Journal of the Chinese Chemical Society, 2002, 49, 797-804 797

Theory of the Stark Effect on Single Molecular Spectroscopy

M. Hayashia*, C. H. Chianga ( ), K. K. Liangb ( ), Y. J. Shiub ( ),

b b
C. H. Chang ( ), D. Y. Wu ( ), F. Y. Lic ( ),
T.-C. Changb ( ), U. Wildd , T. Y. Latychevskaia d and S. H. Linb ( )
a
Center for Condensed Matter Sciences, National Taiwan University, Taipei 106, Taiwan, R.O.C.
b
Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei, Taiwan 106, R.O.C.
c
Department of Applied Chemistry, National Chi Nan University, Nantou 545, Taiwan, R.O.C.
d
Swiss Federal Institute of Technology Zürich, Zürich, Switzerland

In this work, we study a mechanism of the Stark effect on single molecular spectroscopy using the pertur-
bation method. In particular, mechanisms of the induced dipole moment of a molecule imbedded in polar and
non-polar host molecules are theoretically investigated by applying LCAO MO to a guest molecule. Ab initio
calculations are performed to study how the distance between a guest and a host molecule affects the induced
dipole and quadrapole moments. We have found that the induced dipole moment is very sensitive to short
range configurations while the induced quadrapole moment can be affected by longer range configurations.

INTRODUCTION
r r (1-2)
Ĥ F
The first Single-molecular Spectroscopy (SMS) experi- r
r
ment was performed in 1989 using absorption spectroscopy where and F stand for the dipole operator and the applied
and a sophisticated modulation technique. 1 Single molecules elec tric field, re spec tively. Sub sti tuting Eq. (1-2) into Eq.
can be detected and manipulated in various environments. On (1-1) yields,
solid sur faces, for in stance, they can be stud ied us ing the
r r 1 r t r
scanning probe techniques of STM2 and SNOM.3 Single mol- En En F F n F L
0
n
(1-3)
ecules can also be detected in liquids and in biological sam- 2
r r r 0 r
ples us ing flu o res cence ex ci ta tion.4 With the in ven tion of where n represents the dipole moment n n| | n
0
t nn
SMS, the investigation of single dye molecules buried deep and n denotes the polarizability
inside a transparent solid becomes feasible.5-8 r r
t t mn nm
In the SMS literature, experiments on single molecules n nn
2 (1-4)
E m En
0 0
m n
in electric fields are called the Stark effect. The first measure-
r r 0 r 0
ment on single molecules in an electric field were performed Here nm is the tran si tion di pole mo ment nm n| | r .
r r m
in 1992 by Wild et al. 9 for the sam ple of pentacene in p- From Eq. (1-3), one can see that only when n 0 or n F
t
terphenyl crystal. In the following years, the spectral shifts of 0, can we observe the linear Stark effect. Since n 0 for all
single molecule resonances external electric fields were ob- sys tems, the sec ond-order Stark ef fect can usu ally be ob-
served for various host/guest systems: ferrylene in polyethyl- served provided that the field is strong enough.
ene, 10 perylene in n-nonane, 11 terrylene in naphtha leln, 12 Using Eq. (1-3), one can calculate the spectral shift due
dibenzanthanthrene in naphtalene and in HD matrices,13 etc. to the electric field as follows,
According to the time-independent perturbation method,
r r r
to the second-order approximation, the energy of the system Enm En Em ( En0 Em0 ) ( n m ) F
can be expressed as 1 r t t r (1-5)
F ( n m) F L
| H nm | 2 2
En En0 H nn L (1-1)
m n En0 Em0 In other words, the central problem in the linear Stark effect
r r
where H$ ' represents the perturbation. For the Stark effect, H$ ' of SMS is the cal cu la tion of n and m in duced by sol vent
is given by molecules.

Dedicated to the celebration of the seventieth anniversary of Chemical Society the located in Taipei.
798 J. Chin. Chem. Soc., Vol. 49, No. 5, 2002 Hayashi et al.

2. THEORETICAL due to the dipole-electron interaction

2.1. General Consideration r r
e( m R i)
We shall consider a case in which a non-polar molecule V (3-1)
Ri
3
i
is dissolved in a solvent crystal. It should be noted that Wild
r
group has observed the linear Stark effect in the fluorescence where m denotes the dipole moment of AB, a solvent mole-
spec tra of non-polar sol ute mol e cules in both po lar and cule and
non-polar solvent matrices. This means that a dipole moment r r r
can be in duced in the sol ute mol e cule by the po lar or Ri R ri (3-2)
non-polar surrounding (or heat bath). In this section, we shall
offer an interpretation for this phenomenon in terms of a mo- For R ri, it follows that
lecular description based on the perturbation method. r r r r r r
( m ri ) 3( m R )( R ri )
Let us now con sider a mech a nism as to how a di pole V e L (3-3)
R R
3 5
i
moment can be induced by an interaction with environmental
molecules. For this purpose, let V describe the interaction be- and that
tween the sol ute mol e cule and sol vent mol e cules. In this r r r r r r
(m ) 3( m R )( R )
L (3-4)
eg eg
V
0 0
case, electronic wavefunctions of the solute molecule can be e g
R R
3 5

