From High Resolution Spectroscopy to Detailed

Molecular Quantum Dynamics

David Luckhaus
Laboratorium f ur Physikalische Chemie, ETH Z urich (HCI), CH8093 Z urich, Switzerland
present address: Institut f ur Physikalische Chemie, Universitat Gottingen, Tammannstrasse 6,
D37077 Gottingen, Germany
1 Introduction
Understanding the mechanisms of energy redistribution at high rovibrational excitation
is essential to all models of chemical reactions on a microscopic level, statistical or other-
wise. From the chemists point of view the most intriguing aspect lies in the association
of dynamical properties with structural features, e.g. functional groups, in analogy with
the chromophore concept so well established in spectroscopy. It is the possible transfer-
ability of dynamical properties which ultimately establishes the link between molecular
structure and reactivity, arguably the cornerstone of modern chemistry. In this eld
molecular spectroscopy assumes a particularly prominent role not only providing the
means to prepare molecular systems in well dened states but also serving as a unique
probe for the ensuing molecular motion. In combination with detailed modelling, high res-
olution overtone spectroscopy oers an elegant and often complementary alternative
to the direct time resolved approach. The spectral analysis on the basis of microscopic
models for the molecular motion reveals hidden (approximate) symmetries, coupling
hierarchies and constants of the motion on dierent time scales not easily detected in
time dependent experiments [13]. While numerous aspects can be analysed in terms of
algebraic models, often referred to as the eective Hamiltonian approach, only the de-
tailed quantum mechanical model in a coordinate representation can relate the dynamical
features to the molecular structure.
2 The ZMatrix Discrete Variable Representation
Within the BornOppenheimer approximation the Hamiltonian for the nuclear motion
of a molecule in eldfree space takes the following simple form in spacexed Cartesian
center of mass coordinates X

H =
N

a=1

_
h
2
2m
a

2
X
2
,a
_
+ V (X) (1)
h is Plancks constant h devided by 2. N is the number of atoms and m
a
are their masses.
labels the Cartesian axes. V is the potential energy. In principle the Schrodinger
1
equation can be solved directly with the Hamiltonian given in the form of Eq.(1), but
usually one would like to formulate the Hamiltonian in terms of coordinates that are
adapted to the molecules motion, i.e. coordinates that come as close as possible to
a separable picture by minimizing the coupling between dierent degrees of freedom.
Over the years various schemes have been suggested for the derivation of rovibrational
kinetic energy operators [46]. Starting from Eq.(1) the rovibrational Hamiltonian for
any coordinate system can be written in terms of the total angular momentum

J and
generalized vibrational coordinates q
k
and their conjugate momenta p
k
= h/q
k
[7]:

H =
1
2
_

J
t
,

p
t
_
_
I C
C
t
g
_
1
_

J

p
_
+ u + V (2)

J and p are column vectors with components

J

and p
k
, respectively. t indicates the
transpose. I is the instantaneous tensor of inertia and g is the covariant vibrational
metric tensor. C is the Coriolis coupling matrix. u is a mass dependent pseudo potential,
which results from the curvature of the rotational and vibrational coordinates but only
depends on the latter [7].
u(q
1
, q
2
, . . .) =
h
2
8

j,k
{G
jk
f
k
}
q
j
+ f
j

G
jk
4
f
k
(3)
f
j
=

q
j
n

I C
C
t
g

(4)
G
ij
are the vibrational elements of the contravariant metric tensor and | | indicates the
determinant. The only condition the {q
j
} must fulll is that they dene the molecular
geometry unambiguously, i.e. X(q) must be singlevalued. Explicit expressions for the
components of I, C, and g follow immediately:
I

