1618 Volume 55, Number 12, 2001 APPLIED SPECTROSCOPY

0003-7028 / 01 / 5512-1618$2.00 / 0
q 2001 Society for Applied Spectroscopy
Global Phase Angle Description of Generalized
Two-Dimensional Correlation Spectroscopy:
1. Theory and its Simulation for Practical Use
SHIN-ICHI MORITA, YUKIHIRO OZAKI,* and ISAO NODA
Department of Chemistry, School of Science, Kwansei-Gakuin University, 2-1 Gakuen, Sanda, Hyogo 669-1337, Japan (S.-I.M.,
Y.O.); and The Procter and Gamble Company, 8611 Beckett Road, West Chester, Ohio 45069 (I.N.)
The concept of a global phase map derived from generalized two-
dimensional synchronous and asynchronous correlation spectra is
introduced to extract the purely correlational information by inten-
tionally canceling amplitude information. For the practical usage of
a global 2D phase map, a ltering method based on the standard
deviation spectrum obtained from the time series intensity proles
is proposed to remove the effect of small amplitude noise. A simu-
lation created with the use of three synthesized bands with expo-
nential decay has clearly detected the only difference in the char-
acteristic rate constant of the decay process in the global 2D phase
map, although the three bands have different initial values of the
peak intensity amplitudes.
Index Headings: Generalized two-dimensional correlation spectros-
copy; Phase angle; Normalization of the amplitudes.
INTRODUCTION
The basic concept of two-dimensional (2D) infrared
spectroscopy was proposed by Noda in 1986.
13
In the
early stage of 2D correlation spectroscopy, a simple
scheme of cross-correlation analysis was used to generate
synchronous and asynchronous 2D maps from sinusoi-
dally varying dynamic infrared signals. Such dynamic 2D
correlation spectra are very useful in emphasizing spec-
tral features not readily obser vable in conventional one-
dimensional spectra. 2D infrared spectroscopy has been
especially successful in the studies of systems stimulated
by a small-amplitude mechanical or electrical perturba-
tion.
4
However, this type of 2D correlation spectroscopy
has one serious limitation;
13
the time-dependent behavior
(i.e., waveform) of dynamic spectral intensity variations
must be a simple sinusoid to effectively employ the orig-
inal data analysis scheme.
In order to overcome the above limitation, Noda
5
in-
troduced a more generally applicable method in 1993 as
an extension of the original 2D correlation scheme. This
method, called generalized 2D correlation spectroscopy,
is applicable to any transient or time-resolved spectra
having an arbitrar y waveform. Moreover, the extension
to various areas of spectroscopy, e.g., near-infrared, Ra-
man, and uorescence spectroscopy, has become straight-
for ward.
The generalized 2D correlation spectroscopy has pro-
vided new opportunities for analyzing optical molecular
spectra. One can now nd a great number of useful ap-
plications for generalized 2D correlation spectroscopy.
6,7
The advantages of generalized 2D correlation spectros-
copy lie in the following points:
Received 4 April 2001; accepted 6 August 2001.
* Author to whom correspondence should be sent.
(1) Due to the intrinsic deconvolution ability, spectral
features not readily observable in conventional one-
dimensional spectra may be highlighted.
(2) Various inter- and intra-molecular interactions may
be identied through selective correlation of bands.
(3) Spectral responses can be examined concerning
which are in phase or out of phase with each other.
(4) Band overlapping or band shift by the pattern
recognition of two-dimensionally expanded asyn-
chronous peaks can be distinguished.
(5) Systematic band assignments based on the correlation
between various bands can be made.
(6) Correlation study between bands in two different
kinds of spectroscopic techniques (so called heter-
ospectral correlation) can be performed.
Although generalized 2D correlation spectroscopy has
a number of well-recognized advantages, its interpreta-
tion is often not straightfor ward. One of the important
factors that may obscure the information presented by 2D
correlation spectra is that spectral intensity variations
have different amplitudes. In conventional generalized
2D spectroscopy, we calculate dynamic spectra that are
obtained by subtracting a reference spectrum from a se-
ries of original spectra. The amplitudes of dynamic spec-
tra, therefore, correspond to the magnitude of intensity
deviations from the reference spectrum at different fre-
quencies. The amplitude variations for different bands
yield complicated generalized 2D synchronous and asyn-
chronous maps superimposed with overwhelming and of-
ten unwanted spectral amplitude information. One can
often recognize at best the positions and signs of corre-
lation peaks without obtaining any additional useful in-
formation. If one could effectively normalize the ampli-
tude contributions, it would be possible to obtain more
useful and easy-to-interpret peak intensities in the 2D
synchronous and asynchronous maps.
