Journal of Molecular Structure 555 (2000) 43–60

www.elsevier.nl/locate/molstruc

Lifetimes and dissociation pathways of the quasi-bound states of

the Na· · ·FH van der Waals molecule
F. Mrugała a, P. Piecuch b,1,*, V. Špirko b,c, O. Bludský c
a
Institute of Physics, N. Copernicus University, Grudzia̧dzka 5, 87-100 Toruń, Poland
b
Department of Chemistry, Michigan State University, East Lansing, MI 48824, USA
c
J. Heyrovský Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, 18223 Prague 8, Czech Republic
Received 5 January 2000; accepted 15 February 2000

Abstract
The highly reliable potential energy function for the ground electronic state of the NaFH system based on the ab initio multi-
reference configuration interaction calculations [M.S. Topaler, D.G. Truhlar, X.Y. Chang, P. Piecuch, J.C. Polanyi, J. Chem.
Phys. 108 (1998) 5349; V. Špirko, P. Piecuch, O. Bludsky, J. Chem. Phys. 112 (2000) 189] is used to calculate the energies,
widths, and dissociation pathways of the quasi-bound states of the Na·· ·FH van der Waals molecule. Although emphasis is
placed on the quasi-bound states resulting from vibrational excitation of the HF fragment in the complex, the bound states and
the quasi-bound states, in which the HF fragment is not excited, are investigated as well. The study focuses on assessing the
reliability of the earlier stabilization calculations [V. Špirko, P. Piecuch, O. Bludsky, J. Chem. Phys. 112 (2000) 189] by
performing independent close-coupling calculations for the outgoing scattering waves of the NaFH system. The probabilities of
decay of the Na· · ·FH ro-vibrational resonances into various Na ⫹ HF…v; j† channels provide new insights into the dynamics of
dissociation of the Na· ··FH complex. 䉷 2000 Elsevier Science B.V. All rights reserved.
Keywords: Quasi-bound states; van der Waals complexes; Close-coupling approach; Stabilization method; Ro-vibrational states

