other fitted constants is
much less consistent. Values for D range from within 1.5% to
greater than 13% of experiment while q values range from
11724 J. Chem. Phys., Vol. 121, No. 23, 15 December 2004 Higgins et al.

TABLE VIII. Experimental and theoretical constants 共in MHz兲 for other
vibrational states and isotopomers.

Species ( v 1 , v l2 , v 3 ) Constanta Experimental Theoretical

LiOH b
共100兲 B 34 887.76共5兲 34 785.324
D 0.216 40
⌬B 455.09共5兲 452.244
(120 0) B 34 723.44共10兲 34 616.373
D 0.338 78
⌬B 619.41共10兲 621.195
共001兲 B 35 240.8共5兲 35 079.316
D 0.215 47
⌬B 102.0共5兲 158.252
(020 1) B 34 914.168
D 0.354 19
⌬B 323.400
共101兲 B 34 836共1兲 34 627.023
D 0.215 01
⌬B 507共1兲 610.545

Li OH18 c
共000兲 B 34 531.819共9兲 34 428.414
D 0.20940共26兲 0.208 90
⌬B 811.033共9兲 809.154
6
LiOHd 共000兲 B 39 244.82共25兲 39 108.503
D 0.264 19
⌬B ⫺3 901.97共25兲 ⫺3 870.935

LiOD 共000兲 B 31 477.684共4兲 31 391.313

D 0.15173共5兲 0.151 46
⌬B 3 865.168共5兲 3 846.255
共100兲 B 31 021.686
D 0.157 96
(120 0) B 31 158.391
D 0.478 66
共001兲 B 31 224.538
D 0.149 66
FIG. 9. Effects of stretching the O–H bond in terms of 共a兲 ¯␳ for the mini-
共101兲 B 30 876.508
mum energy configuration, 共b兲 potential energy difference between the mini-
mum energy configuration and the linear configuration, and 共c兲 the variation D 0.036 47
of the optimal Li–O bond distance. The break in the ¯␳ and r(LiO) lines (020 1) B 31 357.573
indicates a jump between two competing minimums. CCSD共T兲 values only D 0.459 85
shown. a
⌬B values are calculated relative to the B (000) value of LiOH.
b
Experimental from Ref. 3.
c
Experimental from Table VI of Ref. 4.
within 0.3% to greater than 30% of experiment for LiOH, d
Experimental from the J⫽1←0 transition frequency listed in Table III of
with the range for LiOD even greater. Ref. 4.
Previous experimental studies3,4 of LiOH have reported
rotational lines for vibrational states and isotopomers not in-
cluded in the current experimental work but useful for com-
parison with the current calculation. Table VIII lists the ex-
isotope shifts relative to LiOH for B (000) are within 0.8% of
perimental and theoretical constants for these species and
vibrational states as well as for several vibrational states of the experimental values. The vibrational shifts for the 共100兲
LiOH and LiOD that have not been observed experimentally and (120 0) states of LiOH are predicted to within 0.6%, but
but are used in the structure determination below. Predicted those for the 共001兲 and 共101兲 states are too high by 55% and
20%, respectively. Given the level of agreement between ex-
periment and theory up until this point, it is probable that the
TABLE VII. l-doubling transition frequencies 共in MHz兲 for the (033 0) state experimental values for 共001兲 and 共101兲 are in error.28
of LiOH.
Vibration-rotation interaction constants provide another
J Experimentala Theoretical measure of the quality of the PES by probing the elasticity at
longer ranges than the distortion constants. Table IV lists the
6 1.040共5兲 0.987
7 2.555共5兲 2.481
experimental and theoretical constants determined using Eq.
8 5.635共5兲 5.481 共1兲 from the states studied in the current experiments. The
9 11.323共5兲 11.028 level of agreement is excellent, including the large change in
10 21.255共5兲 20.608 ␣ 2 upon deuteration, indicating that the PES reproduces the
11 37.260共5兲 36.300 bending potential accurately even for the large amplitude vi-
12 62.555共5兲 60.934
brations in the (03l 0) states. Table IX lists constants deter-
a
Reference 3. mined using a variety of expanded data sets fit to

Downloaded 25 Mar 2005 to 128.196.209.95. Redistribution subject to AIP license or copyright, see http://jcp.aip.org/jcp/copyright.jsp
J. Chem. Phys., Vol. 121, No. 23, 15 December 2004 Rotational spectrum of LiOH 11725

TABLE IX. Vibration-rotation constants 共in MHz兲 determined using data from the current and previous studies.

