Sobretonos

Quantum dynamics of overtone relaxation in benzene. I.
5 and 9 mode
models for relaxation from CH(v=3)
Robert E. Wyatt, Christophe Iung, and Claude Leforestier
Citation: J. Chem. Phys. 97, 3458 (1992); doi: 10.1063/1.462981

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Quantum dynamics of overtone relaxation in benzene. I. 5 and 9 mode
models for relaxation from CH{v=3)
Robert E. Wyatt,a) Christophe lung, and Claude Leforestier
Laboratoire de Chimie Theorique, Universite de Paris-Sud, 91405 Orsay, France
(Received 23 January 1992; accepted 15 May 1992)
This series is concerned with the quantum dynamics of overtone relaxation in planar benzene
and in reduced mode planar benzene fragments. In these studies, ultralarge direct
product primitive vibrational spaces (of dimension up to 1010) are contracted to active spaces
of dimension 5000-10000. The contractions are carried out via artificial intelligence tree
pruning algorithms, or a new iterative wave operator pruning algorithm. The exact dynamics
within the active space is then developed via the recursive residue generation method.
In part I of this series, emphasis is placed upon v=3 CH overtone dynamics in the 5 and 9
mode benzene fragments C3H and C 3H 3. Neither system undergoes complete relaxation,
but the survival probability in C3H undergoes large amplitude oscillations with a period
characteristic of stretch-wag interaction in the CH chromophore. For C3H 3, the two
initially nonexcited CH stretch modes do not playa significant role in the dynamics for t < 1
ps. However, modes in both systems that have a high degree of wag motion for the
initially excited chromophore playa significant role at short times. Comparisons with earlier
classical trajectory studies show good correspondence between the classical and quantum
results only at short times, t < 0.1 ps.
I. INTRODUCTION ical results. We start with direct product vibrational basis

A. Overview sets whose dimension is frequently in the range 106_1010
(megabasis to terabasis). Out of this primitive space, we
Intramolecular vibrational energy redistribution select 103_104 states to form the active space. The active
(IVR) continues to attract considerable attention. I- 15 An space may still be too large for direct diagonalization of the
excellent review of theoretical approaches to this topic was Hamiltonian matrix. However, the dynamic and spectro-
recently presented by Uzer. 1 Several experimental and the- scopic features are accurately determined in the Lanczos
oretical groups have focused on the overtone spectra of CH subspace 18 L (dimension M) of the active space through
bonds in various molecules. The benzene molecule, in par- use of the recursive residue generation method,
ticular, challenges both theoretical and experimental meth- RRGM. 19- 22 Of course, we must establish convergence of
ods. the computed properties with respect to the size of the
This series of quantum mechanical studies on the spec- primitive space, the size of the active subspace, and the size
troscopy and dynamics of CH overtones in benzene is of the Lanczos subspace. Reduction from the primitive
aimed at the development and application of methods space to the active space will be accomplished using two
which can handle a very large number of vibrational states. different algorithms. The first, an artificial intelligence
In the first of these studies, referred to as I, we focus upon (AI) tree pruning algorithm, is similar to algorithms that
the detailed dynamics of relaxation from the v=3 CH have found use in chemical dynamics for almost a de-
overtone in the 5 and 9 mode planar nonrotating benzene cade. 23 - 25 The second is quite different and is based upon
fragments, C3H and C 3H 3. (Lu and Hase l6 recently used iterative development of the wave operato~6 0.. The latter
classical trajectories to study CH overtone decay in the method is used for the first time in these studies to select
C3H and C3H3 fragments. Stability analysis of CH periodic states from a very large list of candidates. The overall
orbits in C 3H was reported by Garcia-Ayllon et al.17) In scheme is illustrated by the flow diagram
the following parts of this series, we will study relaxation
from the v= 1,2, and 4 overtones in C3H and C3H 3, relax- primitive space S =A Ell B
ation from the V= 1-4 overtones in a 16 mode planar ben- .u. wave operator iteration
zene model (five CH stretch coordinates are neglected), active subspace A
and relaxation from the v = 1-4 overtones in 21 mode pla- .u. quantum dynamics RRGM
nar nonrotating benzene. In some of these studies, the sen- Lanczos subspace L
sitivity of the dynamics to alterations in the input potential .u.
energy surface will be considered. stick spectrum I( ill)
A unique feature of these studies is the use of ul-
tralarge vibrational basis sets to obtain converged dynam- .u.
autocorrelation function Set)
a) Permanent address: Department of Chemistry and Biochemistry, Uni- The subspaceA inCludes the initial state and the back-
versity of Texas, Austin, Texas 78712. ground states strongly coupled to it. The subspace B con-
3458 J. Chern. Phys. 97 (5), 1 September 1992 0021-9606/92/173458-19$006.00 © 1992 American Institute of Physics
R. E. Wyatt and C. lung: Overtone relaxation in benzene. I 3459
tains states weakly coupled to the A states. The dimension Using both classical and quantum mechanical models,
of the Lanczos subspace is the number of recursion steps M Sibert, Reinhardt, and Hynes (SRH)48,49 made detailed
in the RRGM. A review of computational aspects of such comparisons with the experimental results of Berry et al.
a scheme (except for the wave operator component) has The model involved only kinetic energy coupling in curvi-
been presented elsewhere. 27 linear coordinates, the most important of which was be-
tween the CH stretch (a Morse oscillator) and the contig-
uous CCH in-plane wag (other smaller kinetic coupling
B. Previous studies terms were also included). All anharmonic potential en-
The interpretation of the overtone spectrum of benzene ergy coupling terms were neglected. An important theoret-
in terms of anharmonic CH-stretch vibrations goes back a ical construction used in these studies was that of tiers of
number of years to the experimental studies of Ellis 28 in quantum states; successive tiers were coupled by anhar-
1929. A significant feature is that the frequencies of the monic terms in the Hamiltonian. In the quantum mechan-
overtone spectral peaks follow the Birge-Sponer relation- ical studies, about 700 states in 3 tiers were used and a
ship,29 lUpeak=An - Bn2(n = 1,2,3, ... ). A much more phenomenological relaxation parameter was introduced to
extensive analysis in terms of local modes of vibration was mimic the effect of neglected additional tiers. The spectra
developed by Henry30-3! starting in 1968. An excellent re- predicted by this model appeared to be in good agreement
view 32 of the use of local modes to interpret the spectra of with the experimental data available in 1982. Shi and
highly vibrationally excited molecules was presented by Miller50 have used a semiclassical model with kinetic cou-
Henry in 1977. A number of other studies have also fo- pling in internal curvilinear coordinates to predict correla-
cused on the local mode model. 33-39 tion functions and spectra for local mode relaxation in
In more recent times, during the mid-1970s, Albrecht benzene. Their results are also in good agreement with the
and co-workers developed the thermal lens technique and experimental results of Berry et af. Buch, Gerber, and Rat-
used it to study the absorption spectrum of liquid ben- ner sl have used the kinetic coupling model with a statisti-
zene.40-42 In important studies during the late 1970s and cal wave function approximation to predict overtone
early 1980s, Berry and co-workers recorded V= 1 to 9 over- widths in benzene.
tone spectra of room temperature gas phase benzene using In recent studies, Zhang, Klippenstein, and Marcus 52
the intracavity cw dye laser technique with optoacoustic have formulated the anhannonic vibrational Hamiltonian
detection. 43 They reported broad absorption features; for in curvilinear normal modes and local modes. They then
v=3 the roughly 100 cm-! full width at half maximum performed an Al search to construct small active spaces
(FWHM) asymmetric absorption feature had a broad (dimension -1000) and have computed fundamental and
shoulder on the "red" side. They suggested that near res- overtone spectra for V= 1, 2, and 3 excitations.
onant energy transfer between CH oscillators played a sig- Hase and co-workers 16,53-57 have reported an extensive
nificant role in the relaxation process. These studies by series of trajectory studies 011 overtone relaxation in ben-
Berry et al. stimulated theoretical studies that seemed to zene. They studied the sensitivity of the dynamics to alter-
agree well with the experimental results. ations in the CCH wag potential. In addition, as mentioned
The experimental situation advanced significantly earlier, they studied overtone relaxation in the planar frag-
when Page, Shen, and Lee44,45 reported results from the ments l6 C3H and C3H 3• Comparisons between the current
supersonic molecular beam technique. The V= 1, 2, and 3 quantum studies and the trajectory results will be made in
overtones created by an IR laser were detected through Secs. III and IV.
resonant enhanced 2-photon ionization (R2PI) produced Clarke and CollinsS8 also used classical trajectories to
by a UV laser. The benzene molecules were rotationally study overtone decay in benzene. Their Morse oscillator
cooled to 5 K by the supersonic expansion, which elimi- potential energy surface was similar to the one used in the
nated much of the rotational broadening in the experi- current studies. Comparisons with their work will be pre-
ments of Berry et al. In the beam experiments, the v=3 sented elsewhere in this series.
overtone was centered at 8827 cm - I with a FWHM of Thompson et al. have also used trajectory methods to
< 10 em-I. Recently, Scotoni et al. 46 reported additional study energy flow from excited CH overtones 59,6Q and from
supersonic molecular beam results on the v=3 overtone. various excited CC stretch, CCH wag, and CCC bend nor-
However, instead of R2PI detection, they used a cryogen- mal modes. Several potential surfaces with varying degrees
ically cooled bolometer. Under these beam conditions, the of anharmonicity were used. For relaxation from excited
20 K rotational temperature molecules also exhibited a CH overtones, it was found that low frequency modes do
main peak at 8827 cm- I, but with at least five less prom- not significantly participate in the energy redistribution,
inent bands on the "red" side of the main peak. The most but high frequency modes which possess CCH wag char-
significant of these bands was 57 cm -I red shifted from the acter are very important in absorbing energy.
main band, with peak absorption amounting to about 40% Gomez-Llorente, Hahn, and Taylor6I have presented a
of that exhibited by the main band. Although not directly critique on the use of classical trajectories to study over-
related to the present study, we note that Chernoff, Myers, tone relaxation in planar benzene. Their conclusion is
and Pruett 47 observed high, relatively harmonic, normal quoted " ... because some ofthe trajectories used to simulate
mode overtones of the C-C ring breathing mode up to the quantum flow from the local mode region are blocked
10000 cm- I • and redirected back into the region, and the remainoer
J. Chern. Phys., Vol. 97, No.5, 1 September 1992