1. Introduction [3] and in the studies of the effect of complex forma-

It has been amply documented in the literature that
the ro-vibrational spectra of van der Waals (vdW)
molecules can provide essential and very accurate
information about the nature of intermolecular inter-
actions. Although the majority of spectroscopic
studies of vdW complexes focus on important low-
frequency motions [1,2], there is a growing interest
in the predissociation pathways of quasi-bound states
* Corresponding author. Tel.: ⫹1-517-355-9715; fax: ⫹1-517-
353-1793.
E-mail address: piecuch@cem.msu.edu (P. Piecuch).
1
Internet: www.cem.msu.edu/~piecuch.
0022-2860/00/$ - see front matter 䉷 2000 Elsevier Science B.V. All rights reserved.
PII: S0022-286 0(00)00586-X
tion on the high-frequency monomer modes [4]. The
lifetimes of quasi-bound states of vdW molecules and
state-to-state cross sections for dissociation of these
states into states of monomers may provide detailed
information about intermolecular potentials. In the
case of reactive complexes, which are precursors of
chemical reactions, the lifetimes and dissociation
pathways of quasi-bound ro-vibrational states
may provide detailed spectroscopic information
about the dynamics of elementary chemical
processes.
We have recently studied the bound and quasi-
bound ro-vibrational states of the Na· · ·FH complex
[5]. This very weakly bound system (bound only
44 F. Mrugała et al. / Journal of Molecular Structure 555 (2000) 43–60
by 0.065 eV [5–7] or 0.076 eV [8]) is believed to
be the precursor of the photo-induced charge
transfer or “harpooning” [9,10] occurring in the
electronically excited states of the complex, i.e.
[8,11,12],
Na…FH ⫹ hn ! ‰…Na…FH†ⴱ Š‡ ! ‰Na⫹ ……FH†⫺ Š‡
! NaF ⫹ H; (1)
where the asterisk indicates an electronically
excited complex and the double-dagger designates
an intermediate between reactants and products.
Although recent quantum-scattering calculations
[13,14], based on accurate potential energy
surfaces (PESs) [8] that were obtained using the
multi-reference configuration interaction method
with single and double excitations (the MRCISD
approach; precisely, the MRDCI variant of the
MRCISD method [15–17]), indicate that the domi-
nant channel in the photo-induced Na…FH ⫹ hn
process is photo-dissociation into reactants,
Na…FH ⫹ hn ! ‰…Na…FH†ⴱ Š‡
! Na ⫹ HF or Naⴱ ⫹ HF; …2†
the same calculations indicate that there may be a
possibility of improving the yield of products of
reaction (1) by exciting the Na· · ·FH complex
vibrationally prior to electronic excitation. It is
well-known that the ground-state Na ⫹ HF ! NaF ⫹
H reaction also does not proceed without vibrational exci-
tation of HF [18–23], which is a consequence of the
rather high energy barrier on the ground-state PES
of NaFH (1.26 eV [8]).
Our recent calculations of the quasi-bound states of
Na· ··FH [5], and a significant enhancement of the
infrared absorption line strengths corresponding to
the vr ⬎ 0 ← vr ˆ 0 transitions, when compared to
the isolated HF molecule [24] (vr is the quantum
number for the H–F motion), suggest that one can
contemplate an experiment in which the excitation
of the H–F fragment in the complex prior to electronic
excitation is used to change the dynamics of the
Na…FH ⫹ hn process in favor of charge transfer,
Eq. (1). Indeed, by performing accurate calculations
combining the variational approach to the ro-vibra-
tional problem with the stabilization method of
Mandelshtam et al. [25,26], we provided [5] the strong
evidence for the existence of long-lived ro-vibrational
resonances corresponding to excitation of the H–F
fragment in the complex to vr ˆ 1 and 2. According
to our stabilization calculations [5], the lifetimes of
many vr ˆ 1 states of Na· · ·FH are in a nanosecond
regime. At least some vr ˆ 2 states have lifetimes in a
subnanosecond regime. By performing infinite-order
perturbative calculations based on the adiabatic
separation of vibrational motions to define the unper-
turbed problem [27,28], we demonstrated that the
long-lived resonances of Na· · ·FH are precisely those
that are bound in the adiabatic approximation. The
metastable states of Na· ··FH, which are not bound
in the adiabatic approximation, are usually character-
ized by much shorter lifetimes.
There are two purposes of the present work. First of
all, we would like to complete the earlier studies
[5,24] by providing information about dissociation
pathways of the quasi-bound states of Na· ··FH.
Thus, we calculate the probabilities of decay of the
vr ˆ 0 and 1 states into the Na ⫹ HF…v; j† channels,
where v and j are, respectively, the vibrational and
rotational quantum numbers of the isolated HF
molecule. Calculations are performed using the
close-coupling approach [29,30] to the scattering
states of the NaFH system. The second purpose of
this study is to verify the accuracy of our stabilization
calculations of the vr ˆ 1 quasi-bound states of
Na· · ·FH [5], which were based on the variational
treatment of the ro-vibrational eigenvalue problem,
by performing completely independent close-
coupling calculations of energy positions and widths
of the Na· · ·FH resonances. The stabilization method
used in Ref. [5] and the close-coupling approach to
scattering states used in the present work are so
unrelated that the agreement of the results of both
calculations can be used to argue that the information
obtained in these calculations is trustworthy and can
serve experimentalists in their studies of dynamics of
Na· · ·FH. Indeed, in the stabilization method
employed in Ref. [5], the eigenvalues of energies of
resonance states are obtained by repeatedly calcu-
lating the eigenvalues of the ro-vibrational Hamilto-
nian, while varying the size of the coordinate box in
which the molecule is contained. A plot of the eigen-
values as a function of the size of the box (the
 F. Mrugała et al. / Journal of Molecular Structure 555 (2000) 43–60
stabilization diagram) is used to extract the complex
resonance energies,
e ˆ Eres ⫺ iG=2; …
where the real part (Eres) is the position of the reso-
nance and G is the width (i is the imaginary unit). The
lifetimes of quasi-bound states, t , are then estimated
through the relationship
t ˆ É=G; …
where É ˆ h=…2p† and h is the Planck constant. On the
other hand, in the close-coupling approach, a system
of coupled one-dimensional Schrödinger equations in
the scattering coordinate is solved for the continuum
states of the Hamiltonian, which formally describe the
scattering of Na from HF. The resulting collision-time
delay matrix provides information about the energy
positions and widths of quasi-bound states and
branching ratios for decay of these states into various
Na ⫹ HF…v; j† channels.
The paper is organized as follows. The ground-state
PES of the NaFH system is briefly discussed in
Section 2. The stabilization and close-coupling
approaches and the relevant computational details
are described in Section 3. The results of our calcula-
tions are discussed in Section 4, and Section 5
summarizes our findings.
2. Potential energy surface
In describing the PES of Na· ··FH, which is used in
the stabilization and close-coupling calculations and
in solving the corresponding ro-vibrational problem,
we use the internal Jacobi (or scattering) coordinates:
the H–F distance r ⬅ 兩r兩 (defining the high-frequency
stretching coordinate), the distance R ⬅ 兩R兩 between
Na and the center of mass of HF (defining the vdW
stretching or scattering coordinate), and the angle u
between two Jacobi vectors, r and R (defining the
bending or internal rotation coordinate).
The PES for the ground electronic state of the
NaFH system was described in our earlier paper [5].
It was obtained by refitting the adiabatic potential,
resulting from fitting highly accurate MRDCI ener-
gies of the lowest two 2A 0 states to a 2 × 2 diabatic
45
representation [8], to the following functional form,
X
V…r; R; u† ˆ V 0 ⫹ C…a; b; g†{exp‰⫺a1 …r ⫺ rr †Š}a
a ;b ;g
3†
 {exp‰⫺a2 …R ⫺ Rr †Š}b Pg …cos u†
X
ˆ Ul …r; R†Pl …cos u†; (5)
l
where V0 ; C…a; b; g†; a1, a2, rr, and Rr are the adjus-
4† table parameters and Pg (cos u ) designate the
Legendre polynomials. In order to improve the quality
of PES, additional MRDCI calculations were
performed along the one-dimensional cuts of the adia-
batic potential through the vdW minimum, corre-
sponding to fixing one of the three Jacobi
coordinates at its equilibrium value, while allowing
the remaining two coordinates to vary over the entire
range. The details of these additional MRDCI calcu-
lations can be found in Ref. [5], whereas the details of
the original MRDCI calculations used to construct a
2 × 2 diabatic representation of the lowest two 2A 0
states of NaFH are described in Ref. [8].
Although the PES described in Ref. [5] could
basically be used in the present study, we decided to
refit it. The reason for refitting the PES again is
primarily related to the fact that the close-coupling
calculations for scattering states require that the elec-
tronic potential V…r; R; u† can be given the following
form,
^
V…r; R; u† ⬅ V…r; R; r^ ·R†
…6†
^
ˆ VH–F …r† ⫹ VNa–FH …r; R; r^ ·R†;
^ is the intermolecular potential
where VNa–FH …r; R; r^ ·R†
obtained by subtracting the diatomic potential,
^
VH–F …r† ˆ lim V…r; R; r^ ·R†; …7†
R!∞
^ (as usual, r^ and R
from V…r; R; r^ ·R† ^ are the spherical
angles of the Jacobi vectors, r and R, respectively).
This form of the potential, Eq. (6), is essential for the
correct description of the boundary conditions for
scattering states (coupled equations for partial scat-
tering waves used in the close-coupling calculations
should automatically decouple for R ! ∞; cf. Section
3 for further details).
The PES reported in Ref. [5] can be given the form
46 F. Mrugała et al. / Journal of Molecular Structure 555 (2000) 43–60
Fig. 1. The PES for the ground electronic state of the NaFH system obtained by refitting the earlier MRDCI data [8] augmented with new
MRDCI energies [5] to Eq. (5), where C…a; b ˆ 0; g† ˆ 0 for g 苷 0: The angle u used for plotting the PES is fixed at the value corresponding to
vdW minimum.
of Eq. (6), but only approximately [we can always try
to extract the diatomic potential VH–F …r† from a given
potential V…r; R; u† by studying the limit described by
Eq. (7) for a fixed value of u assuming that, for suffi-
ciently large R values, the potential V…r; R; u† is
virtually isotropic]. In order to obtain the rigorous
decomposition of the total electronic potential
^
V…r; R; u†; Eq. (5), into VH–F …r† and VNa–FH …r; R; r^ ·R†;
we must impose the following condition on the coeffi-
cients C…a; b; g†;
C…a; 0; g† ˆ 0; for g 苷 0; …
so that V…r; R; u†; Eq. (5), does not depend on u for
R ! ∞: The above condition has not been imposed on
the potential reported in Ref. [5] and, in consequence,
V…r; R; u† of Ref. [5] is only approximately indepen-
dent of u in the limit of infinite R. This had no effect
on the stabilization calculations performed in our
earlier study [5], which were based on enclosing the
NaFH system in the coordinate box along the vdW
stretch coordinate R, but would cause problems in the
close-coupling calculations of quasi-bound states
reported here.
Thus, we refitted our earlier PES using the func-
tional form described by Eq. (5), in which the coeffi-
cients C…a; b; g† satisfy the condition (8). The refitted
PES, shown in Fig. 1, involves 125 parameters [121
coefficients C…a; b; g† with the maximum values of a ,
b , and g equal 6, 6, and 9, respectively, and 4 para-
meters a1, a2, rr, and Rr]. These parameters are listed
in Table 1. In constructing the new fit, we considered a
wide range of almost 5000 nuclear geometries, with
energies up to 13,500 cm ⫺1 above the vdW minimum.
The differences between the fitted and calculated
MRDCI energies were usually 5–10 cm ⫺1 or smaller
for energies up to ⬃1000 cm ⫺1 above the vdW
minimum (this includes all bound and vr ˆ 0 quasi-
bound states). For energies up to 4500 cm ⫺1 above the
vdW minimum, including the important vr ˆ 1 quasi-
8†
bound states, they usually were about 10–20 cm ⫺1.
The overall quality of the new fit is as good as in
the earlier work [5]. For example, the standard devia-
tion of the new fit is as small as in the case of the fit
described in Ref. [5] (ca. 60 cm ⫺1).
All essential features of the ground-state PES of the
NaFH system are accurately reproduced by the new
fit. In particular, the geometry of the vdW minimum,
re ˆ 0:9207 A;  Re ˆ 2:4720 A;  ue ˆ 58:92⬚; and the
binding energy of the Na· · ·FH complex, 0.079 eV
below the Na…3s 2 S† ⫹ HF…X 1 S ⫹ † asymptote, agree
very well with the original results reported in Ref. [8].
The slight disagreement with the binding energy
reported in Ref. [5] (0.065 eV) is a consequence of
the fact that the earlier potential reported in Ref. [5]
does not satisfy the condition (8). The new fit predicts
the existence of the saddle point at almost the same
 F. Mrugała et al. / Journal of Molecular Structure 555 (2000) 43–60
nuclear geometry and at almost the same energy as the
 R ˆ 1:981 A;
original diabatic fit [8] (r ˆ 1:630 A;  Hamiltonian defined in the body-fixed molecular
and u ˆ 81:6⬚; energy ⬃ 10; 200 cm⫺1 above the
Na ⫹ HF asymptote).
3. Dynamics of the Na ⫹ HF system below the
reaction threshold: stabilization and close-
coupling calculations of the vr ⱕ 1 quasi-bound
states of the Na···FH molecule
3.1. Stabilization calculations
In the boxing variant [31,32] of the stabilization
method [33], which we used in our earlier study [5]
and use in this work (primarily to obtain new energy
positions resulting from refitting the earlier potential),
the energy positions and widths of resonance states
are obtained by repeatedly calculating the eigenvalues
of the Hamiltonian, while gradually increasing the
volume of the configuration space accessible to a
molecule (defined by the coordinate box). As
mentioned in the Introduction, the complex energies
characterizing individual quasi-bound states are
obtained by constructing the plot of eigenvalues of
the Hamiltonian regarded as functions of the boxing
parameter (the stabilization diagram). The quasi-
bound states are then stabilized as the basis functions
sample the outer regions of the interaction potential,
whereas the eigenvalues corresponding to the true
continuum states decrease monotonically. This can
be seen in the stabilization diagram, which, in the
case of the long-lived quasi-bound states, is always
characterized by the very small variation of the eigen-
values of the Hamiltonian in some finite regions of
values of the boxing parameter and by the rapid
changes in the eigenvalues of the Hamiltonian in
some other regions of values of the boxing parameter,
resulting in a series of avoided crossings between
different energy curves constituting the stabilization
diagram (see Ref. [5] for examples of stabilization
diagrams).
In the case of the ro-vibrational resonances of
Na· · ·FH, the natural choice of the boxing coordinate
is the scattering (or vdW stretching) coordinate R. The
size of the coordinate box along R is designated by
Rmax. The Hamiltonian used to obtain the energies of
the ro-vibrational eigenstates of Na· ··FH for different
47
values of Rmax is the well-known Sutcliffe–Tennyson
frame [34]. This Hamiltonian, designated here by
HSTJ …r; R; u†; which parametrically depends on the
rotational quantum number J, after integrating over
the bending coordinate u and neglecting small
Coriolis terms, reduces to an effective operator HST ⬅
0 0
储具qk兩HSTJ …r; R; u†兩q k 典储; which operates only on func-
tions of the radial variables r and R. We obtain,
具qk兩HST 兩q 0 k 0 典 ˆ ⫺É2 dq;q 0 dk;k 0
"
1 22 1 22
× ⫹ ⫺ q…q ⫹ 1†
2m2 2R2 2m1 2r 2
( )
1 1
 ⫹
2m2 R2 2m 1 r 2
#
J…J ⫹ 1† ⫺ 2k2
⫺
2m 2 R 2
X
⫹ dk;k 0 gl …q; q 0 ; k†Ul …r; R†; (9)
l
where q labels the basis functions describing internal
rotation [the associated Legendre functions 具u兩qk典 ⬅
Q qk …u†Š; k describes the coupling between the internal
and external rotations (k is a good quantum number
only when the Coriolis coupling terms are neglected),
m 1 and m 2 are the appropriate reduced masses (m 1 for
HF and m 2 for the motion of Na relative to HF), and
gl …q; q 0 ; k† ˆ 具qk兩Pl …cos u†兩q 0 k典 …10†
are the Gaunt coefficients [35] describing the coupling
between different bending states.
For each value of Rmax, the eigenvalue problem for
HSTJ …r; R; u† or H , Eq. (9), is solved variationally by
ST
diagonalizing the matrix representing H ST in a basis
set consisting of products of eigenfunctions corre-
sponding to uncoupled one-dimensional Schrödinger
equations describing the low- and high-frequency
stretching motions. As in our earlier work [5], the
basis set functions for the r and R dependencies are
obtained by solving the corresponding one-dimen-
sional Schrödinger equation numerically (i.e. on a
dense grid of points along the r and R coordinates)
using the Numerov–Cooley procedure [36]. Since the
numerical basis functions obtained in this way are
48 F. Mrugała et al. / Journal of Molecular Structure 555 (2000) 43–60