LiOH all experimental dataa LiOH mixed datab LiOD mixed datac

Constant Experimental Theoretical Experimental Theoretical Experimental Theoretical

Be 35 791.5共4兲 35 703.68共4兲 35 811.06共5兲 35 707.72共4兲 31 734.41共1兲 31 651.20共4兲

␣1 485.9共6兲 458.49共3兲 460.72共9兲 458.49共3兲 390.76 390.76共3兲
␣2 179.63共3兲 183.08共2兲 183.68共3兲 187.11共3兲 ⫺4.781共8兲 ⫺1.75共3兲
␣3 127.3共9兲 158.31共2兲 166.40 166.40共3兲 186.26 186.26共3兲
␥ 22 22.291共2兲 22.332共4兲 22.291共2兲 22.332共4兲 11.543共2兲 11.591共4兲
␥ ll ⫺36.9937共6兲 ⫺36.7183共16兲 ⫺36.9937共6兲 ⫺36.7183共16兲 ⫺22.2339共8兲 ⫺22.1639共16兲
␥ 12 5.54共6兲 6.182共9兲 5.54共6兲 6.182共9兲 10.582 10.582共9兲
␥ 13 50共1兲 0.008共20兲 0.008 0.008共20兲 21.53 21.53共2兲
␥ 23 8.083 8.083共9兲 8.790 8.790共9兲
a
Experimental values fit using B v values for 共000兲, (011 0), (020 0), (022 0), (031 0), and (033 0) from this work
and for 共100兲, (120 0), 共001兲, and 共101兲 from Ref. 3. Theoretical values fit using B v values from this work.
b
Theoretical values fit by adding the B v value for (020 1) to the ‘‘all experimental’’ data set. Experimental values
fit by removing the B v values for 共001兲 and 共101兲 from the all experimental data set and fixing ␣ 3 , ␥ 13 , and
␥ 23 at their theoretical values.
c
Experimental values fit using B v values from this work and fixing ␣ 1 , ␣ 3 , ␥ 12 , ␥ 13 , and ␥ 23 at their
theoretical values.

B v ⫽B e ⫺ ␣ 1 共 v 1 ⫹ 12 兲 ⫺ ␣ 2 共 v 2 ⫹1 兲 Finally we compare the charge distribution parameters

⫺ ␣ 3 共 v 3 ⫹ 12 兲 ⫹ ␥ 22 共 v 2 ⫹1 兲 2 ⫹ ␥ ll 共 l 兲 2
⫹ ␥ 12 共 v 1 ⫹ 21 兲共 v 2 ⫹1 兲 ⫹ ␥ 13 共 v 1 ⫹ 21 兲共 v 3 ⫹ 12 兲
⫹ ␥ 23 共 v 2 ⫹1 兲共 v 3 ⫹ 21 兲 .
The first two columns list experimental and theoretical con-
stants determined using B v values for all experimentally
measured vibrational states of LiOH. The disagreement for
the 共001兲 and 共101兲 states noted earlier is apparent in the
large differences between the experimental and theoretical
values for ␣ 1 , ␣ 3 , and ␥ 13 . Although the B v shift is well
predicted for the 共100兲 state, the value of ␣ 1 is quite far off
due to the influence of the large experimental ␥ 13 value. The
next four sets of constants presented in Table IX are deter-
mined from a mix of experimentally measured and theoreti-
cally predicted states for LiOH and LiOD and are used to
derive a semiexperimental equilibrium structure later in this
paper. The theoretical constants are fit using a data set that
includes the (020 1) state in order to determine the value of
␥ 23 . The experimental constants are fit by removing the
questionable states 共001兲 and 共101兲 from the experimental
LiOH data set and fixing the undeterminable constants for
either LiOH or LiOD to their theoretical values. The agree-
ment between experiment and theory for ␣ 1 is much better
for this data set.
observed with the calculated values. Table X lists the experi-
mentally determined dipole moments and quadrupole cou-
pling constants as well as the calculated dipole moments of
several vibrational states. The calculated ␮ a dipole compo-
共3兲 nents show excellent agreement with experiment, falling
within 0.5% for LiOH and 0.9% for LiOD of the experimen-
tally measured values. There is a slight increase in dipole
moment with the LiO stretching vibration but a significant
increase in the dipole moment with the bending vibration,
and as such this is an excellent test of both the calculated
dipole moment surface and the PES. This variation with vi-
brational state follows what is expected given the variation
of the calculated dipole moment with ¯␳ and r(LiO) pre-
sented in Fig. 10. Although the current calculation does not
include quadrupole coupling effects, it is interesting to note
the experimental 7 Li quadrupole coupling constant increases
significantly with bending vibration, indicating a dependence
of the electric field gradient at the 7 Li nucleus on the bending
angle.
The calculated ground state energies are ⫺71 240 cm⫺1
for LiOH and ⫺71 849 cm⫺1 for LiOD, giving zero-point
energies of 2774 and 2165 cm⫺1 for LiOH and LiOD, re-
spectively. Table XI lists calculated energies and structural
parameters for the ground state, the bending states up to
(033 0), and the Li–O 共100兲 and O–H共D兲 共001兲 stretching

TABLE X. Observed 共Ref. 3兲 and calculated dipole moments 共in debye兲 and observed hyperfine constants 共in
kHz兲 of LiOH and LiOD in several vibrational states.