3460 R. E. Wyatt and C. lung: Overtone relaxation in benzene. I
(the majority) are outside the region and do not feel it, = 1 (tPil \II(t» 12. Whereas one speaks of intensities, line
standard studies of the flow of ensembles of trajectories positions, line separations, and widths of envelopes or
designed to mimic packet flow cannot be used to compute other features when viewing the spectrum in the frequency
local mode IVR rates of benzene" (italics added for em- domain, one speaks of exponential vs nonexponential de-
phasis). The term "standard studies" refers to those based cay, uecay times, localization times, recurrence times, os-
upon tracking the time evolution of swarms of trajectories, cillation frequencies, and time scales for "events" when
so that correlation functions and spectra can be computed. viewing the survival probability in the time domain. (An
Instead, it is recommended that the analysis be based upon issue not dealt with here concerns the preparation and de-
stability parameters of trajectories. cay of the initial state; see the discussion by Hutchinson et
Stability analysis of the CH periodic orbit, as a func- al. 62,63)
tion of stretch-wag coupling, was the subject of a study by Terminology introduced by Taylor64 is useful when in-
Garcia-Ayllon, Santamaria, and Ezra. 17 They found that terpreting the stick spectrum. Peaks in the spectrum are
increasing the strength of the stretch-bend coupling stabi- viewed as intramolecular scattering resonances; the reso-
lizes the CH periodic orbit, thereby suppressing overtone nant state, at an energy corresponding to a pole in the S
decay. matrix, strongly overlaps the localized "extreme motion"
state. However, for energies off resonance, direct scattering
dominates, as evidenced by small penetration of the eigen-
C. Interpretation of spectra states ("scattering wave functions") into the localized re-
In relation to their experimental study of benzene over- gion of configuration space.
tone spectra, Page, Shen, and Lee44 discussed a model
D. Coordinate systems for dynamics
which is relevant to the results presented later in this study.
There are two related constructs to analyze the overtone The vibrational anharmonic Hamiltonian for benzene
spectra: the mode picture is based upon zero-order eigen- may be formulated in either internal curvilinear coordi-
states of a model Hamiltonian IfJ, while the eigenstate nates or internal rectilinear coordinates. For example, the
picture is based upon eigenstates of the full Hamiltonian quantum mechanical studies of SRH48 and Zhang et al. 52
H = IfJ + V, which includes anharmonic couplings. In the employed curvilinear coordinates, whereas the classical
mode picture, there is one quantum excitation from the mechanical studies of Hase et al. 16,55,56 have employed rec-
ground state 1tPo) to the "bright" overtone state 1tP,.), tilinear coordinates. There are advantages and disadvan-
which is also referred to as a doorway state. Anharmonic tages connected with either formulation. For curvilinear
coupling between 1tPi) and the optically cold "dark" back- coordinates, the G-matrix elements which enter the kinetic
ground (bath, receptor, or host) states {I tP)} leads to energy are functions of the coordinates, so that the quan-
homogeneous broadening of the overtone spectrum. On the tum mechanical kinetic energy operator is quite complex.
other hand, in the eigenstate picture, each eigenstate of H Usually, the G-matrix elements are Taylor expanded about
has contributions from the bright overtone state and the the equilibrium geometry and only the lowest orders are
various background states, retained in the dynamics. On the other hand, in rectilinear
coordinates, the G-matrix elements are constant, indepen-
l\IIk)=akltPi)+ Lj bkjltP), (1) dent of geometry, and the kinetic energy operator has a
simple form. However, the potential surface or force field is
where j = {hJ2, ... J,,} is a collective index denoting the usually formulated as a series expansion in curvilinear co-
degree of excitation of the various modes, while k is a serial ordinates because of the relatively small number of terms
index rather than a "quantum number." The oscillator involved. Conversion of this potential to rectilinear coor-
strength between the ground state and the kth eigenstate is dinates is quite complicated and many terms may be re-
then quired for convergence.
Recently, lung and Leforestier4 (b) compared dynami-
(2)
cal formulations in these two coordinate systems for the
where a~ = (\Ilk 1(Pi) 2 is the probability of finding the bright CD3H molecule, including all 9 vibrational degrees of free-
overtone state in the kth eigenstate. From another view- dom. Their study focused upon the validity of the kinetic
point, a~ is the degree of localization of the eigenstate approximation in curvilinear coordinates; the Hamiltonian
1\Ilk) on the overtone state. Except for constant factors, contains the kinetic energy operator, which may be trun-
such as (tPilJL 1tPO)2, a plot of a~ vs Ek is a "stick" version cated, and only harmonic potential terms (all anharmonic
of the overtone high resolution spectrum. The variation of potential terms are neglected). The kinetic approximation
spike heights or intensity across the spectrum is produced has been used in a number of previous studies on benzene.
entirely by the variation of the weights of the overtone However, for CH overtone relaxation in CD3H, the kinetic
states in the various eigenstates. One can also transform to approximation gave a poor description for both the spec-
a time-dependent viewpoint by taking the Fourier trans- troscopic and dynamic features. The kinetic energy opera-
form of the stick spectrum; the result is the autocorrelation tor in this study was expanded to high order, with up to
function or survival probability S(t). This is the probabil- 140 terms. Low order expansions, particularly first or sec-
ity at time t that the time evolving wave function 1\II(t» ond order, gave poor results. It thus appears that, from a
overlaps the initially prepared state 1tPi), S(t) computational point of view, the curvilinear description
does not give a simpler approach than one based upon where p is the curvilinear stretch coordinate. In this study,
rectilinear coordinates. we will use the following values (in a.u.) for the 3 Morse
In the present study on C 3H and C 3H 3, the Hamil- parameters: D=0.198 836, a=0.938. These compare with
tonian will be formulated in rectilinear coordinates. The the following values used by Lu and Hase: 16 D=0.175 291,
"pure vibrational" kinetic energy operator will thus be a=0.974. Sensitivity of the dynamics to the values for
treated exactly (nonquadratic vibrational angular momen- these input parameters will be treated in later parts of this
tum terms 11'a11'p. Coriolis, and rotational terms are ne- series. In order to avoid coordinate dependence of the G-
glected), but the price to be paid is that the anharmonic matrix elements Gij(R) which appear when the classical
potential will contain a large number of terms. Develop- kinetic energy and the quantum kinetic energy operator are
ment of the vibrational anharmonic Hamiltonian is de- computed in curvilinear coordinates, we will use rectilinear
scribed in the next section. coordinates {RJ and normal coordinates {QJ to formulate
the Hamiltonian operator.
The "input" force field provided by PFB may be writ-
ten
II. THEORETICAL METHODS
A. Coordinates and kinetic energy
(7)
Four coordinate systems were used at various stages in
this study; they are defined as follows for 21 mode planar
benzene: Oi: U= 1,2, ... ,24), Cartesian (x,y) displacements Using Eqs. (24)-(29) for L\I L 2, and L3 in Hoy, Mills, and
of the 12 atoms from their equilibrium positions; Ri: U Strey,68 the PFB quadratic and cubic force constants were
= 1,2,... ,21), internal curvilinear displacement coordinates, used to generate quadratic, cubic, and quartic force con-
as defined in Table III of Pulay, Fogarasi, and Boggs;6S stants in normal coordinates. The new force field was then
generated from the curvilinear- force field and the L-
R j : (i= 1,2, ... ,21), internal rectilinear displacement coordi-
nates, defined by analogy to the curvilinear coordinates; coefficients using Eq. (11) in Hoy, Mills, and Strey. The
Qi: (i= 1,2, ... ,21), normal coordinates. Conversions be- resulting force field is expressed
tween these four coordinate systems are defined by the
following tensorial or linear transformations:
R=B*o=L*Q= T* R, (3)
R=L,Q=B,o, (4) (8)
where B*, L*, and T* are nonlinear tensor transformations

where the normal mode frequencies are Ar The cubic and
from 0, Q, or R to curvilinear coordinates while L, and
B, are linear transformations from Q and to rectilinear
coordinates. For example, the tensor transformation from
° quartic force constants are used later in Sec. II C to gen-
erate the anharmonic vibrational Hamiltonian. The force
Cartesian to curvilinear coordinates is field may also be expressed in rectilinear coordinates by
first inverting the matrix Ll in Eq. (4); this gives
1 1
Rj= L B'j0P+"2 L BfO~q+6 L Bfro~qOr+'" .
p P.q p,q,r (5) (9)
The successive sets of coefficients defining this transforma-