Table 1
The parameters C…a; b; g† defining the potential energy function V…r; R; u†; Eq. (5), for the ground electronic state of NaFH (in cm ⫺1), used in
this paper. The remaining parameters characterizing V…r; R; u† equal: a1 ˆ 1:15 A  ⫺1 ; a2 ˆ 1:37 A
 ⫺1 ; rr ˆ 0:92 A
 and Rr ˆ 2:47 A


a b g C…a; b; g† a b g C…a; b; g† a b g C…a; b; g†

1 0 0 ⫺431053.165 3 3 1 ⫺8055.999 2 3 4 20791.839

0 1 0 244060.753 1 5 1 2060.010 1 4 4 6163.361
2 0 0 3045963.145 0 1 2 77746.435 0 5 4 ⫺809.809
1 1 0 ⫺1512991.029 1 1 2 ⫺562950.156 5 1 4 ⫺14977.809
0 2 0 ⫺22642.263 2 1 2 1479513.408 4 2 4 15850.609
3 0 0 ⫺7270876.519 3 1 2 ⫺1863553.472 2 4 4 ⫺5397.423
2 1 0 3586158.698 2 2 2 55446.858 1 5 4 510.489
1 2 0 21920.407 4 1 2 1147572.940 0 6 4 127.442
0 3 0 16365.775 3 2 2 ⫺99933.443 1 1 5 18181.747
4 0 0 8022123.387 2 3 2 5682.782 0 2 5 6986.664
3 1 0 ⫺4089703.974 5 1 2 ⫺278286.495 2 1 5 ⫺61752.442
1 3 0 ⫺5437.773 4 2 2 45545.675 1 2 5 ⫺30615.606
0 4 0 ⫺7404.471 3 3 2 ⫺4514.441 0 3 5 ⫺3795.902
5 0 0 ⫺4263328.436 1 5 2 ⫺349.109 3 1 5 63187.378
4 1 0 2258973.955 0 6 2 184.400 2 2 5 60495.750
2 3 0 ⫺10548.986 0 2 3 12361.882 1 3 5 4937.298
1 4 0 4241.534 2 1 3 ⫺92356.753 4 1 5 ⫺19913.483
0 5 0 1724.143 0 3 3 ⫺3841.303 3 2 5 ⫺50880.488
6 0 0 896577.314 3 1 3 289904.292 1 4 5 ⫺3260.463
5 1 0 ⫺485722.315 2 2 3 ⫺138342.116 0 5 5 768.215
4 2 0 ⫺2335.007 1 3 3 33221.263 4 2 5 13480.856
3 3 0 4771.359 0 4 3 ⫺5239.100 2 4 5 2014.629
1 5 0 ⫺654.133 4 1 3 ⫺289333.327 1 5 5 ⫺190.889
0 6 0 ⫺108.499 3 2 3 193822.727 0 6 5 ⫺146.575
0 1 1 ⫺147282.081 2 3 3 ⫺34539.077 0 1 6 ⫺3016.439
1 1 1 885325.358 0 5 3 1473.678 1 1 6 9813.662
0 2 1 32130.767 5 1 3 92608.022 2 1 6 ⫺6765.135
2 1 1 ⫺2006657.112 4 2 3 ⫺69029.198 2 2 6 ⫺4500.326
1 2 1 ⫺88127.897 3 3 3 4493.873 0 4 6 1405.608
0 3 1 ⫺23908.991 2 4 3 5241.361 3 2 6 5502.554
3 1 1 2169812.407 1 5 3 ⫺1249.092 1 4 6 719.483
2 2 1 134180.537 0 6 3 ⫺159.319 0 5 6 ⫺915.199
0 4 1 14937.877 1 1 4 26549.008 3 3 6 ⫺2035.601
4 1 1 ⫺1136579.327 0 2 4 ⫺24451.354 0 6 6 158.938
3 2 1 ⫺102144.218 2 1 4 ⫺49399.110 0 1 7 ⫺650.338
2 3 1 27117.971 1 2 4 51333.519 1 1 7 592.692
1 4 1 ⫺12068.771 0 3 4 12629.976 2 3 7 ⫺1042.506
0 5 1 ⫺2812.615 1 3 4 ⫺34465.672 3 3 7 872.468
5 1 1 233705.956 4 1 4 37183.464 4 1 9 832.893
4 2 1 25777.863 3 2 4 ⫺41086.152 5 1 9 ⫺712.313
2 4 9 7.823

equivalent to many more analytic functions, which are
often used in algebraic approaches to an eigenvalue
problem (e.g. eigenstates of harmonic oscillators), it is
sufficient to use 4 numerical functions for the high-
frequency stretch coordinate r, 15 analytic functions
[associated Legendre functions Q qk …u†] for the bend,
and as little as 60 numerical functions for the vdW
stretch coordinate R to get the converged description
of practically all vr ⱕ 1 quasi-bound states [5].
Without using the numerical basis functions for r
and R (particularly for the latter coordinate), we
would have significant problems in saturating the
energy positions and widths of the vr ˆ 1 resonances
with the basis set, since the basis set for R must be
 F. Mrugała et al. / Journal of Molecular Structure 555 (2000) 43–60
large enough to provide us with a uniform description
of the ro-vibrational problem over a wide range of
values of the boxing parameter Rmax. The bound ro-
vibrational states (which are an obvious byproduct of
the stabilization calculations) are much less
demanding in this regard [5].
Other details of the stabilization method used in the
present work can be found in the original papers by
Mandelshtam et al. [25,26] and in our earlier work [5].
Let us only recall that, after obtaining the functions
En(Rmax) that describe the dependence of the nth
eigenvalue of the Hamiltonian (9) on the size of the
coordinate box along R, we invert the functions
En(Rmax) to obtain the new functions Rmax,n(E), from
which we calculate the total phase shift f (E). The
calculated phase shift is then fitted to a Breit–Wigner
function after subtracting the background phase shift
f b(E), which can be approximated by a low-order
polynomial. The energy positions and widths are
extracted from the formula
 
E ⫺ Eres
f…E† ˆ arctan 2 ⫹ f b …E†: …11†
G waves, C …⫹†JMp …E; gi ; r; R†; i ˆ 1; …; N open ; which are
3.2. Close-coupling calculations
The close-coupling approach and the numerical
procedures used in the calculation of the quasi-
bound states of Na· · ·FH are similar to those described
in Ref. [37]. Thus, we limit our description to the most
essential elements of the approach, which are relevant
to the present calculations.
We are interested in solving the Schrödinger equa-
tion, …E ⫺ H†C ˆ 0; for the continuum states of the
NaFH system, C , where H is the Hamiltonian for
the relative nuclear motion. In order to describe the
configuration of nuclei, we use the standard Jacobi
^ defined in the space-fixed
coordinates, …r; r^ ; R; R†;
laboratory frame [r and R are the Jacobi vectors intro-
duced in Section 2 and …r; r^ † and …R; R† ^ are their
spherical components]. In these coordinates, the
Hamiltonian for the relative nuclear motion takes
the following form:
H ⬅ H…r; R† ˆ K H–F …r† ⫹ KNa–FH …R† ⫹ VH–F …r†
^
⫹ VNa–FH …r; R; r^ ·R†; …12†
49
where
1 ^2 1 ^2 ^
KNa–FH …R† ˆ P …R† ⫹ l …R† …13†
2m2 2m2 R2
and
1 2 1 ^2
KH–F …r† ˆ p^ …r† ⫹ j …^r† …14†
2m 1 2m 1 r 2
are the kinetic energy operators for the R and r
motions, and VNa–FH …r; R; r^ ·R†^ and VH–F …r† are the
intermolecular and diatomic potentials defined by
Eqs. (6) and (7), respectively. We use the notation,
in which P…R†^ ˆ ⫺iɅ2=2R ⫹ 1=R† and l… ^ R†
^ represent
the radial momentum and the angular momentum
operators corresponding to classical motion of the R
vector and p…r†^ ˆ ⫺iɅ2=2r ⫹ 1=r† and j…^ ^ r† are similar
quantities for the r motion; m 1 and m 2 are the appro-
priate reduced masses [cf. Eq. (9)].
Because of our interest in the dynamics of dissocia-
tion of the quasi-bound states of Na···FH, we solve the
Schrödinger equation, …E ⫺ H†C ˆ 0; where H is
defined by Eq. (12), for the partial scattering outgoing
the simultaneous eigenfunctions of the total angular
momentum operator J^ ˆ … j^ ⫹ l†
2 ^ 2 ; its z component
J^z ; and the spatial inversion operator I; ^ with the
eigenvalues J…J ⫹ 1†É2 ; MÉ; and …⫺1†J p; respectively.
Each outgoing wave C …⫹†JMp …E; gi ; r; R† is labeled by
the superindex gi ˆ …v; j; l†i ; where v, j, and l are the
quantum numbers representing a specific quantum
state of the Na ⫹ HF system, from which the given
partial wave has evolved. We use the notation, in
which v and j are the vibrational and rotational
quantum numbers characterizing the ro-vibrational
state of the isolated HF molecule having energy
e…v; j† and l is the quantum number of the rotation
of Na relative to HF (labeling the eigenstates of
l^ ; because of the angular momentum addition
2
rules, the allowed values of l depend on the
choice of J, p, and j [37]). Finally, we use
N open ⬅ N open …E; J; p† to designate the number of
different g ’s that are possible for the given energy
E, total angular momentum J, and parity p, i.e. the
number of open dissociation channels Na ⫹
HF…v; j† consistent with the angular momentum
addition rules and energy conservation, ev; j ⬍ E:
In the close-coupling approach to the atom–diatom
scattering, we assume that we can use the finite basis
50 F. Mrugała et al. / Journal of Molecular Structure 555 (2000) 43–60