LiOH LiOD

( v 1 , v l2 , v 3) ␮ a 共Experimental兲 ␮ a 共Theoretical兲 eQq Li ␮ a 共Experimental兲 ␮ a 共Theoretical兲

共000兲 4.755共2兲 4.755 295.8共15兲 4.711共2兲 4.715

共100兲 4.851共2兲 4.849 299.7共31兲 4.80共1兲 4.809
(020 0) 5.031共2兲 5.039 346.9共21兲 4.89共1兲 4.934
(011 0) 4.898共5兲 4.906 4.813共5兲 4.827
(031 0) 5.133共5兲 5.158 5.002共5兲 5.033

Downloaded 25 Mar 2005 to 128.196.209.95. Redistribution subject to AIP license or copyright, see http://jcp.aip.org/jcp/copyright.jsp
11726 J. Chem. Phys., Vol. 121, No. 23, 15 December 2004 Higgins et al.

states. The calculated vibrational fundamental transition fre-

FIG. 10. Total dipole moment as a function of 共a兲 ¯␳ , the deviation from
linearity for the Li–O–H bond, 共b兲 the Li–O bond length, and 共c兲 the O–H
bond length. From the MP2 dipole moment surface, each with the remaining
two geometric parameters held fixed at their equilibrium values.
quencies for LiOH and LiOD are v 1 ⫽923.2 and 912.9, v 2
⫽318.3 and 245.8,29 and v 3 ⫽3829.8 and 2824.2 cm⫺1. As
far as we know there are no direct gas phase measurements
of these vibrational frequencies and therefore no comparison
with experiment is possible, although a matrix IR study re-
ported v 1 ⫽870.5, v 2 ⫽256.5 cm⫺1 for LiOH and v 1
⫽862.0 cm⫺1 for LiOD.30 Agreement between this work and
the work of Bunker et al.11 is excellent for LiOH for the two
stretching modes, which they predict to be 923 and 3832
cm⫺1, but poor for the bending mode which they predict to
be 289 cm⫺1. DVR3D calculations using the PES of Ref. 11
yield fundamental frequencies of v 1 ⫽921.0, v 2 ⫽293.0,29
and v 3 ⫽3809.5 cm⫺1 for LiOH, which is slightly worse
agreement for the two stretching modes. Given the much
better agreement overall with experiment for this later work,
it is likely the true bending frequency is closer to 318.3 than
to 289 cm⫺1. The angular floppiness of the molecule is illus-
trated by the calculated average deviation from linearity for
the Li–O–H angle ¯␳ , which is 19° in the ground state and
increases to 42° in the (033 0) state for LiOH, and by the
dispersion in this angle, which is 10° for both states. These
values approach those of two weakly bound helium com-
plexes, HeClF and HeOCS, investigated previously by two
of the current authors.31,32
Also of interest in Table XI are the differences in the
energetics and structures for different l values of the same
v 2 . 29 For v 2 ⫽2 the ⌺-⌬ splitting is 32.6 cm⫺1 for LiOH and
15.9 cm⫺1 for LiOD, with the ⌺ state lower in both cases.
The bond lengths are essentially equal but ¯␳ is larger by 2.4°
for LiOH and 2.0° for LiOD in the ⌬ state. Similar results
are seen for v 2 ⫽3, where the ⌸ state is 60.3 cm⫺1 lower for
LiOH and 29.6 cm⫺1 lower for LiOD than the ⌽ state and ¯␳
is 2.6° and 2.0° larger for the ⌽ state for LiOH and LiOD,
respectively.

TABLE XI. Calculated energies, fundamental vibrational frequencies 共in cm⫺1兲, and structural expectation
values 共in Å and deg兲 for LiOH and LiOD.

( v 1 , v l2 , v 3 ) E ⌬E v 0a 具 r(LiO) 典 具 r(OH) 典 具¯␳ 典

LiOH 共000兲 ⫺712 40.2 0.0 1.6001 0.9653 19.0
(011 0) ⫺709 20.8 319.5 318.3 1.6101 0.9671 28.8
(020 0) ⫺706 29.3 611.0 611.0 1.6189 0.9689 33.6
(022 0) ⫺705 94.3 645.9 643.6 1.6194 0.9690 36.0
(031 0) ⫺703 19.7 920.5 919.3 1.6265 0.9707 39.3
共100兲 ⫺703 17.0 923.2 923.2 1.6184 0.9656 19.5
(033 0) ⫺702 57.1 983.1 979.6 1.6277 0.9710 41.9
共001兲 ⫺674 10.4 3829.8 3829.8 1.6007 0.9974 19.4

LiOD 共000兲 ⫺718 48.8 0.0 1.5977 0.9606 16.6

(011 0) ⫺716 01.9 246.9 245.9 1.6057 0.9619 25.1
(020 0) ⫺713 71.4 477.4 477.4 1.6130 0.9632 29.5
(022 0) ⫺713 53.5 495.4 493.3 1.6133 0.9632 31.5
(031 0) ⫺711 33.4 715.4 714.3 1.6197 0.9645 34.8
(033 0) ⫺711 01.8 747.1 744.0 1.6204 0.9647 36.8
共100兲 ⫺709 35.9 912.9 912.9 1.6160 0.9608 17.1
共001兲 ⫺690 24.6 2824.2 2824.2 1.5982 0.9833 16.9
a
See Ref. 29.