tion are denoted B" B2, B3, ... The coefficients B2 and B3 When this transformation is used for each normal coordi-
were defined by Pariseau, Suzuki, and Overend,66 while nate appearing in Eq. (8), the result is
B, was defined by Wilson, Decius, and Cross.67 In addi-
tion, the coefficients L" L 2, L3 in the L* transformation (10)
were defined by Hoy, Mills, and Strey.68
The benzene scaled ab initio force field (their set II) of
Pulay, Fogarasi, and Boggs (PFB)65,69 was used in this This expression, for rectilinear coordinates, is analogous to
study. In this force field, the "raw" ab initio quadratic Eq. (7) for curvilinear coordinates.
force constants were scaled (scale factors of about 0.8-0.9 In terms of normal coordinates, the quantum kinetic
were used) in order to reproduce experimental frequencies. energf operator is given by (in atomic units)
The cubic force constants were not scaled. For in-plane
1 a2
motions, they reported 26 quadratic and 12 cubic force T=--
2
Lr'
r O~r
(11 )
constants in internal curvilinear coordinates. For all inter-
nal curvilinear coordinates, except the overtone excited
CH stretch vibration, the PFB force constants were used. The simplicity of this expression IS one of the advantages of
However, the single overtone excited CH stretch was rep- using normal coordinates. At this stage, the vibrational
resented by the Morse potential, Hamiltonian would be the sum of the expressions in Eqs.
(8) and (11), but the important stretch-wag potential will
(6) be modified before presenting the final result in Sec. II C.
B. Potential for CH chromophore

The stretch-wag potential for the overtone excited CH
bond requires special consideration. In a series of studies
on the CH chromophore in the molecules CD3H, CF3H,
etc., Quack and collobarators70-72 have described a least-
squares fit of the potential in rectilinear coordinates. We
note that the subsequent dynamics was investigated using
the rectilinear coordinate formulation. The benzene force
field has been the subject of a number of studies, many of
which have been recently reviewed by Goodman et al. 73
Goodman and co-workers have reported a number of ab
initio studies of the quadratic benzene force field. 73 Far less
has been reported on the anharmonic force field. In these
studies, we will use the Pulay et al. 65 force field, since they
did provide cubic force constants in internal curvilinear
coordinates. However, the quadratic and cubic terms in the
PFB CH stretch potential will first be replaced by the
Morse potential in Eq. (6). Then, this stretch-wag poten-
tial in curvilinear coordinates (p,{3) will be expanded as a
power series in rectilinear stretch-wag coordinates (r,b).
Finally, normal coordinates will be introduced.
The stretch-wag potential in the PFB force field is
(12)
where k'; is a cubic interaction constant. The numerical
values (in a.u.) for these constants are k2 = 0.3325, k3
= -1.1556, k~ = 0.1179, ki = -0.0255. In order to ex-
tend this potential to higher vibrational energies, the two
stretch terms are replaced by the Morse potential
(13) FIG.!. Contour map of the CH stretch-wag potential in (a) curvilinear
coordinates (p,f3), and (b) rectilinear coordinates (r,b). The contour
where the SUbscript is to emphasize that this is an expan- values (in a.u.) range from 0.002 to 0.038 in increments of 0.002. In both
sion in curvilinear coordinates. A contour map of plots, the abscissa ranges from +0.8 radians to -0.8 radians and the
ordinate ranges from -0.4 to +0.6 a.u. If (x,y) denote Cartesian dis-
Vc (p,{3) is shown in Fig. 1 (a); the abscissa shows {3 over placements of the H atom from equilibrium, then the curvilinear and
the interval [-0.8,0.8] and the ordinate shows p over the rectilinear angles p and b are defined by (see Fig. 1 in Ref. 65 also)
interval [-0.4,0.6], where {3 is in radians and p is in a.u. p= .j2tan- l [xl(r, + y)], b = .[2xlr., where r, = 2.046 a.u. is theequilib-
Since the dynamical calculations will be performed in rium CH distance. Note that b is the first order term in the expansion of
p in displacements (x,y).
rectilinear coordinates, the potential in rectilinear coordi-
nates is expressed as the sum of a Morse potential in the
rectilinear stretch coordinate r, plus the harmonic bend
potential and a correction potential, The correction potential is then expressed as a 24 term
power series, with terms up to the tenth order
(14)
A contour map of Vr(r,b) is shown in Fig. l(b); the ab- Ii(r,b) =I c mn r"b ,
2n (16)
scissa shows b over the interval [-0.8,0.8] and the ordinate m,n
shows r over the interval [-0.4,0.6], where b is in radians 3<m+2n,1O, n= 1,2,3,4, m=0,1, ... ,8. In order to deter-
and r is in a.u. The "banana shaped" valley where V mine the expansion coefficients, a grid was established in
<0.016 a.u. is shown cross hatched. The correction poten- rectilinear coordinates within a rectangular box with r in
tial is formally the potential at point (r,b), computed by the range [rmin,rmax] and b in the interval [ - bmax,bmax].
converting coordinates (r,b) to curvilinear coordinates However, if the potential at a given grid point was larger
(p,{3) and evaluating the potential using the curvilinear than a predetermined value Emax, then this point was re-
expansion in Eq. (13), jected for use in evaluation of the expansion coefficients.
(15) Since the v=3 CH stretch overtone has an energy near
0.04 a.u., the box boundaries were chosen to enclose re-
where (p,{3) and (r,b) refer to the coordinates of the same gions where the potential was less than this value. The box
point. Referring again to Fig. l(b), the correction poten- boundaries (in a.u.) were chosen as rmin= -0.5,
tial Ii (r,b) must bend the contours "down" toward nega- rmax=0.55, and bmax =0.9. Within this box, 506 grid points
tive values of r at increasing values of b. were used (22 along rand 23 along b). In addition, with
TABLE I. Expansion of CH stretch-bend potential in rectilinear coordi- dition. The 24X24 matrix B~ may then be inverted, yield-
nates. ingD = (BD-1R = AR'. Thus, specification of (r,b) fixes
Term Order Coefficient' the two nonzero components of R' from which D is found
by matrix-vector multiplication. Knowledge of D permits
riJl 3 0.104 88 the Cartesian coordinates of all atoms to be computed,
b4 4 0.01830 from which the curvilinear coordinates, and then the po-
illf -0.27846 tential, may be computed.
?If 5 0.30848
rb4 -0.13328
b6 6 -0.02149 C. Vibrational anharmonic HamiltonIan

I'b2 -0.23642
ilb4 0.29429
In this section, the Hamiltonian will be developed for
one overtone excited CH oscillator interacting with all
?If 7 0.12955 other vibrational modes. All modes except the overtone
?b4 -0.36393
excited CH stretch will be referred to as "ring modes". In
rb6 0.08838
rectilinear coordinates {rlt'''''N}, the Hamiltonian may be
bl 8 0.01292 decomposed into a quadratic component which includes
I'lf -0.02464 the kinetic energy, plus an anharmonic vibrational poten-
I'b4 0.27463
ilb6 -0.24415
tial
r71f 9 -0.03347
(17)
?b4 -0.07848
?b6
rb8
0.22390
-0.03138 JIl=~{2 I
ij=1
pg;jJj+ I
ij=1
rj'ijrj},
b10 10 -0.004 81 where gij and f ij are elements of the G matrix and quadratic
"'If 0.03185
force constant matrix, respectively. Normal coordinates for
1'b4 -0.05585
I'b6 -0.06103 the ring and for the CH oscillator will be defined by un-
ilb3 0.11496 coupling the overtone excited CH oscillator (whose recti-
linear coordinate is denoted '1) from the ring (whose co-
"Coefficient in expansion V(r,b) = l:m,n c",,I"lf n, where b is in radians ordinates are denoted '2> ... ,'N)' To do this, we set glj
and V and r are in a.u.
= gjl = Oandflj =f;1 = 0 forj=2, ... ,N. Let the vector of
rectilinear coordinates R be partitioned into stretch and
Emax=0.045 a.u. (9876 cm- I ), 372 points were selected ring components, R = (r1,Rr)t, such that L (an nXn
for use in determining the expansion coefficients. matrix) accomplishes the conversion to normal coordi-
The 24 expansion coefficients in Eq. (16) were deter- nates,
mined by linear least-squares fitting of t::..(r,b) at 372 Q= (QltQr)t,
points. The least-squares analysis in Numerical Recipes74
was used for this purpose. The resulting expansion coeffi- R=LQ, (18)
cients are listed in Table I. At the grid points used in the
LII
fitting procedure, the rms error from this fit was 0.3 L= (
cm - I. Examination of Table I shows that the coefficient o
(0.105) of the cubic term rb 2 is different in sign and about where LII converts rl to the mass-scaled coordinate
four times larger in magnitude from the coefficient
( - 0.025) of the cubic term p{32 in curvilinear coordinates.
QI (L lI = ItcJ,
where itCH is the reduced mass for the CH
bond), and Lr [an (n-l)x(n-l) square matrix] is the
The final point that needs consideration is the conver- transformation matrix to ring normal coordinates.
sion between rectilinear and curvilinear coordinates. (We Transformation of the kinetic energy term in Eq. (17)
will again focus upon 21 mode planar benzene.) In the to normal coordinates is accomplished as follows. First, we
fitting procedure described above, the grid is set up in (r,b) note that the "old" kinetic energy may be written
rectilinear coordinates, and conversion to curvilinear coor-
dinates is required in order to evaluate the potential. The (19)
mechanism for this transformation is provided by Eq. (4), Then, using the transformation of the momentum vector,
which relates the rectilinear coordinates to Cartesian dis- p = (L -I) tp, where P is the "new" momentum vector in
placement coordinates, R = BID, where R is a column normal . coordinates (in classical mechanics, Pj
vector with 21 components and D is a column vector with = aT/aQj) , we obtain
24 components. In order to invert this equation, we first
augment R with three additional components to form R', 2T=P~~ (W)
and augment BI with three additional rows to form B;, by where the transformed G matrix is
imposing three constraints: the center of mass is at the
origin of an (x,y) coordinate system, and the Eckart con- (21)