set, vanish at R ˆ 0; and asymptotically,

s
^ ˆ {F JMp …r; R†}
F JMp …r; R† ^ Nkˆ1 ; …15† …⫹†Jp m
‰H⫺
R!∞
k Ff …E; gi ; R† ! lf …kf R†df ;i
Ékf
to describe the dependencies of the scattering waves
C …⫹†JMp …E; gi ; r; R† on all dynamically relevant coor- ⫺ H⫹ Jp
lf …kf r†Sf ;i …E†Š; for f ⱕ N ; …20†
open
dinates but the scattering coordinate R. We define the
^ in the usual way, namely
basis functions F kJMp …r; R† where H^ lf are the spherical Ricatti–Hankel functions
[38], of the lf-th order,

^ ˆ 1 x…vj† …r†YJMp …^r; R†;

^ 2m 2
F kJMp …r; R† … jl†k …
r k
where x…vj† …r† is the radial ro-vibrational function of
the HF molecule and YJMp ^ are the bipolar
… jl† …^
r; R†
harmonics of parity …⫺1† p [39] (i.e. the irreducible
J
products of surface spherical harmonics depending on
r^ and R^ coupled by the appropriate Clebsch–Gordan
coefficients). Since the basis functions F kJMp …r; R† ^
must describe all open Na ⫹ HF…v; j† channels, we
require that N ⬎ N open :
In this basis set, the partial scattering outgoing
waves, C …⫹†JMp …E; gi ; r; R†; i ˆ 1; …N open ; assume
the following form,
C …⫹†JMp …E; gi ; r; R†
1 X N
^
ˆ F …⫹†Jp …E; gi ; R†F fJMp …r; R†; …
R f ˆ1 f
where the N-dimensional vector of the radial
functions Ff…⫹†Jp …E; gi ; R†; i.e. F…⫹†Jp …E; gi ; R† ˆ
{Ff…⫹†Jp …E; gi ; R†}Nfˆ1 ; satisfies the system of N
coupled Schrödinger equations in the scattering
coordinate R,
‰EI ⫺ HJp …R†ŠF…⫹†Jp …E; gi ; R† ˆ 0: …
The matrix HJp …R† represents the Hamiltonian H,
^ i.e.
Eq. (12), in the basis set F JMp …r; R†;
1
HJp …R† ˆ R F JMp 兩H F JMp ; …19†
R ^
r;R
where 具…典r;R^ designates the integration over r and R ^ potential VNa–FH (VNa–FH ⬇ 0 for R ⱖ R∞ ). The
(all coordinates but R). The system of coupled
equations, Eq. (18), for the radial functions
Ff…⫹†Jp …E; gi ; R†; is the essential element of the
close-coupling approach, and we solve it by numerical
integration on a dense grid of R values.
The radial functions Ff…⫹†Jp …E; gi ; R†; f ˆ 1; …; N;
16† kf2 ˆ …E ⫺ e…v; i† f †;
É2
and SJpf ;i …E† are the elements of the (partial) scattering
matrix SJp …E†; which describe all gi ⬅ …v; j; l†i !
gf ⬅ …v; j; l†f transitions, i; f ˆ 1; …; N open ; between
different channels g that are open for given E, J,
and p. Because of the angular momentum addition
rules, the values of lf ˆ lf …J; p; jf † in Eq. (20) depend
on J, p, and jf [37]. The components of the vector
F…⫹†Jp …E; gi ; R†; corresponding to all closed channels,
i.e. the radial functions Ff…⫹†Jp …E; gi ; R† with f ⬎
N open ; decay exponentially like H⫹ lf …i兩kf 兩R†:
The quasi-bound states of the Na· ··FH complex are
detected and characterized by analyzing the energy
dependence of the collision-time delay (or collision
lifetime) matrices QJp …E† [40], which are defined as
17† follows:
d Jp
QJp …E† ˆ iÉ ‰S …E†Š† SJp …E†: …21†
dE
In the case of the quasi-bound states of Na· · ·FH
studied in this work, which are predominantly the
Feschbach-type resonances, it is convenient to sepa-
rate out from the matrix QJp …E†; Eq. (21), the matrix
Qres;Jp …E†; whose elements are defined as follows [37]:
18†
…⫹†Jp
Qres;Jp
f ;i …E† ˆ 具F …E; gf †兩PC P‰0;R∞ Š F…⫹†Jp …E; gi †典R ;
for i; f ˆ 1; …; N open ; (22)
where P‰0;R∞ Š denotes the projector on the interval
‰0; R∞ Š and R∞ is the range of the intermolecular
operator PC is the projector on the components of
F…⫹†Jp …E; gi ; R†; which correspond to all closed
channels, i.e. …PC †f ;i ˆ df ;i 1…0† for f ⬎ N open
…ⱕN open †; and 具…典R designates the integration
over R.
The two basic parameters of a quasi-bound state,
 F. Mrugała et al. / Journal of Molecular Structure 555 (2000) 43–60
i.e. the energy position Eres and the width G , are
obtained by fitting the function Tr Q Jp …E† [or
Tr Qres;Jp …E†] to the following formula:
G ⫹ 2r…E ⫺ E res †
Tr Qres;Jp …E† ˆ É ⫹ C: …23†
…E ⫺ Eres †2 ⫹ G 2 =4
The fitting procedure may start from determining the
maximum E0 in the resonance structure of Tr QJp …E†
[or Tr Qres;Jp …E†], followed by calculating the initial
estimate of the width through the formula G 0 ˆ
4É=Tr Qres;Jp …E0 †: By calculating a few additional
values of Tr Qres;Jp …E† for the energies E around E0
(for example, at E ˆ E0 ^ G 0 =2†; we can determine
all parameters of the fit (23), including Eres and G . The
stabilization calculations described in Section 3.1, or
even simple estimates of the resonance energy
positions obtained from perturbative calculations for
the quasi-bound states [5], are extremely useful in
identifying the maxima E0 in the resonance structure
of Tr Q Jp …E†; particularly when the density of reso-
nances in a given energy range is large (as is the case
for the vr ˆ 1 states of Na· ··FH).
The partial widths G i, for i ˆ 1; …; N open ; are deter-
mined by fitting the individual diagonal elements of
QJp …E† [or Qres;Jp …E†] to the formula,
Gi
Qres;Jp …E† ˆ É
i;i
…E ⫺ Eres †2 ⫹ G 2 =4
⫹ Ci…0† ⫹ Ci …E ⫺ Eres †: …24†
For the rotationless …J ˆ 0† quasi-bound states of
Na· · ·FH, the index i in the above expression can be
identified with the ro-vibrational state of the HF
molecule, …v; j†i ; since, in this case, l ˆ j (cf. Ref.
[37]). Thus, the ratios G i =G; for i ˆ 1; …; N open ; give
us immediately the branching ratios for decay of the
J ˆ 0 quasi-bound states of the Na· · ·FH complex into
various Na ⫹ HF…v; j† channels.
Although in the above description, we focused on
the close-coupling calculations for the quasi-bound
states, information about the bound-states can be
obtained from these calculations as well. We refer
the reader to Ref. [37] for further details.
3.3. The remaining computational details
The stabilization calculations performed in this
study were somewhat easier than those reported
51
earlier [5], since we mainly focused on the long-
lived vr ˆ 1 quasi-bound states, and for these states
it is sufficient to use 4 numerical basis functions for
the H–F stretch, 15 basis functions for the bend …q ˆ
0–14†; and 60 numerical basis functions for the vdW
stretch in order to obtain the converged values of Eres
and G . The fact that we used the refitted potential,
described in Section 2, had practically no effect on
the calculated widths of the v r ˆ 1 resonances (within
the accuracy of the stabilization approach employed),
so that we could concentrate on the energy positions,
which slightly changed compared to their earlier
values [5] (typically, by 5–10 cm ⫺1; cf. Section 4).
As in the earlier work [5], we varied the boxing para-
meter Rmax between 6.5 and 9.0 Å with the steps 0.005
or 0.01 Å.
As in the earlier paper [5], the assignment of
quantum numbers to states that are bound in the adia-
batic approximation was achieved by performing a
two-step separation of the vibrational modes,
followed by infinite-order perturbative calculations
in which the zero-order problem is defined by the
adiabatic approximation and the non-adiabatic
coupling terms between different vibrational motions
define the perturbation [27,28]. Let us recall that, in
the first step of this procedure, we separate the high-
frequency H–F stretching mode from the low-
frequency stretch and bend motions, obtaining a set
of smaller, two-dimensional effective problems corre-
sponding to different quantum states of the H–F
stretch. In the second step, we replace each two-
dimensional problem in R and u by a system of
coupled one-dimensional Schrödinger equations in R
corresponding to different bending states, which can
be solved variationally or using the close-coupling
approach [5]. The quantum numbers for the high-
frequency stretch, the bend, and the vdW stretch,
resulting from the above procedure, are designated
by vr, vu , and vR, respectively.
The ro-vibrational states of HF, …v; j ˆ 0–jmax †;
used to define the basis set functions F kJMp …r; R†;^
Eq. (16), and to construct the corresponding close-
coupling expansion (17), were the following: (0,0–
19), (1,0–19), (2,0–17), and (3,0–15). The energies
e…v; j† and the corresponding functions x…v; j† …r† were
determined from the HF potential VH–F …r†; Eq. (7)
(the potential of HF extracted from the PES of
NaFH). The system of 74 coupled equations, Eq.
52 F. Mrugała et al. / Journal of Molecular Structure 555 (2000) 43–60