Downloaded 25 Mar 2005 to 128.196.209.95. Redistribution subject to AIP license or copyright, see http://jcp.aip.org/jcp/copyright.jsp
J. Chem. Phys., Vol. 121, No. 23, 15 December 2004 Rotational spectrum of LiOH 11727

TABLE XII. Estimated bond lengths 共in Å兲 of M OH species.k

r 0a r̃ e b r ec

M–O O–H M–O O–H M–O O–H

LiOH 1.594 0.921 1.584 0.953 1.5776共4兲 0.949共2兲

NaOH 1.95d 1.9435e 0.9543e
KOH 2.212f 0.912f 2.200f 0.968f 2.196共2兲f 0.960共10兲f
RbOH 2.316g 0.913g 2.305g 0.965g 2.301共2兲h 0.957共10兲h
CsOH 2.403i 0.920i 2.395i 0.969i 2.391共2兲h 0.960共10兲h
MgOH 1.780j 0.871j 1.767j 0.940j
a
Determined from the rotational constants of the ground vibrational mode.
b
Calculated from B̃ e derived from Eq. 共1兲.
c
LiOH values calculated from experimental ‘‘mixed data’’ B e listed in Table IX.
d
Reference 34.
e
Ab initio values from Ref. 43.
f
Reference 35.
g
Reference 36.
h
Reference 41.
i
Reference 37.
j
Reference 17.
k
Uncertainties for LiOH as discussed in text, others listed when provided in reference.

IV. DISCUSSION
One particular interesting finding is that LiOH exhibits a
positive rotation-vibration interaction constant ␣ 2 for the re-
spective bending modes, and the value for LiOD is negative;
a negative value is expected for linear polyatomic species.33
The usual negative value, however, does not seem to be typi-
cal of the M OH species. A positive ␣ 2 is consistent with the
alkali hydroxide species NaOH,34 KOH,35 RbOH,36 and
CsOH,37 the alkaline earth hydroxide radicals MgOH,17
CaOH,38 SrOH,38 and BaOH,38 as well as AlOH.39 Each of
these species undergoes a significant isotope shift when the
hydrogen is replaced by a deuterium. In every case the value
of ␣ 2 decreases, but only in the cases of CaOD,40 MgOD,17
AlOD,39 and LiOD does the value become negative as ex-
pected. Lide and Matsumura41 have attributed this large iso-
topic shift to an anharmonic contribution in the vibration-
rotation interaction term ␣ 2 , which dominates for the light
M OH species. This is primarily attributed to the low mass of
the hydrogen atom and the relatively weak M – O bond. Ad-
ditionally, there seems to be a trend moving up the periodic
table on the magnitude of the isotope shift. Comparing the
values in Table IV for LiOH/D with those previously re-
ported for KOH/D, RbOH/D, and CsOH/D the isotope shifts
are ⫺191, ⫺34, ⫺22, and ⫺16 MHz, respectively, while for
MgOH/D and CaOH/D they are ⫺114 and ⫺32 MHz, re-
spectively. In each case the value decreases with increasing
mass number on the metal atom. For the LiOH/D system the
experimental values of ␣ 2 are well reproduced theoretically,
as may be seen in Table IV.
Determination of the structure of LiOH is complicated
by the large amplitude bending motion exhibited in all vibra-
tional states and by the differences in bending amplitude be-
tween LiOH and LiOD for the same vibrational state. Sev-
eral different methods have been used to determine the
vibrationally averaged and equilibrium bond distances using
purely experimental and mixed experimental and theoretical
data. Both r 0 and r̃ e bond distances for LiOH/D have been
calculated using purely experimental data and are listed in
Table XII along with those for other M OH species for com-
parison. The r 0 bond lengths are calculated by using the
B (000) rotational constants, while the B̃ e values from Table
IV are used for the determination r̃ e . The r 0 calculation does
not account for zero-point vibrational motion; therefore the
values represent the average projection of the vibrating mol-
ecule onto the inertial axis. The r̃ e values account for some
of the zero-point vibrational motion. As the table illustrates,
there is a significant difference between these values for all
the M OH species listed. In the case of MgOH, the O–H r 0
bond length is 0.069 Å shorter than the r̃ e value 共0.940 Å兲.
This difference likely arises because MgOH is quasilinear,
and the shortened r 0 bond distance is thought to be a dy-
namic effect caused by a quartic potential with a low barrier
across the C ⬁v axis.17,42 For LiOH, the minimum on the po-
tential energy surface corresponds to a linear configuration,
but owing to a nearly flat potential to 90°, LiOH exhibits
large amplitude oscillations that are consistent with its O–H
r 0 bond length being much shorter than its O–H r̃ e bond
length.
To determine an equilibrium structure for LiOH that is
not artificially contaminated by vibrational effects, data from
experiments and calculations have been combined and the
resulting r e values are listed in Table XII. These r e values
were calculated using the experimental B e values for LiOH
and LiOD from Table IX. As an internal check of consis-
tency, r e values were calculated from the purely theoretical
B e values and then compared to the known r e values from
the PES. The resulting r e values are in excellent agreement,
with the B e -derived Li–O and O–H r e values 0.0003 and
0.0002 Å shorter, respectively, than the PES’s r e values.
Given this, the largest uncertainty in the equilibrium struc-
ture results from the use of the theoretical vibration-rotation
constants in the determination of the experimental B e values.
The estimated uncertainties listed in Table XII were deter-
mined by doubling the largest difference between experimen-
tal and theoretical ␣’s or ␥’s and varying the theoretical con-
stants used by plus or minus this amount. The resulting