This "new" G matrix is nonzero on the diagonal (Gu

= 1) and along the row and column which couples the CH
oscillator to the ring. If the overtone excited CH oscillator (30)
corresponds to normal mode number 1 (the modes are
temporarily renumbered to accomplish this), then T may
be written
1 INN A typical term in the stretch-wag potential, such as
T=i>i~ j~2 Pj+PI j~2 GIJ'ft (22) ~b2n then becomes
where the last term provides CH-ring kinetic coupling. N )2n

Transformation of the quadratic potential in Eq. (17) (Ll1)mQj ( j~2 Li,Qj . (31 )
proceeds similarly. Starting with
Expansion of the polynomial was performed symbolically
2V2 =Rt fR, (23) with the algebraic program REDUCE. Each term in Table I
and substituting R=LQ, yields was expanded this way and the sum of all such terms was
added into the anharmonic potential va.
2V2=Q~Q, (24) In summary, the Hamiltonian is partitioned into the
where the transformed quadratic coupling matrix is terms
F=LtfL. (25)
Analogous to the structure of G, F has nonzero elements
only along the diagonal, and in the first row and column. where the normal coordinate ring Hamiltonian and the
As a result, V2 may be written explicitly (Ai = F:(2) quadratic CH-ring coupling terms are
lIN N
V2=2AIQt+ 2 j~2 A,Q]+QI j~2 F1,Qft (26)
(33)
where the last term provides CH-ring quadratic coupling.
In Sec. II A, the PFB force field in curvilinear coordi- N
nates was converted into cubic and quartic terms in recti- TCH-ring=PI I
j=2
G1J'ft (34)
linear coordinates. The resulting cubic and quartic terms,
in rectilinear coordinates, are N
(27) ~H-ring=QI I FI,Qft (35)

j=2
Using the linear transformation to normal coordinates
while ~H-ring and Vrlng-ring are anharmonic CH stretch-
N ring interactions [such as Eq. (31)] and cubic plus quartic
Ri=
k=l
I LikQ/a (28) ring-ring interactions. Note that three terms in Eq. (32)
provide CH-ring coupling; these are quadratic kinetic and
the anharmonic force field in Eq. (27) may be converted to potential coupling, and anharmonic potential coupling.
normal coordinates. For C}H, there are two terms in T CH-ring' two terms in
In order to introduce the Morse potential for the over- ~H-ring, and 7, 6, 8, 8, 15, 15, 22, 22 terms in the third
tone excited CH bond, the quadratic, cubic, and quartic order, fourth order, ... , tenth order components of va. For
terms involving the mass scaled coordinate QI are replaced C}H}, there are four terms in T CH-ring' four terms in
by the Morse potential, Vm(QI). As a result, the CH ~H-ring, and 52, 41, 21, 21, 48, 48 terms in the third order,
stretch Hamiltonian is ... , eighth order components of va. All fifth and higher
order terms arose from CH stretch-wag interaction. The
(29)
number of cubic and quartic terms was restricted by the
The final terms that will be added to the Hamiltonian following criterion. First, the normal coordinates were
are those arising from the anharmonic stretch-wag poten- converted to dimensionless form. Then, the coefficients of
tial in Sec. II B. Once again, we will use the transforma- the various terms were computed and cubic terms were
tions from rectilinear coordinates (r,b) to normal coordi- rejected if the magnitude of the coefficient was < 20
nates, cm -I; the cutoff energy for the quartic terms was 25
cm -I. These restrictions were necessary to limit the num-
ber of terms in the larger 16 and 21 mode systems.
N (30) The normal frequencies and descriptions of the normal
b= 2:
j=2
Li,Qft coonfmates for the 5 and 9 mode models are presented in
Table II. These results are for the full 5 and 9 mode sys-
where "l" now refers to the row index corresponding to the tems, rather than for uncoupled CH-ring systems in Eq.
wag coordinate. For C 3H and C}H3' Eq. (30) becomes (32).
TABLE II. Normal modes for 5 and 9 mode reduced dimensionality For the problem of relaxation from an initial state, lung
models. and Leforestier27 recently presented results for CD3H us-
ing the same algorithm that we used for C3H. For this
Mode O)(cm- I ) Description SymmettY
reason, only a brief summary will be presented here.
5 mode model It is useful to think of the Al tree pruning algorithms in
416 CC-CC bend S the context of a sequence of tiers of states: the initial or
2 1225 CC stretch, CH wag A doorway state Ii) belongs to tier 0, the states directly con-
3 1231 CC stretch, CC-CC bend S nected to Ii) by the Hamiltonian (i.e., states U) for which
4 1472 CO stretch, CH wag A (iIHU):f:O) form tier 1, the states directly connected to
5 3072 CH stretch S
these states form tier 2, etc. The overall basis set is built
9 mode model from the tier states (after discarding multiple copies of
states)
I 402 CC-CC bend=a S
2 1076 CC stretch, a S
(39)
3 1167 CC stretch, CH wag A
4 1345 terminal CH wag A The set S is composed of the active states A and the non-
5 1432 terminal CH wag S active states B. The aim of the pruning algorithm is to
6 1462 CHwag A
3061
select the set A prior to performing the dynamics. Schemat-
7 CH stretch S A!
8 3073 terminal CH stretch A ically, S = A EBB -+ A.
9 3086 CH stretch S Now, assume that tier t has been generated and that
"Reflection symmetry (A=antisymmetric, S=symmetric) in plane con- one state in this tier, U), has been expanded to produce a
taining overtone excited CH bond. set of states in the next tier. One of the new candidate
states in tier t+ 1 is Ik); should this state be retained? The
decision is made on the basis of two criteria: (a) If the
D. Primitive basis set zero-order energy of state Ik) is within an energy separa-
The primitive (or uncontracted) basis set for the vi- tion !1E of the initial state, then the state is examined by the
brational dynamics consists of the direct product of har- next criterion, otherwise it is immediately rejected. (b)
monic oscillator functions for all ring normal modes times The global performance indicator from the initial state Ii)
Morse oscillator functions for the overtone excited CH is updated along the path leading to state Ik)
stretch. Thus for 5 mode planar C 3H and 9 mode planar
C 3H 3, the basis functions are denoted
T.rit+l) _ W(t)
Wic - j lfJ-14k}) .
(jIHI
(40)
IVI) IV2) IV3) IV4) Ivs) = I V\l V2,V3,V4,VS)0, (36)
If I Wit+l) I > 1, it is reset to unity to reduce the impor-
IVI) IV2) IV3) Iv.) Ivs) IV6) IV7) Iv8') IV9) = IVI,V2"",V9) 0, tance of near resonant states on the subsequent search. The
(37) selection criterion is then-retain Ik) if I Wkt + 1) I) W min
(predetermined tolerance); otherwise reject it.
where modes 5 or 8, labeled in order of increasing energy,
This algorithm is very similar to the best incomplete
are the Morse CH oscillators. For C 3H 3, modes 7,8, and 9
paths search recently used by Lederman and Marcus. 25
are all high frequency CH modes. For mode i, the vibra-
In order to use the Al tree pruning algorithm, four
tional quantum number ranges from 0 to v:nu. As a result,
parameters must be specified: !1 E, energy window size;
the dimension of the primitive direct product space is (M
Wmin' selection threshold; N p maximum number of tiers to
is the number of modes),
explore; d, number of retained states (dimension of A). Of
M
course, these parameters are not independent. The compu-
d= IT (v:nu+ 1). (38) tational effort scales with the values specified for these pa-
i=1
rameters; results will be presented in Sees. III and IV.
The value of d is frequently > 106, so two methods were This search algorithm can be parallelized if the com-
developed to select prior expectations as to what are the puter architecture permits this. The parallel version has
dynamically important states. Contraction of the primitive been tested on the IBM3090-600 and the Cray Y-MP8/
space to build the active space is the topic of the next 864. Some results are presented in Table IV of Ref. 27.
section.
2. Wave operator sorting algorithm
E. Construction of active space
The wave operator sorting algorithm will be used for
1. Artificial Intelligence tree pruning algorithm the first time in these studies of overtone relaxation. Going
One method that will be used to contract the primitive back in history about 50 years, the wave operator n was
space is based upon artificial intelligence tree pruning al- introduced into scattering theory by Moller26 and played a
gorithms. In the context of quantum dynamics, various major role in the effective Hamiltonians developed by
algorithms of this type have been used since the early 1980s Bloch76,77 and des Cloizeaux. 78 Various perturbative tech-
by Tietz and Chu,23 Chang and Wyatt,24 Lederman and niques for effective Hamiltonian theories were introduced
Marcus,zs lung and Leforestier,27 and Colbert and Sibert. 75 by L6wdin,79,80 Brandow,81 Lindgren,82 and others. A use-
J. Chem. Phys., Vol. 97, No.5, 1 September 1992