A well-known procedure for the normalization of a set
of amplitude variations is to divide them by the standard
deviation. In general, this method is valid for random
noise. More specically, this normalization technique
works most effectively for amplitude variations obeying
a linear relationship. Another normalization method is to
use a scale between the maximum and minimum value
in the intensity prole. However, this approach also does
not work well as a normalization technique for strongly
nonlinear responses.
The discussion on peak intensities in generalized 2D
correlation maps was reported by a few researchers.
811
Mu ller et al.
8
proposed the idea of relative phase in the
APPLIED SPECTROSCOPY 1619
2D infrared correlation spectroscopy, where the pertur-
bation and responses were limited to sinusoidal systems.
A benet of such a relative phase concept was that one
can cancel amplitude information. Recently, Noda
9
ex-
panded the idea of relative phase in the sinusoidal sys-
tems to nonperiodic systems in generalized 2D correla-
tion spectroscopy. This expanded relative phase angle
was named as a global correlation phase angle. Accord-
ing to Noda,
9
this global correlation phase angle serves
as a semi-quantitative index, although it lacks any direct
physical signicance, like a phase shift obser ved in si-
nusoidal signals. Ekgasit and Ishida
10
attempted the use
of normalized spectra. However, their approach requires
a priori knowledge of waveforms, making the practical
utility of their analysis rather limited. Buchet et al.
11
also
presented an idea similar to the global phase angle for
discriminating physically meaningful correlation peaks
from artifactual correlation peaks. Generalized 2D cor-
relation phase maps with normalized amplitude based on
the global phase angle seem to be a reasonable approach.
However, there is one major problem for the practical
usage of phase maps: articially enhanced noise contri-
butions often associated with such normalization of the
spectral amplitude.
In this article, we start with the development of a basic
concept of global phase. We then report an illustrative
simulation example, which employs exponentially decay-
ing bands. A new signal ltering scheme based on the
use of a standard deviation spectrum has been proposed
to blind unwanted noise contributions. In the following
paper,
12
we report an application of the global phase angle
description of generalized 2D correlation to actual ex-
perimental data. As an example, temperature-dependent
infrared transmission spectra of an eleven-layer Lang-
muir-Blodgett (LB) lm of 2-dodecyl-7,7,8,8-tetracyan-
oquinodimettane (dodecyl-TCNQ) are investigated.
While the idea of global phase angle description has
implicitly been included in the classical generalized 2D
correlation map, this is the rst time that the idea has
been applied to a realistic spectra with a nite level of
noise contribution, as often encountered in actual exper-
imental systems.
THEORETICAL BACKGROUND
Sinusoidal Systems. The simplest form of 2D IR cor-
relation spectra can be obtained by using a sinusoidal
perturbation and responses as originally proposed by
Noda.
2,3
Sinusoidal responses with a xed period T ob-
served at frequencies n
1
and n
2
are represented by
y 5 a(n )cos[2pt /T 1 u ] 1 b(n ) (1)
1 1 1 1
y 5 a(n )cos[2pt /T 1 u ] 1 b(n ) (2)
2 2 2 2
where a(n
j
), t, u
j
, and b(n
j
) are amplitude, time, phase lag,
and offset value of the sinusoidal responses at the
frequency of n
j
( j 5 1 or 2), respectively. The synchro-
nous and asynchronous correlation intensities can be ob-
tained as
1
F(n , n ) 5 a(n )a(n )cos(u 2 u ) (3)
1 2 1 2 1 2
2
and
1
C(n , n ) 5 a(n )a(n )sin(u 2 u ) (4)
1 2 1 2 1 2
2
We now introduce the normalized synchronous and
asynchronous correlation functions and combine these
functions with the concept of a correlation phase. In a
sinusoidal system, these amplitudes, a(n
1
) and a(n
2
), can
be regarded as radii of assumed uniform circular motions
of response vectors (i.e., phasors) on a complex phase
plane derived from the sinusoidal responses. Thus, one
can obtain normalized asynchronous and synchronous
functions as
F(n , n )
1 2
F (n , n ) 5 5 cos(u 2 u ) (5)
n 1 2 1 2
1
a(n )a(n )
1 2
2
C(n , n )
1 2
C (n , n ) 5 5 sin(u 2 u ) (6)
n 1 2 1 2
1
a(n )a(n )
1 2
2
Such representations of F
n
(n
1
, n
2
) and C
n
(n
1
, n
2
) are
straightforward extensions of the basic concept of 2D
correlation. Now one must consider the phase relation-
ship manifested in the 2D correlation analysis. The phase
difference between the two responses at the frequencies
n
1
and n
2
can be determined as follows:
C (n , n )
n 1 2
Q(n , n ) 5 arctan 5 u 2 u (7)
1 2 1 2
5 6
F (n , n )
n 1 2
Thus, for sinusoidally varying signals, one can obtain
F
n
(n
1
, n
2
), C
n
(n
1
, n
2
), and Q(n
1
, n
2
) with the simple nor-
malization of the amplitude from Eqs. 5, 6, and 7.