Downloaded 25 Mar 2005 to 128.196.209.95. Redistribution subject to AIP license or copyright, see http://jcp.aip.org/jcp/copyright.jsp
11728 J. Chem. Phys., Vol. 121, No. 23, 15 December 2004
largest changes in r e values were used to determine the un-
certainties listed.
The r e values determined from the mixed experimental-
theoretical analysis agree well with the PES values and with
several recent high-level ab initio calculations,9,10,13,14 as
well as with the original estimates by Freund,3 but disagree
with those published previously by McNaughton et al.4 In
particular, their O–H equilibrium bond length is 0.9691共21兲
Å and their Li–O equilibrium bond length is 1.5816共10兲 Å;
these are 0.02 and 0.004 Å longer, respectively, than those
determined in the current study. The Li–O discrepancy is not
major, but the O–H discrepancy is, particularly in light of
discussions on the nature of bonding in LiOH and the nature
of the OH fragment within LiOH. In addition, several recent
computational papers on LiOH have used the McNaughton
r e values as an experimental comparison for the calculated
LiOH structure, and in each case the calculated values have
been ⬃0.02 Å shorter than the McNaughton values.9,10,13,14
Although the McNaughton values are taken as experimental
values, it should be remembered that they were derived using
a semirigid bender model fit to the experimental data and
while adjustments were made to account for the different
vibrationally averaged O–H distance upon deuteration, no
adjustment was made for the different bending amplitude.
This may lead to significant error in the O–H equilibrium
bond length determined by this method. Also listed in Table
XII are r e values for other alkali hydroxide species deter-
mined from experiment for KOH,35 RbOH,41 and CsOH,41
and from ab initio calculations for NaOH.43 In each case the
O–H r e values are 0.02–0.03 Å shorter than the values de-
termined using the semirigid bender method.44 Given this,
and the excellent agreement between theory and experiment
in the current study, we conclude the O–H equilibrium bond
distance in LiOH is 0.949共2兲 Å.
As mentioned in the Introduction, LiOH is the molecule
that lies between bent H2 O and linear Li2 O, and therefore it
is instructive to compare these three molecules in terms of
structure and bonding. Breckenridge and co-workers have
performed extensive spectroscopic studies45– 47 of Li2 O and
have found it to be a ‘‘very ‘floppy’ ionic molecule.’’46 Using
dispersed fluorescence and stimulated emission pumping47
they have determined its Li–O r 0 bond length to be 1.611共3兲
Å, 0.017 Å longer than the r 0 bond length determined here
for LiOH. They did not experimentally determine an r e bond
length, but Koput and Peterson48 calculated an r e for Li2 O at
the CCSD共T,Full兲/cc-pCVQZ level of 1.6159 Å, 0.040 Å
longer than the r e calculated for LiOH at the same level in
this study 共see Table V兲. This apparent discrepancy between
differences in r 0 and r e values is most likely due to dynamic
effects; r 0 is a measure of the Li–O bond’s projection onto
the inertial axis, and in the case of LiOH the inertial axis
closely follows the Li–O bond whereas for Li2 O the Li–O
bond would make a substantial angle with the inertial axis as
it undergoes large amplitude bending vibrational motion. The
O–H r e distance in H2 O is 0.958 Å,49 0.009 Å longer than
the r e determined here for LiOH. In fact, the O–H r e of
0.949 Å in LiOH is substantially shorter than either the hy-
droxyl radical, r e ⫽0.970 Å, 50 or the hydroxide anion, r e
⫽0.964 Å. 51 The O–H stretching frequency is blueshifted
Downloaded 25 Mar 2005 to 128.196.209.95. Redistribution subject to AIP license or copyright, see http://jcp.aip.org/jcp/copyright.jsp
Higgins et al.
FIG. 11. Minimum energy path as a function of 1/r(Li–H). Note the x axis
uses an inverse scale. Dashed line is a linear fit with slope⫽27 205 Å cm⫺1.
considerably from these as well, with the calculated funda-
mental frequency for LiOH equal to 3829.8 cm⫺1, while it is
measured to be 3755.8 cm⫺1 for the v 3 mode of H2 O, 52
3569.6 cm⫺1 for the hydroxyl radical,53 and 3555.6 cm⫺1 for
the hydroxide anion.51 These differences between the OH in
LiOH and the hydroxyl radical or the hydroxide anion chal-
lenge the simple view of LiOH as either an undistorted ionic
molecule comprising Li⫹ (OH) ⫺ , or of Li interacting with
some combination of OH between OH radical and OH⫺ .
Further evidence against the simple ionic view is the fact that
Hartree-Fock level calculations, which should do well for
electrostatic interactions, recover only 64% of the CCSD共T兲
binding energy.
In terms of angular rigidity, the valence field bending
force constant k ␦ /l 1 l 2 derived using the theoretical bending