ful synthesis of these studies was presented by Klein. 83 The first few orders of the perturbative development of the
More recently, Durand,84 Gadea,85 and Jolicard86,87 have X operator are then easily derived
presented formal analysis or approaches aimed at compu-
X(1) = (E!} _J{J)-IQoVPo.
tational algorithms. However, our aim is not the develop-
ment of effective Hamiltonians, but the use of rigorous X(2)= (E!} -J{J) -IQO( VX(1) _X(1) V) Po, (51)
techniques to guide the selection of important states from
the vast number of candidates in the primitive space. X(3) = (E!} -J{J) -IQo( VX(2) _X(2) v -X(1) VX(1) ) Po·
As a prelude to the wave operator, we first define two
projection operators in the standard way: let Po project In terms of matrix elements of the X operator, the various
onto the initial/reference state Ii), while Qo projects onto perturbative corrections can be written
all other vectors in the primitive space
X~)=(kIX(p)li). (52)
Po=li)(il, Qo= L Ik)(kl, Po+Qo=l, (41) These equations provide a means for constructing X ki' term
k:f=i by term.
where the states Ii), Ik) are eigenvectors of J{J. The Mol- However, rather than using Eq. (51), we have used the
ler wave operator a (which is a projector, a 2 = a, but a is distorted-wave iterative equations for X developed by Joli-
not unitary at=Fa -I) is defined to map Ii) into the cor- card. 88 These equations, which will not be reproduced
responding eigenvector (as the perturbation V = H here, involve the use of X(p) to update the Hamiltonian at
- J{J turns on) each iteration step,
(42) d p) = (l_X(p-l) )H( 1+X(P-l»,
where 1'1') is assumed to obey intermediate normalization, dO) =0. (53)
(43) Assume now that we have performed several iterations
We then partition a into Po and a part which mixes into of the X operator equations and as a result have generated
l'I'i) contributions from vectors in the Qo space, a large number of nonzero matrix elements, X ki' The states
(44)
Ik) are then reordered such that those having the largest
magnitudes of X ki are up near the top of the list. Then,
where the second term introduces the transition operator from the reordered list, the top N a states are selected to
(or reduced wave operator). Using Eqs. (41)-(44), the form the active space; states Na + 1, ... ,N are discarded for
eigenvector can be written consideration of the dynamics. Of course, we must verify
the convergence of the dynamics with respect to the value
l'I'i)=li)+ L Ik)Xk ;. (45) of N a •
k:f=i In order to use the wave operator pruning algorithm,
where the matrix element of the X operator, X ki two parameters must be specified: N;. number of X-
= (kIXli), measures the contribution of Ik) in 1'1'). In operator iteration steps; d, number of retained states
the following development, we will use the magnitude of (=Na ). The computational effort scales with the values
X ki to provide a criterion as to whether state Ik) should be specified for these parameters; results will be presented in
included in the active space. However, we first need to Secs. III and IV.
compute these matrix elements. One feature the wave operator selection algorithm
It is straightforward to show that the wave operator shares with the Al/tree pruning algorithm is that succes-
obeys the nonlinear equation, 82 sive tiers of states are generated. However, the selection
criteria are quite different in the two methods. For exam-
[a,J{J] = va-ava, (46) ple, the wave operator algorithm does not use an energy
or, in terms of the X operator, this equation becomes window, !l.E' In practice, some states with large detunings
from the initial state are selected in the wave operator
[J{J,x] = -Qo( I-X) V( l+X)Po' (47)
approach.
An equivalent nonlinear equation can be derived from Eq.
(47), F. The recursive residue generation method
Qo( 1-X)H( 1+X)Po=O. (48) The final issue to be dealt with is determination of the
dynamics within the active subspace. Since the dimension
This equation for X has the formal solution
of the active subspace may still be relatively large
X = (Ej -J{J) -IQO( I-X) V( 1+X)Po' (49) ( > 103), an efficient means is required to generate the cor-
relation function and the spectrum.
Equation (49) is useful because perturbative solution The recursive residue generation method (RRGM) in-
for X can be developed by using the substitutions troduced by Nauts and Wyatt 19 in 1983, is a versatile
method which allows one to study spectroscopic and dy-
(50) namic properties of multistate systems. Through use of the
V ..... A.X(I) +A(2)X(2) + ... Lanczos tridiagonalization algorithm,18 the computation
and storage of all eigenvectors is avoided. The RRGM has of the eigenvector matrix), and (ila)2, referred to as a
been reviewed recently,22 and its application to IVR in residue, represents the probability of finding the initial
CD3H has been described in some detail. 4,21 Consequently, state in eigenvector 1a). A plot of (il a)2 vs Ea is the
we will only present a very brief summary here. spectrum of the system. The spectrum and the autocorre-
lfthe eigenvectors 1a) (a = 1,2, ... ,N) are known, the lation function are related through a Fourier transform.
survival amplitude, or autocorrelation function, of the ini- This whole procedure works well when N is not too large,
tial state 1i) is given by say N < O( 103 ). On the other hand, when N > 103, it is
N not possible (nor even desirable) to find all eigenvectors;
A(t)=(ile-iHtli)= L (ila)2e- iEat, (54) after all, the survival amplitUde and spectrum depend upon
a=l information in only one row of the NXN eigenvector ma-
and the survival probability is S(t) = 1A (t) 12. The quan- trix.
tity (il a) is an eigenvector coefficient (in row i, column a The RRGM handles this problem by recursively gen-
1.0 - . - - - - - - - - - - - - - - - - - - - . . , 1.0.,..------------------,
O.B O.B
0.6 0.6
...J ...J
« «
> >
:>
a:
:>
a:
:l :l
CI) CI)
0.4 0.4
0.2 0.2
o 10000 20000 30000 40000 50000 o 10000 20000 230000 40000 50000
(8) TIME(au) (e) TIME(au)
1.0 - . - - - - - - - - - - - - - - - - - - - - ,
O.B
...J 0.6
~
:>
a:
FIG. 2. Survival probability vs time (in a.u.) for relaxation from
:l C 3H(v = 3). (a) Terms through fourth order in the CH stretch-wag
CI) 0.4 potential were included in the dynamics. (b) Terms through sixth order
in the CH stretch-wag potential were included in the dynamics. (c)
Terms through eighth order in the CH stretch-wag potential were in-
cluded in the dynamics.
0.2
o 10000 20000 30000 40000 50000

(b)
TIME(au)

erating the residues and eigenvalues; the projections (i! a) TABLE III. C 3H energies associated with eigenvectors which have resi-
are generated without knowledge of the eigenvectors. due I (aI3vs)OI2 larger than 0.01. The zero-order basis set used in this
Through use of the Lanczos algorithm, each recursion step calculation is the following: vrnax=8 for all 5 modes. Converged results are
obtained in such a basis set.
develops one pair of new diagonal and off-diagonal ele-
ments in the tridiagonal representation of the Hamiltonian. Energy (em-I)" Residue
After M recursion steps, M residues and eigenvalues are
8351.6 om
produced from the tridiagonal matrix. In practice, approx- 8486.4 0.Q2
imations to the largest residues are developed first and 8493.2 0.01
smaller residues (the "grassy" part of the spectrum) are 8554.1 0.05
filled in as recursion proceeds. The most intense portion of 8782.2 0.44
8856.4 0.28
the spectrum fills in quickly, but weak spectral lines may be
difficult to converge. 'Energies are relative to the 10,0, ... ,0) ground state eigenvalue.
In applications of the RRGM, most of the computa-
tional effort is devoted to computing matrix-vector prod-
ucts, HV, where H is the (usually sparse) Hamiltonian methods. Finally, the validity of the following widely used
matrix. In our applications, considerable attention was de- assumptions will be examined: (i) truncation of the
voted to optimizing the efficiency of this operation by ex- stretch-wag anharmonic potential expansion to the fourth
plicitly utilizing the sparse structure of H through the for- order; (ii) limitation of the primitive basis set to near-
mation of transition vectors. 21,89 resonant states.
A. Anharmonic expansion of V(r,b)
III. OVERTONE RELAXATION IN C3 H
Recent studies3,4(b) concerning the CD3H molecule
Study of the C3H system is a good starting point to
have shown that an expansion to the sixth order of the
examine various aspects of IVR. Firstly, the energy relax-
kinetic C-H stretch-bend coupling is required. These stud-
ation can be accurately and easily studied in this small
ies have achieved an exact expansion of the stretch-bend
system. Such an investigation will be very helpful in later
coupling. We have reconsidered this problem for the
analysis of relaxation energy in 21 mode planar benzene.
C 3H and C3H3 systems, where an exact expansion cannot
Secondly, the RRGM applied directly to the primitive
be accomplished. In these two systems, convergence of the
space, without contraction, provides exact results in this 5
survival probability requires an eighth order expansion of
mode system. Thus, the viability of our new wave operator
the C-H stretch-bend coupling. In order to illustrate the
contraction algorithm can be established. This work will
effect of these high order terms, the survival probability of
thus illustrate the complementarity of three calculational
the v=3 CH overtone state is displayed in Fig. 2 where the
C 3H system is described by an anharmonic potential de-
veloped either to the fourth order [Fig. 2 (a)], the sixth
o~------------------~--------------, order [Fig. 2(b)], or the eighth order [Fig. 2(c)]. These
curves show that the results converge quite slowly. How-
ever, the tenth order development gives exactly the same
results as the eighth order one. Similar conclusions have
been also drawn for the C3H3 system. Consequently, in this
study, the C-H stretch-bend coupling has been expanded
to the eighth order. Comparison of Figs. 2(b) and 2(c)
shows that a higher order expansion of the anharmonic
potential does not necessarily increase the rate of energy
relaxation.
TABLE IV. Projection of the two eigenstates Ia) and Itl) on the zero-
order basis set. Only projections greater than 0.01 are shown.
Zero-order states Ii) 0 l(al llOl 2 I (tll llol 2