Table 2 Origin 2000 systems from Silicon Graphics (one

The energies of the bound ro-vibrational states of the Na···FH available to us locally, equipped with two 250 MHz
molecule (in cm ⫺1) with the rotational quantum number J ˆ 0:
The energies are given relative to the corresponding Na(3s 2S) ⫹
R10000 processors, and another one, located in
HF(X 1S ⫹; v ˆ 0, j ˆ 0) dissociation thresholds. For the variational Eagan, Minnesota, equipped with 128 300 MHz
and close-coupling calculations performed in this study, these disso- R12000 processors). We benefited from large
ciation thresholds are located at 2698.999 and 2699.015 cm ⫺1 above memories available to us and from using Silicon
the potential minimum, respectively. We use the notation, in which Graphics/Cray Scientific Library routines. Large,
vr, vu , and vR are the vibrational quantum numbers of the H–F
stretch (r), the bend (u ), and the vdW stretch (R), respectively
multi-processor computers turned out to be extremely
useful, since we could divide an effort equivalent to
vr vu vR E (VAR)a E (CC)b hundreds of diagonalizations of the ro-vibrational
Hamiltonian corresponding to different values of
0 0 0 ⫺443.669 ⫺443.648
0 0 1 ⫺338.081 ⫺338.081 Rmax into several independent calculations, which
0 1 0 ⫺266.773 ⫺266.752 could run in parallel on several processors. The
0 0 2 ⫺245.942 ⫺245.941 remaining calculations were performed on Pentium
0 0 3 ⫺168.741 ⫺168.747 PC computers.
0 1 1 ⫺163.979 ⫺163.969
0 0 4 ⫺102.898 ⫺102.898
0 1 2 ⫺77.167 ⫺77.159
0 0 5 ⫺51.455 ⫺51.494 4. Discussion of results
0 2 0 ⫺14.371 ⫺14.427
0 0 6 ⫺5.072 ⫺5.069 In order to test the consistency and correctness of
a
Numerically exact (i.e. saturated with the basis-set size) ener- our numerical procedures, we first performed the
gies obtained variationally using the Hamiltonian defined by Eq. calculations for the bound states. The results of
(9). The basis set consisting of 4 numerical functions for the high- close-coupling calculations were tested against the
frequency stretch, 15 functions for the bend, and 60 numerical variational approach based on the diagonalization of
functions for the vdW stretch was employed.
b
The close-coupling calculations using 74 basis functions
the Sutcliffe–Tennyson Hamiltonian, Eq. (9), with the
^ Eq. (16).
F kJMp …r; R†; basis sets that yield the converged bound-state ener-
gies. A comparison of the bound-state energies
obtained in variational and close-coupling calcula-
(18), arising for J ˆ 0; was integrated up to tions is presented in Table 2.
R∞ ˆ 25:5 A,  with the stepsize 0.01 Å. The saturation The results of both calculations agree to within
of the results of the close-coupling calculations, with 0.05 cm ⫺1 and, in most cases, the agreement is even
respect to the size of the basis set F JMp …r; R†;^ Eq. better (the ⬃0.01 cm ⫺1 differences). The bound-state
(15), was investigated by increasing the number of energies obtained here and those reported in Ref. [5]
^ up to 80. All our tests indicate
functions F kJMp …r; R† agree to within 10 cm ⫺1 or better, which is reasonable,
^ obtained
that the final set of 74 functions F kJMp …r; R†; since the accuracy of our previous [5] and present fits
from the HF ro-vibrational states (0, 0–19), (1, 0–19), of PES for energies below the Na…3p 2 P† ⫹
(2, 0–17), and (3, 0–15), gives the fully converged HF…X 1 S ⫹ † asymptote is 5–10 cm ⫺1. The only essen-
results. The collision-time delay matrices Q Jp(E) and tial difference between the present and earlier results
Q res,Jp(E), Eqs. (21) and (22), respectively, and their for the bound-state energies is the appearance of the
energy derivatives (helpful in searching for the reso- …vr ; vu ; vR † ˆ …0; 2; 0† state in the present calculation.
nance energies), were evaluated using the appropriate This additional state increases the total number of the
versions of the generalized log-derivative method J ˆ 0 bound states supported by the shallow
[30,41,42]. minimum on the ground-state PES of NaFH to eleven
All ro-vibrational, stabilization, and close-coupling (the number of bound states obtained earlier [5] was
calculations were performed using our original ten). This is a consequence of the fact that the refitted
computer codes. The most expensive part of the stabi- potential, described in Section 2, is characterized by
lization calculations, i.e. the construction of the stabi- the slightly deeper vdW well and by a better treatment
lization diagrams, was performed on the two different of the asymptotic …R ! ∞† region, compared to the
 F. Mrugała et al. / Journal of Molecular Structure 555 (2000) 43–60 53

Table 3 The number of the vr ˆ 0 quasi-bound states stabi-

The energies Eres (in cm ⫺1) relative to the Na(3s 2S) ⫹ HF(X 1S ⫹; lized in the earlier study [5] and the number of the
v ˆ 0, j ˆ 0) dissociation threshold (2699.015 cm ⫺1 above the
potential minimum) and widths G (in cm ⫺1) and the dissociation
vr ˆ 0 resonances obtained in the present close-
pathways of the v r ˆ 0 quasi-bound vibrational …J ˆ 0† states of the coupling calculations differ (eight vr ˆ 0 resonances
Na···FH complex obtained in the close-coupling calculations with with J ˆ 0 were obtained here and ten vr ˆ 0 reso-
^ Eq. (16)
74 basis functions F kJMp …r; R†; nances with J ˆ 0 were obtained in Ref. [5]). It is also
quite difficult to establish the correspondence between
Eres G Branching into Na ⫹ HF(v ˆ 0, j) channels a
the vr ˆ 0 resonances obtained here and in Ref. [5],
jˆ0 1 2 3 4 since the vr ˆ 0 quasi-bound states are not bound in
the adiabatic approximation and no quantum numbers
0.074 ⬍1(⫺5) 1.000 – – – –
7.81 0.536 1.000 – – – –
that could help us can be assigned to them. For this
56.39 0.459 0.999 0.001 – – – reason, in Table 3 we list only the results of the
95.83 0.235 0.682 0.318 – – – present close-coupling calculations, which might be
100.54 0.617 0.353 0.647 – – – somewhat more trustworthy for the low-energy scat-
181.37 1.260 0.118 0.846 0.036 – – tering states near the Na ⫹ HF…v ˆ 0; j ˆ 0† dissocia-
331.77 0.125 0.026 0.240 0.686 0.048 –
418.07 0.388 0.017 0.137 0.219 0.626 0.000
tion threshold than the stabilization calculations. On
the other hand, there are a few striking similarities
a
The decay probabilities obtained by calculating the ratios G i =G between the results shown in Table 3 and the energy
for all open channels i (see the text for further details).
positions and widths of the rotationless vr ˆ 0 reso-
nances listed in Table 4 of Ref. [5]. Let us briefly
comment on these similarities.
potential obtained in Ref. [5]. The number of rotation- The states in Table 3 with the energies Eres ˆ
less bound states obtained here is still somewhat 95:83; 181.37, 331.77, and 418.07 cm ⫺1 relative to
smaller than the number of the J ˆ 0 bound states the Na ⫹ HF…v ˆ 0; j ˆ 0† dissociation threshold
resulting from the calculations reported in Refs. [539.50, 625.04, 775.44, and 861.74 cm ⫺1 relative to
[8,12] (fourteen bound states were obtained in Ref. the …vr ; vu ; vR † ˆ …0; 0; 0† bound state; cf. Tables 2 and
[12]). This might be related to the fact that the calcu- 3] seem to correspond to the quasi-bound vr ˆ 0 states
lations reported in Ref. [12] were based on the with the energies Eres ˆ 528:6 or 541.6, 619.8, 776.6,
complete separability of vibrational motions in the and 857.3 cm ⫺1, relative to the …vr ; vu ; vR † ˆ …0; 0; 0†
internal Jacobi coordinates and neglected terms that bound state, listed in Table 4 of Ref. [5]. For these
couple different modes (cf. Ref. [5] for additional states, the agreement between the widths obtained in
comments). It is, therefore, possible that some the stabilization and close-coupling calculations is
highest-energy bound states obtained in Ref. [12] quite good. Indeed, the close-coupling calculations
belong to the category of the very sharp resonances give 0.235, 1.260, 0.125, and 0.388 cm ⫺1 (see Table
located just above the Na ⫹ HF…v ˆ 0; j ˆ 0† disso- 3) and the stabilization calculations give 0.267 or
ciation threshold. Resonances of this type are usually 0.181, 1.055, 0.170, and 0.527 cm ⫺1, respectively
characterized by the very small widths and are very (see Table 4 in Ref. [5]). However, there are other
similar to the lowest-energy vr ˆ 0 resonance shown vr ˆ 0 quasi-bound states listed in Table 3, whose
in Table 3. Different ways of performing the ro-vibra- energies are in the immediate vicinity of the Na ⫹
tional calculations may always slightly change the HF…v ˆ 0; j ˆ 0† dissociation threshold, which can
total number of the calculated bound states, if there hardly be identified with the states resulting from
are states in the immediate vicinity of the dissociation the stabilization calculations. Thus, at this point, we
threshold. can only conclude that the stabilization and close-
Although the main purpose of this study is the coupling calculations agree very well for all vr ˆ 0
calculation of the energies, widths, and decay prob- resonances, except for those whose energies are very
abilities of the vr ˆ 1 quasi-bound states, we should close to the Na ⫹ HF…v ˆ 0; j ˆ 0† threshold. It is quite
comment, at least in a few words, on the results likely that we will never be able to obtain a good
obtained for the vr ˆ 0 resonances (see Table 3). agreement between the results of the stabilization
54 F. Mrugała et al. / Journal of Molecular Structure 555 (2000) 43–60