vibrational frequency and theoretical 共000兲 structure for
LiOH is 2.98 N/m, and for Li2 O and H2 O k ␦ /l 2 is equal to
1.37 共Ref. 47兲 and 70.3 共Ref. 54兲 N/m, respectively. Com-
paring to other XY Z linear triatomic molecules, k ␦ /l 1 l 2 is
equal to 20 and 37 N/m for HCN and OCS, respectively.54
Clearly, LiOH is much closer in nature to Li2 O than H2 O and
is considerably more floppy than typical linear triatomic
molecules.
Excellent agreement is shown with the results of
rotation-vibration calculations using a three-dimensional ab
initio PES for vibrations involving up to three quanta in the
bending mode. Moreover, the charge distribution as seen by
the electric dipole moment is also in excellent agreement. We
may thus examine the origin of the potential. Perhaps the
simplest explanation of the linearity of LiOH is that of el-
ementary electrostatic repulsion of Li⫹ and H⫹ . Figure 11
shows the calculated potential along the angular minimum
energy path as a function of 1/r(Li–H). It is noteworthy that
indeed the bending potential is a linear function of
1/r(Li–H) up to a bond angle of at least 90°. If the bending
potential is due to electrostatic repulsion between the partial
Li and H charges, the slope of this line would give the prod-
uct of the partial charges. The value obtained by fitting the
slope is 0.23e 2 , which falls somewhere between the product
of partial charges calculated using either Mulliken or Natural
J. Chem. Phys., Vol. 121, No. 23, 15 December 2004
population analysis at the MP2/acvqz level. For r(LiO)
greater than 1.72 Å and r(OH) greater than 1.30 Å, the con-
figuration of minimum energy is no longer linear. This indi-
cates that the view of the bending potential as due to the
electrostatic repulsion between Li and H is too simple. This
is perhaps the point at which the electrostatic repulsion no
longer dominates the orbital effects. Unfortunately, current
experiments do not sample the bond lengths at which this
structural change takes place, which is calculated to occur at
v 1 ⫽7, more than 6100 cm⫺1 above the ground state, or at
v 3 ⫽10, more than 31 000 cm⫺1 above the ground state.
V. CONCLUSION
In summary, there is excellent agreement between the
predictions of the proposed unadjusted potential energy sur-
face from a high-level electronic structure calculation and the
observed rotational transitions of a number of bending vibra-
tional levels of LiOH and LiOD. We have predicted vibra-
tional transition frequencies which further will test the reli-
ability of the potential energy surface. In particular, the
fundamental v 3 transition of LiOH is predicted to be almost
100 cm⫺1 above the v 3 transition of H2 O. This prediction is
essentially untested by the present experimental data. The
soft bending mode v 2 is predicted to be a factor of 5 below
that of H2 O. In simplest view the linearity and soft angular
rigidity of LiOH is fit by the model of Coulombic repulsion
between Li and H.
ACKNOWLEDGMENTS
The authors wish to thank Dr. Phil Bunker for valuable
comments and for supplying code for the calculation of the
PES in Ref. 11. This research is supported by the National
Science Foundation under NSF Grant Nos. CHE-98-17707
and CHE-01-38521.
1
See, for example G. L. Miessler and D. A. Tarr, Inorganic Chemistry, 3rd
ed. 共Pearson Prentice Hall, Upper Saddle River, NJ, 2004兲, Chap. 3.
2 wherein they use the hypothetical J⫽0 level of these states.
A. Büchler, J. L. Stauffer, W. Klemperer, and L. Wharton, J. Chem. Phys.
39, 2299 共1963兲.
3 31
S. M. Freund, Ph.D. thesis, Harvard University, Cambridge, MA, 1970.
4
D. McNaughton, L. M. Tack, B. Kleibömer, and P. D. Godfrey, Struct.
Chem. 5, 313 共1994兲.
5
H. Lischka, P. Čársky, and R. Zahradnı́k, Chem. Phys. 25, 19 共1977兲.
6
D. J. DeFrees, B. A. Levi, S. K. Pollack, W. J. Hehre, J. S. Binkley, and J.
A. Pople, J. Am. Chem. Soc. 101, 4085 共1979兲.
7 35
J. S. Binkley, J. A. Pople, and W. J. Hehre, J. Am. Chem. Soc. 102, 939
共1980兲.
8
C. W. Bauschlicher, Jr. and S. R. Langhoff, J. Chem. Phys. 84, 901 共1986兲.
9
E. P. F. Lee and T. G. Wright, Chem. Phys. Lett. 352, 385 共2002兲.
10
M. B. Sullivan, M. A. Iron, P. C. Redfern, J. M. L. Martin, L. A. Curtiss,
and L. Radom, J. Phys. Chem. A 107, 5617 共2003兲.
11
P. R. Bunker, P. Jensen, A. Karpfen, and H. Lischka, J. Mol. Spectrosc.
135, 89 共1989兲.
12
L. V. Gurvich, G. A. Bergman, L. N. Gorokhov, V. S. Iorish, V. Y. Le-
onidov, and V. S. Yungman, J. Phys. Chem. Ref. Data 25, 1211 共1996兲.
13
A. Schulz, B. J. Smith, and L. Radom, J. Phys. Chem. A 103, 7522 共1999兲.
14
P. Burk, K. Sillar, and I. A. Koppel, J. Mol. Struct.: THEOCHEM 543, 223
共2001兲.
15
J. Tennyson, J. R. Henderson, and N. G. Fulton, Comput. Phys. Commun.
86, 175 共1995兲; J. Tennyson, M. A. Kostin, P. Barletta, G. J. Harris, O. L.