perturbed by V
where
0
V 0

L
0 e g 0
g g
Eg0 Ee0
e (2-1) r r
eri
0 0
e g
eg e g
. (3-5)
i
and
0
V 0
Similarly, we have
L
0 e e 0
e e e (2-2)
e e E 0
e E 0
e
V
0 0
e e

where, for ex am ple, | g and | e de note the elec tronic r r r r r r

(m ) 3( m R )( R )
wavefunctions of the ground and elec tron i cally ex cited ee e e
L (3-6)
R R
3 5

states, respectively. The induced dipole-moments can be de-

fined as
2.3 A non-polar molecule dissolved in a non-polar crystal
r ind r 0 r 0
g g g g g
(2-3) In this section, we shall consider the case of a non-polar
molecule dissolved in a non-polar crystal. Suppose that we let
and A repre sent the sol ute mol e cule while we let D rep re sent a
solvent molecule. Then the interaction between them can be
r ind r 0 r 0
e e e e e
(2-4) written by
r t r
rD D
rD
V e
2 i i
Substituting Eqs. (2-1) and (2-2) into Eqs. (2-3) and (2-4), re- (4-1)
2 rD
6
D i
spectively, yield
t
i

where D denotes the polarizability tensor of D,

r ind V r
0 0

2
e g 0 0
L (2-5) r r
g
Eg
0
Ee
0 g e
t nn nn
e g
D
2 (4-2)
and n En En
r
Here n ' n is the tran si tion mo ment of D. t
r ind V r t
0 0

L (2-6) I
e e 0 0
2 For an isotropic D molecule, we notice that D D
e e e
Ee Ee
0 0
e e and Eq. (4-1) becomes
e
2

2.2 A non-polar molecule dissolved in polar molecules V D

(4-3)
2 rDi
4
From Section 2.1, we can see that the central question D i
where
in this problem is the calculation of 0e ' |V | 0g and 0e ' ' |V | 0e . r r
1 1 4( RDA rAi )
In this section, we shall first consider the case of a non-polar L (4-4)
rDi RDA RDA
4 4 6
molecule dissolved in polar molecules. The V in this case is
Theory of the Stark Effect on Single Molecular Spectroscopy J. Chin. Chem. Soc., Vol. 49, No. 5, 2002 799

It follows that and

r r
2 D ( RDA e g ) 1 ( 5 1) ( 5 1)
V L (4-5) [ ] (5-8)
0 0
4 a b c d
e g 2 2
RDA
6
D
5 5
r r where { i} and {Wi} represent the atomic orbitals and orbital
2 D ( RDA eg )
V L
0 0
e g
(4-6) energies, respectively. It follows that
RDA
6
D

and 0
| | (5-9)
r r
g 1 1 2 2

2 D ( RDA e g )
V L.
0 0
e g
(4-7)
D RDA
6
0 1
e1
(| 1 1 2 3
| | 1 1 2 3
|) (5-10)
Here the sum over D refers to the summation over the solvent 2
molecules. 1
0
In con clu sion, in this sec tion based on the use of the e2
(| 1 1 2 4
| | 1 1 2 4
|) (5-11)
perturbation method we propose a theory of linear Stark ef- 2
fect for non-polar molecules dissolved in a polar matrix and a where, for ex am ple, | 1 1 | de notes the Slat er de ter mi-
non-polar matrix. For the latter, the induced dipole moment nant. The energy of each state corresponding to Eqs. (5-9)-
arises from the asymmetric orientation of the solvent motion (5-11) can be, respectively, given by
in the solvent cage and/or from the structure asymmetry of
Eg 2W1 2W2
0
the solvent cage. (5-12)

APPLICATION Ee 2W1 W2 W3
0
(5-13)
1

LCAO MO method
In this section, we shall show how induced dipole mo- and
ments can be expressed in terms of molecular orbital theory.
Ee 2W1 W2 W4 .
0
For sim plic ity, let us ap ply the the o ret i cal re sults to the B (5-14)
2

elec trons of bu ta diene. No tice that the LCAO-MO method

gives us Using Eqs. (5-9)-(5-11), we obtain

( 5 1) (5-1)
W1 r ind 0
V 0
r
L
s g
2 g 2 0
g
0
s
s g E 0
g E 0
s
1 ( 5 1) ( 5 1)
(5-2) V r
0 0
1
[ a b c d
] e1 g
0 0
5 5 2 2 2 g e1
E 0
g E 0
e1