Table 4 They are, however, important for studies of the non-

The energies and widths (Eres and G , respectively, both in cm ⫺1) of reactive scattering of Na from HF at low collision
the v r ˆ 1 quasi-bound vibrational …J ˆ 0† states of the Na···FH
complex obtained in variational and close-coupling calculations.
energies [6,7] and they may be important in future
The energies are given relative to the corresponding Na(3s 2S) ⫹ spectroscopic studies of the Na· ··FH complex. It is,
HF(X 1S ⫹; v ˆ 0, j ˆ 0) dissociation thresholds. For the variational therefore, encouraging to observe that we can get a
and close-coupling calculations performed in this study, these disso- reasonable and fairly consistent description of many
ciation thresholds are located at 2698.999 and 2699.015 cm ⫺1 above of these states, using the close-coupling and stabiliza-
the potential minimum, respectively. The meaning of vr, vu , and vR
is the same as in Table 2
tion approaches.
When compared to many vr ˆ 1 states, the vr ˆ 0
…VAR† a …CC† c
vr vu vR E res G (VAR)b E res G (CC)c resonances are usually short-lived (their lifetimes are
of an order of 0.01 nanosecond [5]). As the results in
1 0 0 3526.11 0.004 3526.99 0.004
1 0 1 3640.36 0.012 3641.28 0.013 Table 3 indicate, the lowest-energy vr ˆ 0 resonances
1 1 0 3691.18 0.008 3692.01 0.012 dissociate primarily into Na and HF…v ˆ 0; j ˆ 0†:
1 0 2 3744.17 0.017 3745.02 0.016 With the increase of the resonance energy, the disso-
1 1 1 3801.56 0.025 3802.49 0.027 ciation pattern changes in favor of the rotationally
1 0 3 3836.75 0.012 3837.40 0.009
excited …j ˆ 1–3† states of HF. At the same time, the
1 2 0 3884.51 0.028 3885.55 0.030
1 0 4 3903.39 0.015 3904.11 0.010 range of j values that significantly contribute to the
1 1 2 3922.58 0.003 3923.10 0.003 decay of the Na…FH…vr ˆ 0; J ˆ 0† resonances into
1 0 5 3960.88 0.035 3961.46 0.027 the Na ⫹ HF…v ˆ 0; j† channels increases, from a
1 1 3 3987.65 0.028 3988.25 0.026 single j value for the lowest energy states to 3–4
1 0 6 4011.58 0.009 4011.68 0.003
values of j for the higher-energy vr ˆ 0 resonances
1 2 1 4026.30 0.002 4027.01 0.005
1 x x0 4034.44 0.153 that we managed to identify and characterize.
1 y y0 4134.35 0.698 The energy positions and widths of the vr ˆ 1 reso-
1 z z0 4550.48 0.214 nances obtained in the close-coupling and stabiliza-
a tion calculations are compared in Table 4. The
Numerically exact (i.e. saturated with the basis-set size) ener-
gies obtained using the stabilization method and the variational existence of many long-lived vr ˆ 1 states (t of an
approach employing the Hamiltonian defined by Eq. (9). The order of a nanosecond) has been noticed in Ref. [5]
basis set consisting of 4 numerical functions for the high-frequency and firmly confirmed in the present calculations. Since
stretch, 15 functions for the bend, and 60 numerical functions for the the widths of the vr ˆ 1 quasi-bound states obtained
vdW stretch was employed.
b here, using the stabilization approach, are virtually
Numerically exact (i.e. saturated with the basis-set size) widths
obtained using the stabilization method and the variational approach (within the accuracy of the stabilization method) iden-
employing 4 numerical functions for the H–F stretch, 20 functions tical to those reported earlier [5], the widths resulting
for the bend, and 50 numerical functions for the vdW stretch. The from the stabilization calculations, which are listed in
results taken from Ref. [5]. Table 4, have simply been taken from Ref. [5], where
c
The close-coupling calculations performed in this study with 74
^ Eq. (16). a very thorough analysis of the basis-set dependence
basis functions F kJMp …r; R†;
of these widths has been carried out. On the other
and close-coupling calculations for the low-energy hand, the energy positions of the vr ˆ 1 resonances
resonances states, whose energy positions and widths are slightly affected by the new fit of PES obtained in
are extremely sensitive to tiny changes in the descrip- this work. Thus, the Eres values listed in Table 4 corre-
tion of the asymptotic part of the corresponding spond to the stabilization and close-coupling calcula-
outgoing waves. From this point of view, it is quite tions performed in this study. It must be emphasized,
interesting and encouraging to see that there is still a however, that the differences between the energies of
reasonable agreement between the results of the stabi- the vr ˆ 1 states obtained here with the refitted PES
lization and close-coupling calculations for the vr ˆ 0 and those obtained in Ref. [5] with the previous fit
states with higher energies. vary only between 1 and 8 cm ⫺1, so that they are
Clearly, the vr ˆ 0 quasi-bound states cannot be not bigger than the standard deviation of the fit of
very important for studies of the photo-induced PES in this energy region.
charge transfer in Na· · ·FH described in Section 1. The most striking observation is that the results of
 F. Mrugała et al. / Journal of Molecular Structure 555 (2000) 43–60 55

Table 5
The decay probabilities for the vr ˆ 1 quasi-bound vibrational …J ˆ 0† states of the Na···FH vdW molecule into the Na ⫹ HF…v ˆ 0; j† channels
resulting from the close-coupling calculations using 74 basis functions F kJMp …r; R†; ^ Eq. (16). The decay probabilities were obtained by
calculating the ratios G i =G for all open channels i (see the text for further details). The Na…FH…v r ˆ 1; vu ; vR † states below the Na ⫹ HF…v ˆ
1; j ˆ 0† threshold (predominantly, the Feshbach-type resonances). The meaning of vr, vu , and vR is the same as in Table 2

(vr, vu , vR)

v j (1,0,0) (1,0,1) (1,0,2) (1,0,3) (1,0,4) (1,0,5) (1,0,6) (1,1,0) (1,1,1) (1,2,0) (1,1,2) (1,1,3)