a
m
a
(e

x
a
) (e

x
a
) (5)
C
j
=

a
m
a
(e

x
a
)
x
a
q
j
(6)
g
jk
=

a
m
a
x
a
q
j

x
a
q
k
(7)
e

( = x, y, z) are unit vectors along the Cartesian coordinate axes , and x

a
is the
Cartesian coordinate vector of atom a, all referring to the (rotating) moleculexed centre-
of-mass coordinate system. Even if other approaches may be more convenient to derive
analytical expressions for the metric tensor elements, Eqs.(27) are exact and completely
general. They are particularly suitable in combination with grid based representations
2
of the Hamiltonian where the metric tensor elements can be calculated by numerical
dierentiation and pointwise inversion without any further algebra [8, 9]. The Zmatrix
DVR combines this approach with a exible denition of the geometry in terms of local
polar coordinates and a generalized Chebychev discrete variable representation (DVR,
see [10] for a recent review of DVR methods): the result is a method for the treatment
of rovibrational dynamics with a very wide range of applicability. It includes the exact
treatment of all six vibrational degrees of freedom of tetratomic molecules up to high
excitation energies, not only in the semirigid limit (CH
2
O) but also including large
amplitude torsion (H
2
O
2
) and inversion (NH
3
) dynamics [8]. Most importantly, Eqs.(2
7) are not limited to the exact fulldimensional treatment of intramolecular dynamics.
Rather the Z-matrix DVR provides a unied approach to vibrational quantum dynamics
including the fulldimensional treatment as a special case. Recent applications include
multidimensional models of the torsioninversion tunneling [11,12] and photodissociation
dynamics [13] of hydroxylamine (NH
2
OH) as well as the intermolecular rovibrational
dynamics of CH
+
3
Rg dimers (Rg=He,Ne) [14].
3 Normal Coordinate Models for High Excitations
A particularly simple form of the kinetic energy arises for normal coordinate models. Here
the covariant tensor g is diagonal so that the kinetic energy becomes almost separable as
long as Coriolis couplings can be neglected in Eq.(2):

H = hc
_
3N6

k=1

k
2
p
2
k
_
+ V (q
1
, q
2
, ..., q
3N6
) (8)
q
k
= Q
k

k
hc
h
2
(9)
Q
k
are the usual massweighted normal coordinates and
k
are the corresponding har-
monic wavenumbers. This formulation has been particularly useful for deriving clamped
coordinate models (i.e. setting q
k
, p
k
= 0 except for a few dynamically relevant coor-
dinates) to describe the approximate separation of light atom CH stretchbend chro-
mophore dynamics from the remaining vibrations of the molecular frame (see refs.
[2, 3, 15, 16] and references cited therein). A physically intuitive justication for this
approximation lies in the small displacements of the molecular frame coordinates even
though the chromophore vibrates with fairly large amplitudes. The vibrational angu-
lar momentum coupling roughly scales with the inverse tensor of inertia, which is small
and approximately constant for a suciently large molecular frame as long as its average
excitation remains low. An analogous reasoning usually justies the neglect of pseudo
potential and vibrational angular momenta within the chromophore subspace [15, 16]. In
contrast to local internal coordinate descriptions normal coordinate models account for
the small amplitude vibration of the molecular frame up to quadratic contributions. By
no means limited to semirigid CH chromophores (CHXYZ [2, 3, 1517], CH
2
O [18]), this
ansatz is generally valid for systems with XH vibrations, including molecules with amino
3
(NH) and hydroxyl (OH) groups. Its validity extends to the bound dynamics of molecules
with oppy degrees of freedom, such as internal rotation or inversion [11, 12, 19, 20],
as long as the characteristic time scales associated with the large amplitude motion are
suciently dierent from those of the (fast) bound dynamics.
The formulation of the model Hamiltonian in reduced normal coordinates q
k
(eq.8) al-
lows for a useful scaling procedure to correct for small deciencies typical for ab initio
calculated model potential energy surfaces. In general such calculations tend to overes-
timate harmonic wavenumbers. In the harmonic limit this error can be removed exactly
by replacing the reference wavenumber
k
in (eq.8) with

scaled
k
=
_

exp
k

ab initio
k
_
2

k
(10)
where
ab initio
k
and
exp
k
are the calculated and the experimental fundamental wavenum-
bers, respectively. Provided anharmonicities are small (a few percent) this scaling proce-
dure oers a simple and ecient way for adjusting ab initio calculated potential energy
functions with only a single parameter per dimension. As this parameter is directly deter-
mined from observed fundamental transitions the method allows for a true prediction of the
overtone spectrum. Deviations between calculated and observed transition wavenumbers
are typically halved compared with pure ab initio results. The scaled normal coordinate
model was instrumental in analysing the mode specicity of the rovibrational dynamics
underlying the overtone spectrum of hydroxylamine (NH
2
OH) from the far infrared up to
the visible range of the spectrum [11, 12, 21]. Combining this approach with reaction path
models for the various large amplitude motions yielded an almost complete picture of the
intramolecular energy ow in NH
2
OH up to excitations close to the dissociation limit.
This includes the large amplitude limit of the NOH bending motion, the isomerization to
ammonia oxide (NH
3
O) via intramolecular proton transfer.
4 Adiabatic Reaction Path Models
With Eqs.(27) vibrational coordinates need not be given in closed form in terms of
the molecular geometry. An important class of coordinates for the description of large
amplitude motions in larger molecules, are the reaction path coordinates, loosely dened
as a path on the potential energy hypersurface connecting reactants and products. The
remaining coordinates required for a complete parameterization of the molecular geometry
can be dened as normal coordinates by projecting the displacement along the reaction
path out of the molecular conguration space at each value of the reaction path coordinate
[22]. For an Natomic nonlinear molecule Eqs.(27) lead to the following rovibrational
Hamiltonian in terms of a large amplitude (reaction path) coordinate q and a set of 3N7
normal coordinates Q, their conjugate momenta (