1 3vs)0 0.28 0.44
1 2u4+ 2vS)O 0.38 0.21
o 3 6 9 12 15 14v4+ VS)0 0.04 0.04
16v4)O 0.01
m{cm- 1 ) x 10- 3 0.03 0.06
I V2+ V4+ 2vS)O
12~+2vs)O om om
FIG. 3. Residue spectrum for relaxation from C 3H(v = 3). The quantity I V2+ 3v4+ VS)0 0.04 0.05
log(residue/maximum residue) is plotted on the ordinate; the energy (in 12v3+ 2vS)O 0.01
cm- I ) is shown on the abscissa. The two most intense lines occur at 8831 IV3+ 2vS)O om 0.02
and 8760 cm- I (relative to the 10,0, ... ,0)° reference state); the residues Total 0.80 0.84
are 0.421 and 0.348, respectively.
B. Energy spectrum states which are responsible for these two lines, an active
The stick spectrum of the v = 3 CH overtone state has space containing 1500 states was built using the Bloch for-
been calculated and is displayed in Fig. 3. We have repro- mulation. A direct diagonalization of the Hamiltonian was
duced, in Table III, the eigenenergies associated with res- then used for this small basis set. Such calculations show
idues I (a I3vs)O 12 larger than 0.01. The two eigenvectors that the zero-order states which are strongly connected to
which are associated with the two larger residues will be the 13vs)O state are 12v4 + 2vs)o, 14v4 + vs)o, 16v4)O, IV2
denoted la) and 1m. Their energies (Ea = 8782.2 cm- I + V4 + 2vs)O, 12v2 + 2vs)o, /2V3 + 2vs)O, and IV3 + 2vs)o.
and Ep = 8856.4 cm -I, respectively) are separated by 70 The exact projection of these zero-order states on the two
cm -I. This result is related to a recent experimental eigenstates la) and 1m was calculated using the RRGM
study46 of the v=3 overtone in benzene where two absorp- (see Table IV). Such results demonstrate that there is a
tion peaks were located around 8800 cm -I, at a separation strong Fermi resonance between the 13vs)O and 12v4
of about 60 cm - I. In order to determine the zero-order +2vs)o.
1.0 . , . . . - - - - - - - - - - - - - - - - - - . . , 1.0 . - - - - - - - - - - . , ; ; , . . . . - - -_ _ _ _ _.,
0.8 0,8
0,6 0,6
-l -l
<{ «
>
> ;;:
;;:
II: II:
::> ::>
CI) CI)
0,4 0,4
0.2 0,2
0.0 +-....--...,.--.,...l.c:.....,...---,.----r--..-""T-....,.......;;-! 0.0 -t--...,.--r-,...--I--,..--Ti'-....,...--r--....-~

a 10000 20000 30000 40000 50000 o 10000 20000 30000 40000 50000
lal (e)
TIME(au) TlME(au)
1.0 - , - - - - - - - - - - - - - - - - - - -.....
0.8
-l 0.6
~
;;:
II:
::>
CI) 0,4 FIG. 4. Survival probability vs time (in a.u.) for relaxation from
C 3H (v = 3). The Al tree pruning algorithm was used to build the active
space. Only states within the energy window t::..E were selected. (a) t::..E
= lOOOcm- l , (b) t::.. E = 3000cm- l , (c) t::.. E = 6OOOcm- l .
0.2
0.0 +-....--...,.--.,--,...---,.---=l~~-_._-....,...--!
a 10000 20000 30000 40000 50000 -
(bl TIME(au)
c. Time evolution of the v=3 state 1. Active space definition: Influence of the detunlng
parameter, 4.E
Following this analysis of the spectrum, we focus at-
tention on the dynamic behavior of the v=3 state and seek Firstly, the role played by distant nonresonant states
answers for the following crucial questions: (i) How long during the IVR will be investigated because a detuning
does energy remain in this C-H stretch when the system is parameter, A E, is used in the AI/tree pruning algorithm in
initially represented by the 13vs)0 state?; (ii) If irreversible order to build the active space. In order to check this ap-
or reversible IVR occurs, which zero order states are sig- proximation, we have performed a series of calculations
nificantly populated?; (iii) Which anharmonic coupling using the Alltree pruning algorithm in which we system-
terms are responsible for this dynamic behavior? atically increased the maximum detuning allowed: only
1.0 - . - - - - - - - - - - - - - - - - - - - . . , 1.0 - , - - - - - - - - - - - - - - - - - - - - ,
0.8 - 0.8
0.6 0.6
--l --l
« «
> >
:> :>
a:
a:
:J :J
en 0.4
en 0.4
0.2 0.2
0.0~~~1~~1~-~1~~1r-~~~~~~~~~1~
o 00 000 000 00 00 0 00 0 00 000 000 000

'l-0o .,0 '60 '000 ,,000 ,,'/,.0 " ..0 "tOO ,,'00 '/,.00
(el
(al TIME(au) TIME(au)
1.0 - - . - - - - - - - - - - - - - - - - - - - - ,
0.8 -
--l 0.6-
~
:>
a:
:J
en 0.4 -
FIG. 5. Survival probability vs time (in a.u.) for C3H: (al initial state
10,0,0,0,3); (b) initial state 10,0,0,2,2); (e) initial state 10,1,0,1,2).
0.2
y
O.O~~~I~~I~~~-r~~~,-~.-.-T-~r-~
~ w ~ ~ ~ ~ •
o 00 cPO 000 000 000 000 000 000 000 000
'l-00 .,0 '60 '00 ,,00 ,,'/,.O " ..A "tOO ,,'00 '/,.00
(b) TIME(au)
those states located within I1E from the initial 13vs}o state 1.0 -r-------------------.
may be retained. The survival probability of this initial
state is shown in Fig. 4, where the detuning parameter is
successively fixed at 1000 cm- i [Fig. 4(a)], 3000 cm- i
0.8
[Fig. 4(b)], and 6000 cm- i [Fig. 4(c)]. We notice in Fig.
4(a) that the use of too small a value for the I1E parameter ~
drastically modifies the results. Thus, limitation of the di-
mension of the active space using a restrictive value for en
I1E can change the IVR in the molecule in an erroneous
z 0.6
0
j:::
way. Therefore, in the following, the parameter I1E has «
been fixed at 6000 cm -1. -I
::l
I
I
•
a. I
0 0.4
a. I
,,
. , .
I •
I
2. Long time evolution
Survival probability calculations for several different I "i
zero-order states were performed with our three different I
0.2 I
methods for long time scales (a few picoseconds). All of
•
,,,
these calculations were carried out using a large zero-order I
basis set because we were interested in the long time scale

evolution of the system. Similar converged results have 0.0
,
been obtained with all three methods and are reproduced 0 10000 20000 30000 40000 50000
in Fig. 5 for three different initial states, Ii)o = I 3vs)0 [Fig. (8) TIME(au)
5(a)]; bi)O =12v4 + 2vs)0 [Fig. 5(b)]; li)O =1 v2 + V4
+ 2vs} [Fig. 5(c)]. The states in Figs. 5(b) and 5(c) were 1.0
chosen because they are strongly connected to the 13v5}0
state. (The time axis in this and all other figures showing
survival probabilities is labeled in a.u. We note that the CH
fundamental frequency corresponds to 450 a.u. or 0.011 0.8
ps.) Consequently, it is interesting to compare their dy-
namic behavior in order to explain why irreversible IVR
does not occur when the system is initially represented by
en
the 1 3v5) 0 state. Z 0.6
o
~
3. Nature of the IVR -I
::l
a.
In order to determine what happens to the initial en- oa. 0.4
ergy of the v=3 overtone, we built an active space contain-
ing 2000 zero-order states using five wave operator itera- ,....
tion steps. Converged calculations in such an active space
..
• I
.. • I
are obtained for times smaller than 50 000 a. u. (1.2 ps). 0.2
",
Exact diagonalization of the Hamiltonian matrix could be
achieved in this space. Consequently, using one calcula-
tion, the population of all of the zero-order states could
.~
,, .u .,• (t t
easily be determined. In Fig. 6(a), the probability of find-