However, the above process of obtaining Q(n
1
, n
2
) is
not applicable in a straightfor ward manner for nonper-
iodic signals. The following process of directly calculat-
ing Q(n
1
, n
2
) may be more effective, as will be discussed
later:
C(n , n )
1 2
Q(n , n ) 5 arctan (8)
1 2
5 6
F(n , n )
1 2
Equation 8 implies that F(n
1
, n
2
) and C(n
1
, n
2
) with rather
complicated amplitude information can be directly re-
duced to Q(n
1
, n
2
) without any conscious normalization
of amplitude.
Nonperiodic Systems. It is now well recognized that
for any type of nonperiodic perturbation and responses,
one can obtain generalized 2D correlation maps. The the-
oretical framework needed to obtain the generalized 2D
correlation function was developed by Noda.
5
The prac-
tical computational method of generalized synchronous
and asynchronous spectrum, F(n
1
, n
2
) and C(n
1
, n
2
), was
also proposed by Noda.
13
The generalized synchronous correlation function F(n
1
,
n
2
) is equivalent to the time-average of the product of
dynamic spectral intensity variations measured at two dif-
ferent spectral variables, n
1
and n
2
. The generalized asyn-
chronous intensity variation C(n
1
, n
2
), on the other hand,
is calculated by the time-domain Hilbert transformation
of dynamic spectra.
13
For the dynamic spectral intensity
variation at n
2
, the Hilbert transformation along the time-
domain axis is carried out to produce the mathematically
orthogonal function, equivalent to the signals phase shift-
ed by 90 degrees. The generalized asynchronous corre-
lation function C(n
1
, n
2
) thus becomes identical to the
1620 Volume 55, Number 12, 2001
FIG. 1. Simulated spectra for calculating a phase map from the gen-
eralized 2D correlation spectra. The three bands have Gaussian form
and obey the exponential decay for the time axis.
time-average of the product between the dynamic spectral
intensity variation at n
1
and the phase-shifted dynamic
spectral intensity variation at n
2
.
To extract the information on the degree of correlation,
the use of global phase, which can be obtained by the
procedure described in Eq. 8, becomes especially con-
venient. For a pair of simple sinusoidally varying spectral
intensities, the correlation phase angle represents the ac-
tual phase difference between the two signals. For non-
periodic signals having complicated waveforms, the glob-
al correlation phase angle no longer has any simple phys-
ical meaning, such as a xed time delay. However, it still
ser ves as a convenient index to estimate the similarity
between two nonperiodic signals.
SPECTRAL ANALYSIS
The generalized 2D synchronous and asynchronous spec-
tra were calculated using a software called 2D-Pocha
composed by D. Adachi (Kwansei-Gakuin University). The
generalized 2D phase maps were calculated in Microsoft
Excel 97 with data sets exported from 2D-Pocha.
PHASE MAP WITH A BLINDING FILTER
As already pointed out, a practical application of glob-
al 2D phase maps has not been successfully carried out
in the past because of the unintentional enhancement of
noise, especially in the baseline region with a low level
of signals. The cancellation of amplitude information re-
sults in the exaggeration of noise contribution in some
parts of the global phase maps. To generate more infor-
mation-rich 2D phase maps, the use of a standard devi-
ation spectrum is proposed as a convenient basis for de-
veloping a noise ltering scheme.