0 0 0.001 0.002 0.003 0.006 0.005 0.005 0.012 0.000 0.001 0.001 0.002 0.001
1 0.003 0.004 0.007 0.016 0.012 0.012 0.031 0.000 0.002 0.004 0.004 0.003
2 0.003 0.004 0.007 0.015 0.012 0.012 0.032 0.000 0.002 0.003 0.005 0.003
3 0.004 0.005 0.009 0.023 0.017 0.017 0.049 0.000 0.002 0.004 0.009 0.004
4 0.011 0.013 0.023 0.058 0.041 0.042 0.119 0.001 0.003 0.011 0.023 0.009
5 0.019 0.020 0.037 0.098 0.066 0.067 0.198 0.000 0.004 0.016 0.045 0.014
6 0.016 0.016 0.032 0.104 0.061 0.063 0.242 0.000 0.001 0.012 0.087 0.011
7 0.000 0.001 0.003 0.025 0.007 0.009 0.145 0.012 0.019 0.010 0.163 0.023
8 0.119 0.139 0.166 0.096 0.158 0.142 0.013 0.076 0.190 0.166 0.241 0.220
9 0.309 0.308 0.405 0.382 0.455 0.371 0.112 0.086 0.274 0.271 0.115 0.341
10 0.492 0.466 0.298 0.165 0.110 0.251 0.033 0.717 0.460 0.480 0.253 0.350
11 0.021 0.025 0.012 0.010 0.055 0.010 0.007 0.111 0.042 0.021 0.048 0.021
12 0.000 0.000 0.000 0.001 0.001 0.001 0.003 0.000 0.001 0.000 0.005 0.001
13 – – 0.000 0.000 0.001 0.000 0.002 0.000 0.000 0.000 0.000 0.001

the stabilization and close-coupling calculations for
the vr ˆ 1 quasi-bound states, which are bound in
the adiabatic approximation (both calculations using
the same PES), are virtually identical (see Table 4).
The energy positions resulting from both calculations
differ by 1 cm ⫺1 or less. The agreement between the
widths obtained in both calculations is excellent as
well. The fact that two entirely different mathematical
formalisms, the stabilization approach, which is
strongly tied to calculations of the ro-vibrational
bound states, and the close-coupling approach, in
which we directly solve the Schrödinger equation
for the continuum states, yield almost identical reso-
nance energies and widths gives credence to our
earlier prediction of the existence of the long-lived
quasi-bound states of Na· ··FH corresponding to exci-
tation of the HF fragment to vr ˆ 1.
It seems that the very good agreement between the
results of stabilization and close-coupling calculations
is obtained only for the long-lived vr ˆ 1 resonances,
which are characterized by rather small widths G and
which are bound in the adiabatic approximation.
Larger differences between the calculated resonance
energies and widths are observed for the higher-
energy v r ˆ 1 states, which are short-lived and
which are, most likely, not bound in the adiabatic
approximation. Examples of such states are the three
states listed at the bottom of Table 4 and obtained in
the close-coupling calculations [the …1; x; x 0 †; …1; y; y 0 †;
and …1; z; z 0 † states]. We could not assign quantum
numbers vr, vu , and vR to these states, so that they
are, most likely, not bound in the adiabatic approxi-
mation. As in the case of some vr ˆ 0 resonances, we
could not precisely determine which higher-energy
vr ˆ 1 quasi-bound states identified in the earlier
stabilization calculations [5] correspond to states
…1; x; x 0 †; …1; y; y 0 †; and …1; z; z 0 † obtained in the present
close-coupling calculations (this is why we left blank
spaces in Table 4). At this point, we can only spec-
ulate that the vr ˆ 1 state with the energy Eres ˆ
4550:48 cm⫺1 above the Na ⫹ HF…v ˆ 0; j ˆ 0†
dissociation threshold [designated in Table 4 as
…1; z; z 0 †; located at 4994.15 cm ⫺1 above the lowest
bound state; cf. Tables 2 and 4] corresponds to the
vr ˆ 1 resonance, stabilized in the previous study
[5], with the energy Eres ˆ 4995:7 cm⫺1 above the
(0,0,0) state (see Table 4 in Ref. [5]). The latter
state has the width G equal to 0.345 cm ⫺1, and the
state with E res ˆ 4550:48 cm⫺1 obtained in the
present close-coupling calculations has G equal to
0.214 cm ⫺1 (see Table 4). Although the remaining
two states at the bottom of Table 4 [the …1; x; x 0 † and
…1; y; y 0 † states] have energies that look very similar to
energies of some high-energy v r ˆ 1 states reported
56 F. Mrugała et al. / Journal of Molecular Structure 555 (2000) 43–60

Table 6
Same as Table 4 for the Na…FH…vr ˆ 1; vu ; vR † quasi-bound states
with J ˆ 0 above the Na ⫹ HF(v ˆ 1, j ˆ 0) threshold

(vr, vu , vR)

v j (1,2,1) (1,x,x 0 ) (1,y,y 0 ) (1,z,z 0 )

0 0 0.002 0.000 0.000 0.000

1 0.006 0.001 0.000 0.000
2 0.006 0.001 0.000 0.000
3 0.007 0.001 0.000 0.000
4 0.017 0.003 0.000 0.000
5 0.026 0.005 0.000 0.001
6 0.020 0.005 0.000 0.002
7 0.004 0.001 0.000 0.004
8 0.172 0.004 0.001 0.015
9 0.424 0.014 0.002 0.052
10 0.174 0.009 0.000 0.118
11 0.117 0.000 0.001 0.100
12 0.031 0.000 0.000 0.062
13 0.000 0.001 0.000 0.050
1 0 0.000 0.953 0.272 0.005
1 – – 0.723 0.044
2 – – – 0.036
0 14 – – – 0.008
1 3 – – – 0.462
4 – – – 0.039