J
q
and

P, respectively), and the angular
momentum

J
x,y,z
:
4

H =
_

J
_
t

J
_
+

P
2
k
+ u(q,

Q) + V (q,

Q) (11)
=
_
I C

C
_
1
(12)
This form closely resembles the DarlingDennison normal coordinate Hamiltonian with
the usual denitions [23]. The only dierence is that the angular momentum operators

J
and have a fourth element referring to the reaction path coordinate, with corresponding
elements of I and C :
I
q
= e

a=1
_
(s
a
s

a
) +
3N7

k=1
Q
k
_
2
_

ak
s

a
_
+
3N7

l=1
Q
l
_

ak

am
_
__
(13)
I
qq
= |s

+

k
Q
k
|
2
(14)
C
k,q
= s

k
+
3N7

l=1
Q
l
_

l
_
t

k
(15)
The prime denotes the derivative with respect to q.

k
are displacement vectors with
respect to the massweighted Cartesian reference geometry s(q), which denes the reaction
path. So far the formalism is exact. Within the RPH model we now introduce the
adiabatic ansatz for the eigenfunctions
(n)
m
(Q, q) of the full Hamiltonian

H:

(n)
m
(Q, q) =
(n)
m
(q)
n
(Q; q) (16)
_

n
|

H|
n

Q
E
(n)
m
_

(n)
m
(q) = 0 (17)
The semicolon indicates a parametric dependence on q and
Q
the integration over Q.
In the exact adiabatic picture
n
(

Q; q) are the eigenfunctions of the Hamiltonian for

J
q
= 0. Here we approximate them by a product of 1D harmonic oscillator eigenfunctions

(k)
n
k
(Q
k
; q) so that n becomes a multiindex.

n
(Q; q) =
3N7

k=1

(k)
n
k
(Q
k
; q) (18)
Except for the high OH stretching overtones [24] we completely neglect the Qdependence
of I and C, Eq.(11). Compared with the neglect of the anharmonicities and the direct
product ansatz of eq.(18) this only leads to minor additional errors but substantially
5
simplies the calculation. Thus eq.(17) reduces to the 1D motion in q with eective
adiabatic channel potentials
n
(q) for each level n.
_

n
|

J
q

qq

J
q
|
n
+
n
(q) E
(n)
m
_

(n)
m
(q) = 0 (19)

n
(q) =
3N7

k=1
_
n
k
+
1
2
_

k
+
1
2

,=x,y,z,q

n
|

|
n
+ u(q,

0) + V (q,

0) (20)

(n)
m
(q) are the eigenfunctions associated with adiabatic channel (n). This approach has
been validated for the torsional stereomutation tunneling in hydrogen peroxide both
against exact adiabatic channel calculations and against fully coupled results [25] on
a global 6D potential energy hypersurface [26]. It was possible to analyse the pronounced
mode selectivity observed experimentally in the rovibrational spectra. The phenomenon
was shown to result from the adiabaticity of the torsional quantum dynamics, which was
found to be preserved up to very high OH stretching excitations, possibly even beyond
the OO dissociation limit. With the simplications of Eqs.(1620) the adiabatic reaction
path model can be extended to much larger polyatomic systems as demonstrated with its
application to the 36dimensional (36D) inversion tunneling dynamics of aniline [27].
5 Conclusion
The continuing progress in computer technology keeps extending the range of systems
whose quantum dynamics can be treated (numerically) exactly in all degrees of freedom.
But it seems doubtful that much insight is to be gained from such a calculation for -
say - a DNA molecule even if it were feasible. True chemicalphysical understanding will
always come from simplied models to describe regularities and approximate symmetries.
There is a large variety of approaches to choose from of which this short survey could
only sketch a few. In the quantum dynamics of large amplitude motion, however, a
common feature seems to be emerging with the phenomenon of vibrational adiabaticity.
Exploring its dynamical implications for intramolecular energy redistributions as well
as for reactive processes will be one of the major challenges in the eld of molecular
quantum dynamics.
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7
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CH
3
OH and
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8