ing the system in the 13vs}0 (continuous line), the 12v4 o 10000 20000 30000 40000 50000
+ 2vs)0 (dashed line), and the IV2 + V4 + 2vs}0 (light (b) TIME(au)
dashed line) states are shown. All the other zero-order
states have an averaged population smaller than 0.05. In FIG. 6. (a) Survival probability vs time (in a.u.) for C 3H for the initial
Fig. 6(b), we show the total probability of finding the state 10,0,0,0,3), and the transition probability from this state to the two
system in all zero-order states IVi,V2,V3,V4,V5,)0 with Vs ei- states, 10,0,0,2,2}, and 10,1,0,1,2). (b) Total probability vs time (in a.u.)
ther equal to 2 (continuous line), or 1 (dashed line), or a for states with CH(v=2), CH(v= 1), and CH(v=O).
(light dashed line). Consequently, if no fast irreversible
energy relaxation occurs from the 13vs)o state, it is because
this state is strongly connected via a Fermi resonance to performed using a zero-order basis set where the V4 quan-
the 12v4 + 2vs}0 state which in tum is weakly coupled to tum number was forced to zero. In this case, no energy
the other zero-order states. Thus to a first approximation, relaxation, even reversible, occurs; the population of the
the energy flow is governed by this strong Fermi resonance 13vs)0 state is always greater than 0.85. Thus, the third
which is responsible for the quasiperiodicity of the 13vs)0 state IV2 + V4 + 2vs)0 plays a minor role and is responsible
survival probability. In order to illustrate the crucial role for the slow relaxation out of the C-H chromophore. The
played by vibrational mode 4, calculations of IVR were dynamic behavior of this state [Fig. 5 (c) J is novel com-

pared with the 13vs}O state; a very fast and irreversible tion periods are evident: high amplitude, low frequency
energy relaxation occurs when the state IV2 + V4 + 2V5)O is oscillations (period 1'"= 10 000 a.u.); intermediate ampli-
initially populated. If it were coupled strongly to the chro- tude oscillations with 1'"=2000 a.u.; and low amplitUde,
mophore, the energy relaxation from the 13vs)0 state high frequency oscillations with 1'"=700 a.u. On the time
would be irreversible. scale shown in this figure, there is incomplete relaxation,
However, in spite of the crucial role played by this which implies that the spectrum should show a relatively
Fermi resonance, we cannot neglect the other states. For large residue on one eigenstate. Examination of the spec-
example, there is an average probability of more than 15% trum shows that this is indeed the case: the four largest
of finding the system in a zero-order state associated with residues and associated energies are (these energies are
an energy located more than 1000 cm -I from the initial relative to the 10,0, ... ,0)° reference state) 0.694 (at
state. This probability is spread over a myriad of nonreso- 0.03957 a.u.), 0.070 (at 0.03902), 0.048 (at 0.03863),
nant states. and 0.032 (at 0.03773 a.u.). The last 3 residues occur at
The quantum survival probability in Fig. 2ec) differs energies on the "red" side of the peak. In addition, the
significantly from classical trajectory results (see Fig. 3 in energy difference between the two states with the largest
Ref. 16). In the classical case, the probability shows residues (0.03957-0.03902=0.000 55 a.u.) approxi-
damped oscillatory behavior (period -0.25 ps_104 a.u.), mately matches the energy gap, I:l.E, associated with the
declining to about 0.2 at t=l ps (41300 a.u.). The quan- long period oscillation in Fig. 7(a) (1:l.E = 2rr/104
tum results in Figs. 2(c) and 5(a) show persistent long =0.000 63).
term oscillations with a period -20000 a.u. However, at
very short times, up to t-0.1 ps -4000 a.u., the rapid C. Nature of the IVR
initial decrease in Set) is reflected in both the classical and The modes which are important in receiving energy
quantal results. from the initially excited CH bond may be identified by
setting vmax=O in selected modes. Figures 7(b) and 7(c)
IV. OVERTONE RELAXATION IN C3H3 show a series of results in which vmax=O in one or more
A. Anharmonic expansion of V{r,b) modes. The number of active modes is 7 or 6, respectively,
in these two plots. First, in Fig. 7(b) the survival proba-
We now consider relaxation from the v=3 CH over-
bility is shown for the case where vmax=O in modes 7 and
tone in the 9 mode model system C 3H 3• Stretch motion in
9, which are the initially nonexcited "end" CH stretches.
the "middle" overtone excited CH bond is treated as a
The other parameters specifying this calculation are as fol-
Morse oscillator and the same expansion of the stretch-
lows: maximum quantum numbers in each mode=6X8, 0,
bend potential is used here as in the study on C 3H. The
6, 0; size of active space = 6000; number of X-operator
tenth order expansion in Table I was again employed, and
iterations=5. Comparison of Figs. 7(a) and 7(b) shows
some preliminary dynamical calculations were done in-
that Set) is almost the same for t < 10 000 a.u., and that for
cluding anharmonic potential terms through the sixth, sev-
longer times the average values for Set) are very similar.
enth, eighth, or ninth orders. The correlation functions
One difference is that the peak value of set) in Fig. 7(b)
(for t < 50 000 a.u.) were very similar for dynamical cal-
(about 0.6) is less than in Fig. 7(a) (about 0.75); this
culations involving the eighth and ninth order potentials,
implies slightly less localization in the initially excited CH
so all further calculations employed the eighth order ex-
bond at later times. However, it is clear that the CH oscil-
pansion. The two terminal (nonexcited) CH oscillators, in
lators neighboring the one that is initially excited do not
contrast to the middle oscillator, were not treated as Morse
play a major role in removing energy from the initially
oscillators, but were described by potential terms in recti-
excited bond.
linear coordinates (through fourth order), as discussed in
In contrast to this result, Fig. 7 (c) shows the survival
Sec. II B. Altogether, 4 kinetic and 235 potential coupling
probability when vmax=O in modes 6,7, and 9. In this case,
terms were used in the vibrational anharmonic Hamil-
the survival oscillates primarily between the values 0.7 and
tonian.
0.8. The high frequency oscillation noted earlier in Figs.
7(a) and 7(b) is also present in Fig. 7(c). For C 3H 3, mode
B. Time evolution of the v=3 state
6 has an important contribution from the in-plane CH wag
The survival plot, Set), for relaxation from v=3 is coordinate and this mode is in Fermi resonance with the
shown in Fig. 7(a). The primitive basis included the states initially excited CH oscillator. As for C 3H, stretch-wag
0,1,2,3 in each mode, so the total basis set size was interaction is very important in the overtone relaxation
49 =262 144. The Bloch wave operator contraction scheme process.
(with 4 iteration steps to develop the X operator) was used From the three survival plots in Fig. 7, we conclude
to form active spaces of dimension 3000, 6000,and 9000. that CH oscillators adjacent to the initially excited oscilla-
The latter two results differed very little; the results in Fig. tor are not extremely important during the first picosecond
7(a) were obtained using an active space of dimension of the relaxation process, but that modes involving the
6000. From Fig. 7(a), we note the following features: (1) contiguous in-plane wag are very important.
at early times (t < 5000 a. u.), S (t) drops quickly to about The classical trajectory calculations (which were per-
0.3; (2) at longer times (5000a.u. <t<50000a.u.),S(t) formed on a different force field) of Lu and Hase l6 show
oscillates between 0.3 and 0.7; (3) three dominant oscilla- some similarities with the present calculations, including

1.0 , . . . - - - - - - - - - - - - - - - - - - . . , 1.0-r--------------------------------~
0.8 0.8
0.5 0.6
-1 -1
c( c(
> >
:>a: :>
a:
::J ::J
en 0.4
en 0.4
0.2 0.2
a 10000 20000 30000 40000 50000 o 10000 20000 30000 40000 50000
(a) TIME(au) (e) TIME(au)
1.0 .......- - - - - - - - - - - - - - - - - - - - - - - - - . . ,
0.8
-1 0.5
~
:>
a:
::J
FIG. 7. Survival plot for relaxation from the V= 3 CH overtone in
en 0.4
C 3H 3. The abscissa is time in a.u. The active space dimension is 6000 and
800 Lanczos recursion steps were used. (a) The primitive space has
vmax =3 in all modes. (b) Same as (a), except vmax=O for modes 7 and 9,
the other two CH modes. (c) Same as (b), except that vmax=O for mode
0.2
6.
0.0 +-.. . . .-..,--"T""--r--r--r---,---r-......,...-....,

a 10000 20000 30000 4ODon 50000
(b) TIME(au)
the following: (1) the two terminal CH stretches are not V. COMPARATIVE DYNAMICS: C3H VERSUS C3H3
important in removing energy from the middle excited CH
oscillator; (2) the contiguous in-plane wag is very impor- Comparison of the survival plots for v=3 CH overtone
tant in the dynamics; (3) the initial rate of decay in the relaxation in C 3H [Fig. 2(c)] and C3H3 [Fig. 7(a)] shows
survival probability [P(n,t) in the classical case] up to large amplitude recurrence oscillations in C3H3 which vary
about t=3000 a.u. is very similar. A dissimilar feature in between 0.0 and 0.7, with an average around 0.35, while
this comparison is that the classical probability P(3,t) for C3H 3, the less well structured oscillations vary between
shows oscillatory decay for t> 5000 a.u. [with P(3,t) 0.3 and 0.7, with an average around 0.5. On averaging over
=0.25 when t=50 000 a.u.] whereas the quantal survival time, neither system, at least for several ps, undergoes
oscillates between 0.3 and 0.7. Decay of the v=3 overtone "complete" relaxation, with S < 0.1 (where S is a time
is suppressed relative to the classical results. average over say 0.5 ps). In order to trace the origin of the