in the previous stabilization study [5], the widths

obtained in both calculations differ too much to
make any reasonable claims at this point. The reasons
for the observed differences between the results of the
present close-coupling calculations and earlier stabi-
lization calculations for the short-lived vr ˆ 1 states
that are not bound in the adiabatic approximation [5]
will be investigated in the future.
Interestingly enough, practically all vr ˆ 1 states,
which are bound in the adiabatic approximation (and
characterized by the well-defined quantum numbers vr,
vu , and vR), are located below the Na ⫹ HF…v ˆ 1; j ˆ
0† threshold (cf. Tables 4 and 5). The only exception is
the (1,2,1) state, which appears to be bound in the adia-
batic approximation in spite of the fact that its energy
seems to lie above the Na ⫹ HF…v ˆ 1; j ˆ 0†
threshold (this may be caused by several factors, e.g.
the inaccuracies in our PES). The states that are not
bound in the adiabatic approximation [for example,
the …1; x; x 0 †; …1; y; y 0 †; and …1; z; z 0 † states in Tables 4
and 6] have energies above the Na ⫹ HF…v ˆ 1; j ˆ
0† dissociation threshold. It seems, therefore, that
there is a simple rule that applies to the Na···FH
Fig. 2. The probabilities of decay of the vr ˆ 1 quasi-bound states of
the Na···FH complex, which are bound in the adiabatic approxima-
tion, into the Na ⫹ HF…v ˆ 0; j† channels: (a) the …vr ˆ 1; vu ˆ
0; vR † states with vR ˆ 0–6; (b) the remaining …vr ˆ 1; vu ; vR † reso-
nances.
resonances: all or practically all J ˆ 0 quasi-bound
states …vr ; vu ; vR †; which are bound in the adiabatic
approximation, have energy positions located below
the Na ⫹ HF…v; j ˆ 0† threshold with v ˆ vr : This rule
seems to work for the vr ˆ 1 resonances and it clearly
works for all vr ˆ 0 states studied in this work [indeed,
the vr ˆ 0, J ˆ 0 states, which have energies below the
Na ⫹ HF…v ˆ 0; j ˆ 0† threshold, are bound, so that
they are automatically bound in the adiabatic approxi-
mation]. It might be interesting to look at other systems
and other states of Na···FH to see to what extent this rule
is general.
 F. Mrugała et al. / Journal of Molecular Structure 555 (2000) 43–60
The fact that the rotationless vr ˆ 1 states, which
are bound in the adiabatic approximation, lie below
the Na ⫹ HF…v ˆ 1; j ˆ 0† threshold and that the J ˆ
0; vr ˆ 1 states, which are not bound in the adiabatic
approximation, have energies above the Na ⫹ HF…v ˆ
1; j ˆ 0† threshold has an effect on the dissociation
pathways of the vr ˆ 1 states. The vr ˆ 1 states,
which are bound in the adiabatic approximation,
decay into the Na ⫹ HF…v ˆ 0; j† channels (see
Table 5). The remaining vr ˆ 1 states decay into the
Na ⫹ HF…v ˆ 1; j† and Na ⫹ HF…v ˆ 0; j† channels
(see Table 6).
These different dissociation pathways of the vr ˆ 1
states below and above the Na ⫹ HF…v ˆ 1; j ˆ 0†
threshold have interesting implications on the
observed distributions of the final j values. Indeed,
since the vr ˆ 1 states of Na· · ·FH, which are bound
in the adiabatic approximation, cannot decay into the
Na ⫹ HF…v ˆ 1; j† channels, the large amount of the
vibrational energy stored in these states (ca.
4000 cm ⫺1) must partially be converted into signifi-
cant rotational excitation of the HF product molecule.
The results in Table 5 confirm this expectation (see,
also, Fig. 2). The rotationally excited HF…v ˆ 0; j†
molecules, with j as high as 9–11, are the dominant
products of the decay of the Na…FH…vr ˆ 1; J ˆ 0†
resonances below the Na ⫹ HF…v ˆ 1; j ˆ 0†
threshold. On the other hand, the lowest energy
Na…FH…vr ˆ 1; J ˆ 0† states, which are not bound
in the adiabatic approximation and lie above the Na ⫹
HF…v ˆ 1; j ˆ 0† threshold [the …1; x; x 0 †; …1; y; y 0 †;
and …1; z; z 0 † states in Tables 4 and 6] decay primarily
into the Na ⫹ HF…v ˆ 1; j† states with low j values
[e.g. j ˆ 0 in the case of the …1; x; x 0 † state, or j ˆ
0; 1 in the case of the …1; y; y 0 † state]. The HF…v ˆ
1; j† molecules with larger j values [e.g. j ˆ 3 in the
case of the …1; z; z 0 † state] are produced only when the
energy Eres of a given vr ˆ 1 resonance is significantly
above the Na ⫹ HF…v ˆ 1; j ˆ 0† threshold. This
resembles the decay patterns observed for the vr ˆ 0
resonances, which decay into the Na ⫹ HF…v ˆ 0; j†
channels with small j values only if their energy posi-
tions are just above the corresponding Na ⫹ HF…v ˆ
0; j ˆ 0† dissociation threshold [for other vr ˆ 0 reso-
nances, with larger energies Eres, the rotationally
excited HF…v ˆ 0; j† molecules are obtained].
Finally, we would like to comment on the relation-
ship between the distribution of j values character-
57
izing the product HF…v ˆ 0; j† molecules and the
quantum numbers characterizing the vr ˆ 1 quasi-
bound states, which are bound in the adiabatic approx-
imation (see Table 5 and Fig. 2). It seems that excita-
tion of the vdW stretching mode (from vR ˆ 0 to 6)
broadens the range of j values characterizing the final
Na ⫹ HF…v ˆ 0; j† channels and shifts the average j
value towards j ˆ 0; from three values of j … j ˆ
8–10† that give the significant decay probabilities
for vR ˆ 0 to about nine values of j … j ˆ 1–7; 9; 10†
that essentially contribute to the rotational product
distribution for vR ˆ 6 [cf. Table 5 and Fig. 2a]. Even-
tually, when vR ⬎ 6; so that the corresponding vr ˆ 1
states of Na· ··FH are no longer bound in the adiabatic
approximation, we observe a significant redistribution
of the final j values, with j ˆ 0 or 1 being now the
dominant channels, since most of the energy released
in the decay of the Na…FH…vr ˆ 1; J ˆ 0† states,
which lie above the Na ⫹ HF…v ˆ 1; j ˆ 0† threshold,
remains stored in the vibrationally excited, HF…v ˆ
1; j†; molecules. It seems that excitation of the bend
has a small effect on the final rotational product distri-
bution. Larger effect is observed only when excitation
of the bend is accompanied by excitation of the vdW
stretch [as in the case of the (1,1,2) state, which
dissociates into Na ⫹ HF…v ˆ 0; j† channels with j ˆ
4–11; cf. Table 5 and Fig. 2b].
5. Summary and concluding remarks
A highly reliable analytical representation of the
potential energy function for the ground electronic
state of the NaFH system was used to evaluate the
energies and widths of the quasi-bound ro-vibrational
states of the Na· · ·FH vdW complex. An emphasis was
placed on a comparison of the previously published
[5] and newly obtained results of the stabilization
calculations with the results of the converged close-
coupling calculations. The probabilities of decay of
the quasi-bound states of Na· · ·FH into individual
Na ⫹ HF…v; j† channels were obtained using the
close-coupling approach. Although we focused on
the quasi-bound states, in which the HF fragment in
the complex is excited to vr ˆ 1; information about
the lower-energy vr ˆ 0 resonances and bound states
was obtained and analyzed as well.
It was demonstrated that the converged stabilization
58 F. Mrugała et al. / Journal of Molecular Structure 555 (2000) 43–60
calculations, using the approach developed by
Mandelshtam et al. [25,26] and exploited earlier in
Ref. [5], and the closed-coupling calculations, based
on the ideas and algorithms described in Refs.
[30,37,41,42] and in Section 3 of this paper, lead to
virtually identical results for all bound and vr ˆ 1
quasi-bound states, which are bound in the adiabatic
approximation. The results of the close-coupling
calculations for the vr ˆ 0 resonances, which do not
lie in the immediate vicinity of the Na(3s 2S) ⫹
HF(X 1S ⫹; v ˆ 0, j ˆ 0) dissociation threshold, also
turned out to be very similar to those obtained with the
stabilization method. Larger differences between both
types of calculations were observed only for the
v r ˆ 1 resonances above the Na…3s 2 S† ⫹ HF…X 1 S ⫹ ;
v ˆ 1; j ˆ 0† threshold and for the vr ˆ 0 resonances
in the immediate vicinity of the Na…3s 2 S† ⫹
HF…X 1 S ⫹ ; v ˆ 0; j ˆ 0† threshold.
The excellent agreement between the fully
converged close-coupling and stabilization calcula-
tions for the vr ˆ 1 quasi-bound states, which are
bound in the adiabatic approximation, means that
we can rely on either method, if we are to provide
the most essential characteristics (energy positions
and widths) of these states. In particular, our earlier
claim that there exist many long-lived resonances that
correspond to excitation of the H–F mode in the
complex to vr ˆ 1 has now a very solid support in
the form of the results of very accurate close-coupling
calculations.
We noticed that practically all vr ˆ 1 states of
Na· ··FH, which are bound in the adiabatic approxima-
tion, have energies below the Na…3s 2 S† ⫹
HF…X 1 S ⫹ ; v ˆ 1; j ˆ 0† dissociation threshold.
The vr ˆ 1 states above the Na…3s 2 S† ⫹
HF…X 1 S ⫹ ; v ˆ 1; j ˆ 0† threshold are not bound in
the adiabatic approximation. Clearly, a similar remark
applies to the vr ˆ 0 resonances, which must necessa-
rily lie above the corresponding Na…3s 2 S† ⫹
HF…X 1 S ⫹ ; v ˆ 0; j ˆ 0† threshold (otherwise, the
vr ˆ 0 states would be the bound states).
We demonstrated that the vr ˆ 1 quasi-bound
states, which are bound in the adiabatic approxima-
tion, decay into the Na ⫹ HF…v ˆ 0; j† channels with
large j values. The states above the Na…3s 2 S† ⫹
HF…X 1 S ⫹ ; v ˆ 1; j ˆ 0† threshold primarily decay
into the Na ⫹ HF…v ˆ 1; j† channels. The excitation
of the vdW stretching mode increases the range of j
values characterizing the Na ⫹ HF…v ˆ 0; j† channels,
into which the Na…FH…vr ˆ 1; J ˆ 0) states that are
bound in the adiabatic approximation decay.
In the future, we hope to be able to extend our
close-coupling calculations to vr ˆ 2 states, at least
to those vr ˆ 2 states, which are bound in the adia-
batic approximation [below the Na…3s 2 S† ⫹
HF…X 1 S ⫹ ; v ˆ 2; j ˆ 0† threshold]. Information
about some of these states has already been provided
in our earlier work [5], and we hope that this informa-
tion will facilitate the close-coupling calculations for
the vr ˆ 2 states. The close-coupling calculations
become a lot easier, if the approximate energy posi-
tions of the quasi-bound states of interest are a priori
known.
The detailed information about energies, widths,
and dissociation pathways of the vr ˆ 1 and 2 reso-
nances provided here and in Ref. [5], particularly
about the states, which are characterized by the longer
lifetimes, may play a critical role in assessing the
feasibility of the experiment mentioned in Section 1
and in Refs. [5,24] in which excitation of the H–F
stretching mode in the complex prior to electronic
excitation of Na· · ·FH could be used to explore new
dynamical scenarios for the photo-induced charge
transfer in vdW molecules. Information about the
vr ⬎ 0 quasi-bound states may also be useful in accu-
rate state-to-state description of the ground-state
Na ⫹ HF ! NaF ⫹ H reaction [22,23] (for the
experimental studies of this reaction, see Refs. [18–
20]). The vr ˆ 0 resonances are essential for the
understanding of the non-reactive scattering of the
Na atoms from the HF…v ˆ 0; j† molecules [6,7].
The fact that we now have a reliable theoretical
methodology at hand that allows us to extract reason-
ably accurate information about the ro-vibrational
resonances of the Na· ··FH vdW molecule means
that, in the future, we may be able to provide a great
deal of information about the dynamics of other
complexes formed by the alkali and alkaline-earth
metal atoms and halides, which have recently been
studied in several laboratories [11,43–59].
Acknowledgments
One of us (PP) would like to thank Profs Henryk
Ratajczak and Austin Barnes for the invitation to
 F. Mrugała et al. / Journal of Molecular Structure 555 (2000) 43–60
contribute to this special issue of the Journal of
Molecular Structure. He would also like to thank
Profs Henryk Ratajczak and Jan Baran for inviting
him to speak at the “Vth International Conference
on Molecular Spectroscopy.” This work has been
supported by the startup funds provided to one of us
(PP) by the Michigan State University (MSU) and by
the MSU Intramural Research Grant Program (the
New Faculty, Science and Engineering Award
received by PP). Some of the calculations reported
in this paper (parallel calculations of stabilization
diagrams) were performed on the R12000 based 128
processor Origin 2000 supercomputer in Eagan,
Minnesota. We would like to thank Silicon Graphics
Incorporated for providing one of us (PP) with an
access to this resource. Additional support by the
Grant Agency of the Academy of Sciences of the
Czech Republic (Grant No. A4040806) is gratefully
acknowledged. Finally, one of us (PP) would like to
thank Prof. John C. Polanyi and Dr Andrew J. Hudson
for many stimulating discussions and considerable
interest in the results reported in this paper.
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