Modifying Eq. 8, a practical global phase map free
from exaggerated noise can be calculated as follows:
Q(n , n )
1 2

arctan{C(n , n ) /F(n , n )}
1 2 1 2
if F(n , n ) . d and F(n , n ) . d
1 2 1 2
5 (9)
blind (i.e., not defined value)

otherwise

where d is a small threshold value of mathematical blind-

ing lter. In this paper, the parameter d is selected in the
standard deviation spectrum of signal measured at wave-
number n. The selection of d is not very rigorous, but we
recommend setting the value of d at ten times a standard
deviation value in the baseline region. The standard de-
viation spectrum SD(n) is given by the square root of F(n,
n). This standard deviation lter is set to be rather con-
servative such that the potentially artifactual inuence
from the contribution of any weak signal regions will be
rejected. This approach has the pragmatic simplicity and
clarity suitable for securing the robustness of the operation.
SIMULATION
By using simulated spectra (Fig. 1), a procedure for
calculating a global phase map from the generalized 2D
correlation synchronous and asynchronous maps is dem-
onstrated. Three bands, A, B, and C, obeying the expo-
nential decay along the time axis, are used for the sim-
ulation of the global phase angle map (Fig. 1). We as-
sume a Gaussian form to describe the peak shape of these
bands, represented by
21
2
(n 2 m )
j
y (n, t) 5 I exp exp(2k t)
j j j
2
5 6
5
j 5 A, B, and C (10)
where I
j
is the initial value of peak maximum intensity,
m
j
is the peak maximum position, and k
j
is the charac-
teristic rate constant of the decay process. In this simu-
lation, for the bands A (m
A
5 20), B (m
B
5 50), and C
(m
c
5 80), we set the initial values and the rate constants
as I
A
5 1.0, I
B
5 0.20, and I
C
5 0.50, and k
A
5 0.1, k
B
5 0.2, and k
C
5 0.1, respectively. It is noted that I
j
rep-
resents the scaling factor to determine only the amplitude,
while k
j
reects exclusively the exponential decaying
waveform of the band, independent of the amplitude. We
add random noise to the intensity variation, whose stan-
dard deviation is about 0.001.
We rst calculate synchronous and asynchronous 2D cor-
relation maps by the usual method (Figs. 2a and 2b). It is
easy to observe the basic correlation patterns in the corre-
lation maps. However, these two maps are hopelessly dom-
inated by the amplitude information. Therefore, we tend to
miss the detailed quantitative feature of nonlinear responses
in the asynchronous map. In Fig. 2a, synchronous correla-
tion peaks concerned with the band B are not visible at all
due to the small amplitude of band B. Moreover, it is im-
possible to discuss the signicance of peak heights in either
the synchronous or the asynchronous map. In order to cal-
culate the global 2D phase map masked by Eq. 9, we used
the standard deviation spectrum (Fig. 3). The global phase
map thus calculated is shown in Fig. 4.
Compared to conventional 2D correlation maps, a glob-
al 2D phase map is much more straightforward for ex-
tracting the pure correlational information. The global 2D
phase map (Fig. 4) shows temporal correlation of time-
dependent behavior without being obscured by any am-
plitude information. We used degrees as a unit of global
phase angle. Note that the masked region, determined by
the blinding condition (Eq. 9), is distinguished from the
correlated region as the undened value. For a nonperiodic
system, the asynchronous axis does not usually present any
APPLIED SPECTROSCOPY 1621
FIG. 2. (a) Synchronous and (b) asynchronous 2D correlation spectra
calculated by the conventional method.
FIG. 4. The global 2D phase map.
FIG. 3. The calculated standard deviation spectrum. The parameter d
is set as shown in this gure.
tangible physical meaning beyond a collective mathemat-
ical projection. Although it is difcult to rigorously discuss
the quantitative meaning of the global phase intensities
aside from certain specialized cases, we can still use the
global phase angle as a convenient semi-quantitative index
for detecting the nature of nonlinear responses.
CONCLUSION
In this paper we have demonstrated the practical usage
of the global phase map derived from the generalized 2D
synchronous and asynchronous correlation maps. To
make this approach applicable to realistic data containing
a substantial level of noise, a ltering scheme based on
the standard deviation spectrum of dynamic spectra has
been proposed. It has been found that one can cancel the
amplitude information and accentuate the purely corre-
lational information by using the generalized 2D phase.
In the following paper, we report the rst example of the
application of the generalized 2D phase map method to
experimental data.
While we have focused on a simulation of the band
intensity variations as the rst step, the other factors
band shifts and broadeningsmust be discussed in order
to interpret the maps in more detail. We will treat these
simulations in the near future.
ACKNOWLEDGMENT
The authors thank Mr. Y. Nagasaki (School of Science, Kwansei-
Gakuin University) for valuable discussion and continuous encourage -
ment.
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