1.0 -r--------------------, 1.0--r-------------------------~
0.8 0.8
0.6 >-
I- 0.6
...J
::J
~ co
:>
cr:
«
co
:J 0
en 0.4 cr: 0.4
Q.
0.2 0.2
0.0~-~--~-~--r_~-~--~--_r-~__1
a 10000 20000 30000 40000 50000 o 10000 20000 30000 40000 50000
TIME(au) TIME(au)
FIG. 8. C3H3 v=3 survival probabilities when the cubic anharmonic force FIG. 9. C3H3 transition probabilities from 3vs to the state (2v8+2v6),
constant F266 is scaled by a factor a: a=O.75 (-); a=O.50 (---). when the cubic anharmonic force field is scaled by a factor a: a=O.75
(-); a=O.50 (---).
differences between these systems, we performed a series of

additional calculations in which some feature (set of force
constants) in the anharmonic force field for each molecule stretch, we ran two additional calculations, where all CH
was altered. chromophore anharmonic terms (arising from r"'b n ) were
First, consider C 3H 3. Through a systematic series of included, but in "run A" all other cubic and quartic terms
runs, we determined that S(t) is very sensitive to a single were eliminated, while in "run B" the cubic terms arising
cubic anharmonic term in normal coordinates. This term is from only the RiRi terms were included. The survival plot
F 266 Q2(ft" where F 266 = -0.2920 X 10- 6 = -137
from run A closely resembled the C 3H survival, while the
cm -I. Sensitivity of the survival probability to scaling of survival plot from run B closely resembled the C3H3 re-
this term is demonstrated in Fig. 8, which shows S(t) sults.
when F266 is reduced by a factor a, where a=0.75 and The importance of mode 6 in the C3H3 dynamics can
a=0.50. As a is decreased, the amplitude of the pulsations be appreciated by referring back to Eq. (30), which shows
increases, and when a=O, we recover the C 3H dynamics that the in-plane wag coordinate b has a dominant contri-
shown in Fig. 2 (c). In addition, Fig. 9 shows the transition bution from Q6' Thus, the chromophore anharmonic terms
probability to the combination state (2vS+2v6)' As a is r"'b n will bring in terms involving Q6 to various powers. In
decreased, from a=0.75 to a=0.50, the maximum transi- addition, mode Q6 has the dominant contribution to the
tion probability increases, such that when a=O, we recover two 'CC stretch coordinates, while mode Q2 also has a
results similar to that for C3H in Fig. 6(a), for the transi- significant contribution. In addition, when the rectilinear
tion 3vS ..... 2v4+2vS' which are the corresponding mode la- CC stretch coordinates are expressed in normal coordi-
bels for C 3H. nates,
For C3H 3, F 266 is the cubic anharmonic term of largest R 1= O.OO39Q2 - O.OO24Q3 + O.OO19Q4 + 0.0042Qs
magnitude (all of the others have magnitudes < 73
cm- I , except for FS66 which is -125 cm- I ). We then +O.OO68Q6'
examined the origin of the cubic anharmonic force con-
stants in normal coordinates, in terms of contributions R2 = O.OO39Q2 + O.OO24Q3 - O.OO19Q4 + O.0042Qs
from the internal rectilinear coordinates. These studies re- -O.OO68Q6'
vealed that the cubic CC stretch anharmonic terms Ri,
R~, RiR 2 , and RIR~, have the largest contributions to the it is seen that Q2 and Q6 make major contributions.
cubic anharmonic coefficients F ijk in normal coordinates. For C 3H; a similar series 'of investigations were con-
These RiRi terms contribute -116 cm- I (or 85%) to the ducted, but in this case it was found that scaling the
F 266 coefficient. In order to confirm the sensitivity of S(t) RiRi CC stretch anharmonic terms did not significantly
to cubic anharmonic terms originating from the CC alter the amplitude of the osciilations in the survival plot,
J..Chem. Phys., Vol. 97, No.5, 1 September 1992
although the time at which S(t) reached maximum or energy transfer process foc t< 0.2 ps and for later times
minimum values did vary slightly. they play a minor role.
(e) Fermi resonance between mode 6 (CH wag) and
mode 8 (CH stretch) is very important in the dynamics.
VI. CONCLUSIONS
A. Summary: What did we learn? B. Discussion: Limitations and outlook
A detailed study has been presented on the quantum The present studies have been restricted to 5 and 9
dynamics of the 5 and 9 mode benzene fragments C3H and mode model benzene fragments. The fragments are planar
C 3H 3• Converged results were obtained using basis sets of and, except for the CH overtQne excited bond, they are
dimension up to about 216000. For C3H, three dynamical initially unexcited. The quantum dynamics was treated to
methods gave the same autocorrelation functions and spec- high accuracy, but the vibrational anharmonic Hamil-
tra. For C 3H 3, a new algorithm was developed and applied tonian is not known to high accuracy. We consider the lack
to contract the large primitive vector space into a much of an accurate anharmonic force field to be the limiting
smaller active space. The new wave operator contraction feature in our ability to interpret or predict experimental
method is based upon iterative development of an approx- results on benzene.
imate transition operator X, followed by sorting of the In part 2 of this series,9O a 16 mode model of benzene
vectors in the primitive space according to the magnitude will be considered (the 5 initially unexcited CH stretch
of the X-operator matrix elements. Following construction modes are neglected). Sensitivity of the results to alteration
of the active space, the RRGM was used to accurately of the anharmonic force field will be described and com-
compute spectra and correlation function, without comparisons will be made with experimental results. In part
puting eigenvectors. This scheme is capable of handling III, full 21 mode planar benzene will be considered with
dynamical problems with a huge number of states. primitive vibrational spaces of dimension 1010 states. In
For the 5 mode C 3H system, 3 calculational methods later parts of this series, computational aspects of AI and
(RRGM applied directly to the primitive space, and two wave operator contraction algorithms will be considered,
methods for constructing the active space) were used. The and a new ab initio force field will be introduced.
major results are
(a) An eighth order expansion of V(r,b), the CH ACKNOWLEDGMENTS
stretch-wag potential, is necessary for convergence of the
spectrum and the survival probability. This research was supported by the Robert Welch
°
(b) The 13vs) initial state projects primarily onto 2 Foundation and the National Science Foundation. For ac-
cess to the Cray Y-MP8/864, we thank the University of
eigenstates near 8800 cm~1 which are separated by 70
cm- I . Texas Center for High Performance Computing. For ac-
(c) Both of these eigenstates project strongly onto the cess to the Cray-2 at NCSA, we thank the National Science
Fermi resonant pair of basis states 13vs)O and 12v4 Foundation. Robert E. Wyatt wishes to thank the Univer-
+ 2vs)oand less strongly onto IV2 + V4 + 2vs)o. sity of Paris-Sud (Orsay) for an invited Professorship, dur-
Cd) As a result, the survival probability of the 13vs)O ing which this work was initiated. In addition, he thanks
initial state shows quasiperiodic large amplitude oscilla- Profs. Howard Taylor and William Hase for helpful dis-
tions which persist for at least 4 ps. cussions.
(e) At early times, the survival probability drops rap-
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Quantum dynamics of overtone relaxation in benzene. I.

Citation: J. Chem. Phys. 97, 3458 (1992); doi: 10.1063/1.462981

Additional information on J. Chem. Phys.

I. INTRODUCTION ical results. We start with direct product vibrational basis

J. Chern. Phys., Vol. 97, No.5, 1 September 1992

J. Chern. Phys., Vol. 97, No.5, 1 September 1992

R=L,Q=B,o, (4) (8)

where B*, L*, and T* are nonlinear tensor transformations

The successive sets of coefficients defining this transforma-

J. Chern. Phys., Vol. 97, No.5, 1 September 1992

B. Potential for CH chromophore

J. Chern. Phys., Vol. 97, No.5, 1 September 1992

b6 6 -0.02149 C. Vibrational anharmonic HamiltonIan

J. Chern. Phys., Vol. 97, No.5, 1 September 1992

This "new" G matrix is nonzero on the diagonal (Gu

where the last term provides CH-ring kinetic coupling. N )2n

(27) ~H-ring=QI I FI,Qft (35)

J. Chern. Phys., Vol. 97, No.5, 1 September 1992

J. Chem. Phys., Vol. 97, No.5, 1 September 1992

J. Chern. Phys., Vol. 97, No.5, 1 September 1992

o 10000 20000 30000 40000 50000

J. Chern. Phys., Vol. 97, No.5, 1 September 1992

Zero-order states Ii) 0 l(al llOl 2 I (tll llol 2

J. Chern. Phys., Vol. 97, No.5, 1 September 1992

1.0 . , . . . - - - - - - - - - - - - - - - - - - . . , 1.0 . - - - - - - - - - - . , ; ; , . . . . - - -_ _ _ _ _.,

0.0 +-....--...,.--.,...l.c:.....,...---,.----r--..-""T-....,.......;;-! 0.0 -t--...,.--r-,...--I--,..--Ti'-....,...--r--....-~

J. Chern. Phys., Vol. 97, No.5, 1 September 1992

o 00 000 000 00 00 0 00 0 00 000 000 000

J. Chern. Phys., Vol. 97, No.5, 1 September 1992

basis set because we were interested in the long time scale

easily be determined. In Fig. 6(a), the probability of find-

J. Chern. Phys., Vol. 97, No.5, 1 September 1992

J. Chern. Phys., Vol. 97, No.5, 1 September 1992

0.0 +-.. . . .-..,--"T""--r--r--r---,---r-......,...-....,

J. Chern. Phys., Vol. 97, No.5, 1 September 1992

1.0 -r--------------------, 1.0--r-------------------------~

differences between these systems, we performed a series of

J..Chem. Phys., Vol. 97, No.5, 1 September 1992

J. Chern. Phys., Vol. 97, No.5, 1 September 1992

J. Chern. Phys., Vol. 97, No.5, 1 September 1992

Anda mungkin juga menyukai

where B, L, and T* are nonlinear tensor transformations