Polyansky, J. Ramanlal, and N. F. Zobov, Comput. Phys. Commun. 163,
85 共2004兲.
16
L. M. Ziurys, W. L. Barclay, Jr., M. A. Anderson, D. A. Fletcher, and J. W.
Lamb, Rev. Sci. Instrum. 65, 1517 共1994兲.
Downloaded 25 Mar 2005 to 128.196.209.95. Redistribution subject to AIP license or copyright, see http://jcp.aip.org/jcp/copyright.jsp
Rotational spectrum of LiOH 11729
17
A. J. Apponi, M. A. Anderson, and L. M. Ziurys, J. Chem. Phys. 111,
10919 共1999兲.
18
MOLPRO is a package of ab initio programs written by H.-J. Werner and P.
J. Knowles, with contributions from R. D. Amos, A. Bernhardsson, A.
Berning et al.
19
C. Hampel, K. Peterson, and H.-J. Werner, Chem. Phys. Lett. 190, 1
共1992兲.
20
cc-pCVnZ and aug-cc-pCVnZ basis sets were obtained from the Exten-
sible Computational Chemistry Environment Basis Set Database, Version
10/21/03, as developed and distributed by the Molecular Science Comput-
ing Facility, Environmental and Molecular Sciences Laboratory which is
part of the Pacific Northwest Laboratory, P.O. Box 999, Richland, Wash-
ington 99352, USA, and funded by the U.S. Department of Energy. The
Pacific Northwest Laboratory is a multiprogram laboratory operated by
Battelle Memorial Institute for the U.S. Department of Energy under Con-
tract No. DE-AC06-76RLO 1830. Contact David Feller or Karen Schu-
chardt for further information.
21
T. H. Dunning, Jr., J. Chem. Phys. 90, 1007 共1989兲.
22
D. E. Woon and T. H. Dunning, Jr., J. Chem. Phys. 103, 4572 共1995兲.
23
S. F. Boys and F. Bernardi, Mol. Phys. 19, 553 共1970兲.
24
See EPAPS Document No. E-JCPSA6-121-011446 for complete lists of
ab initio energies and dipole moments and a Fortran subroutine to calcu-
late the potential. A direct link to this document may be found in the
online article’s HTML reference section. The document may also be
reached via the EPAPS homepage 共http://www.aip.org/pubservs/
epaps.html兲 or from ftp.aip.org in the directory /epaps/. See the EPAPS
homepage for more information.
25
Modified from W. H. Press, B. P. Flannery, S. A. Teukolsky, and W. T.
Vetterling, Numerical Recipes: The Art of Scientific Computing 共Cam-
bridge University Press, New York, 1986兲, Chap. 3.
26
Certain unphysical geometries, such as O–Li–H, are included in the
spline input for completeness and required special attention in fitting and
generating extra points.
27
The use of ¯␳ to denote the deviation from linearity is from J. T. Hougen,
P. R. Bunker, and J. W. C. Johns, J. Mol. Spectrosc. 34, 136 共1970兲 and is
used in Ref. 11.
28
The J⫽1←0 lines for the 共001兲 and 共101兲 states of LiOH were measured
in a molecular beam from an effusive source at 1400 K 共Ref. 3兲. A thermal
distribution gives a population of 2.0% and 0.8% relative to the 共000兲 state
for the 共001兲 and 共101兲 states, respectively, and it is unlikely that these
states were observed under the reported experimental conditions. In addi-
tion, there are approximately 14 states that lie energetically between the
reported (120 0) and 共001兲 states, although an alternate assignment of the
observed transitions cannot be determined.
29
Fundamental vibrational frequencies and energy splittings for v 2 ⫽0 states
are calculated by subtracting the rotational energy, hcB v 关 J(J⫹1)⫺l 2 兴
from the energy for the lowest J level of the state, in contrast to Ref. 11
30
L. Manceron, A. Loutellier, and J. P. Perchard, Chem. Phys. 92, 75 共1985兲.
K. Higgins, F.-M. Tao, and W. Klemperer, J. Chem. Phys. 109, 3048
共1998兲.
32
K. Higgins and W. Klemperer, J. Chem. Phys. 110, 1383 共1999兲.
33
C. H. Townes and A. L. Schawlow, Microwave Spectroscopy 共Dover, New
York, 1975兲.
34
P. Kuijpers, T. Törring, and A. Dymanus, Chem. Phys. 15, 457 共1976兲.
E. F. Pearson, B. P. Winnewisser, and M. B. Trueblood, Z. Naturforsch. A
31A, 1259 共1976兲.
36
C. Matsumura and D. R. Lide, Jr., J. Chem. Phys. 50, 71 共1969兲.
37
D. R. Lide, Jr. and R. L. Kuczkowski, J. Chem. Phys. 46, 4768 共1967兲.
38
D. A. Fletcher, M. A. Anderson, W. L. Barclay, and L. M. Ziurys, J. Chem.
Phys. 102, 4334 共1995兲.
39
A. J. Apponi, W. L. Barclay, Jr., and L. M. Ziurys, Astrophys. J. Lett. 414,
L129 共1993兲.
40
B. P. Nuccio, A. J. Apponi, and L. M. Ziurys, J. Chem. Phys. 103, 9193
共1995兲.
41
D. R. Lide and C. Matsumura, J. Chem. Phys. 50, 3080 共1969兲.
42
P. R. Bunker, M. Kolbuszewski, P. Jensen et al., Chem. Phys. Lett. 239,
217 共1995兲.
43
E. P. F. Lee and T. G. Wright, J. Phys. Chem. A 106, 8903 共2002兲.
44
R. D. Brown, P. D. Godfrey, B. Kleibömer, and D. McNaughton, J. Mol.
Struct. 327, 99 共1994兲.
45
D. Bellert and W. H. Breckenridge, J. Chem. Phys. 114, 2871 共2001兲; D.
Bellert, D. K. Winn, and W. H. Breckenridge, Chem. Phys. Lett. 337, 103
共2001兲; 355, 151 共2002兲; J. Chem. Phys. 119, 10169 共2003兲.
11730 J. Chem. Phys., Vol. 121, No. 23, 15 December 2004 Higgins et al.

46 51
D. Bellert, D. K. Winn, and W. H. Breckenridge, Chem. Phys. Lett. 348, N. H. Rosenbaum, J. C. Owrutsky, L. M. Tack, and R. J. Saykally, J.
39 共2001兲. Chem. Phys. 84, 5308 共1986兲.
47
D. Bellert, D. K. Winn, and W. H. Breckenridge, J. Chem. Phys. 117, 3139 52
G. Herzberg, Molecular Spectra and Molecular Structure, Electronic
共2002兲. Spectra and Electronic Structure of Polyatomic Molecules 共Van Nostrand,
48
J. Koput and K. A. Peterson, J. Chem. Phys. 116, 9255 共2002兲. Princeton, NJ, 1966兲.
49
P. Jensen, S. A. Tashkun, and V. L. G. Tyuterev, J. Mol. Spectrosc. 168, 53
T. Amano, J. Mol. Spectrosc. 103, 436 共1984兲.
271 共1994兲. 54
50
K. P. Huber and G. Herzberg, Molecular Spectra and Molecular Structure, G. Herzberg, Molecular Spectra and Molecular Structure, Infrared and
Constants of Diatomic Molecules 共Van Nostrand Reinhold, New York, Raman Spectra of Polyatomic Molecules 共Van Nostrand Reinhold, New
1979兲. York, 1945兲.

Downloaded 25 Mar 2005 to 128.196.209.95. Redistribution subject to AIP license or copyright, see http://jcp.aip.org/jcp/copyright.jsp