( 5 1)
W2 (5-3) 0
e2
V 0
g r
2 2 0
g
0
e2
(5-15)
E 0
g E 0
e2

1 ( 5 1) ( 5 1)
[ ] (5-4)
r ind V r
2 a b c d 0 0
2 2
L
s
5 5 e1 0 0
e1
2 e1 s

s e1 Ee 0
E 0
s
( 5 1) 1

W3 (5-5)
V r
0 0
2 g e1 0 0
2 e1 g

1 ( 5 1) ( 5 1) Ee 0
1
E 0
g

3
[ a b c d
] (5-6)
2 2 V r
0 0
5 5 e2 e1 0 0
2 e1 e2
(5-16)
( 5 1) Ee 0
Ee 0

W4 (5-7) 1 2

2 and
800 J. Chin. Chem. Soc., Vol. 49, No. 5, 2002 Hayashi et al.

r ind r ind r ind r r r r

r r
e1 g e1 g
m (eRba ) 3( m R ){R (eRba )}
Vmr ( R ) (5-21)
V r
0 0
R R
3 5
g e1 0 0
4 e1 g
Ee0 1
E g0
On the other hand, for a non-polar mol e cule dissolved in a
V r
0 0
e2 g
2 0 0
non-polar crystal, we obtain
r
g e2
E g0 Ee0 2

r ind r ind r ind eRba r

0
e2
V 0
e1 r e1 g e1 g C( ) V ( RDA ) (5-22)
D
0 0
2 e1 e2 (5-17a) D
Ee0 1
Ee0 2
where
r r
or r 2 D
{RDA (eRba )}
r ind r ind r ind V ( RDA ) . (5-23)
RDA
D 6
e1 g e1 g

V r Given the molecular properties for each case, one can

0 0
g e1 0 0
4 e1 g
roughly estimate the difference of induced dipole moment by
W3 W2
using Eq. (5-19) or Eq. (5-22).
V r
0 0

2
e2 g
0
g
0 Ab initio study
e2
W2 W4 In the previous section, we have shown, using LCAO
V r MO, molecular mechanisms of the induced dipole moment for
0 0
e2 e1 0 0
2 e1 e2 (5-17b) the two cases: (1) a non-polar molecule dissolved in polar mol-
W3 W4
ecules and (2) a non-polar molecule dissolved in a non-polar
or
r ind r ind r ind crystal. In this section, to understand the induced dipole and
e1 g e1 g induced quadruple moments more realistically, we shall apply
the ab inito calculation method to compute these induced mo-
2 2 V 3 r
4 2 3 2 ments of a model system. For this purpose, we consider a
W3 W2 model system consisting of a ethylene molecule and a rare gas
2 4 V 2 r molecule. This model is one of the simplest mod els for a
2 2 2 4
non-polar molecule dissolved in a non-polar crystal. For the
W2 W4
calculation method, we employ the Gaussian package14 and
4 V 3 r apply DFT with B3YKLP and 6-311+g** basis set to the
2 3 4 (5-17c)
W3 W4 ground state and that CIS with the same basis set to the excited
state. The main focus in this computation is to present the in-
Substituting the dipole moments and energies yields (see Ap-
duced moment as a function of the distance between the ethyl-
pendices A and B)
ene and the rare gas molecule. Table 1 lists the calculated di-
r ind r ind r ind
e1 g e1 g pole moments of the ethylene and He system as a function of
the distance between the two molecules. Fig. 1, for example,
2 2 V 3 (3 5)
4 ( eRba ) shows a geometry used for the calculation of ethylene and He
( 5 1) 2 (5 5)
4 V 3 2
2 ( eRba )
(5-18)
5

For a non-polar molecule dissolved in polar molecules,

Eq. (5-17) becomes (see Appendix C)
r
r ind r ind r ind eRba
e1 g e1 g C( ) Vmr ( R ) (5-19)
Side view Top view
where
2
4 3 5 8 Fig. 1. A geometry used for the calculation of ethylene
C and He at a distance of 3 Å.
(1 5) 2 (5 5) 5 (5-20)
Theory of the Stark Effect on Single Molecular Spectroscopy J. Chin. Chem. Soc., Vol. 49, No. 5, 2002 801

at a distance of 3 Å. Table 2 lists the calculated induced rare gas atom. From Fig. 2A, one can see that the induced di-
quadrapole moment of this system. pole moment of the ethylene+He system quickly decreases as
Fig. 2 shows the cal cu lated in duced di pole and qua- the distance increases larger than 1 Å and it becomes almost
drapole moments for ethylene+He, ethylene+Ne, and ethyl- zero with the distance larger than 2 Å. Within 2 Å similar
ene+Ar as a function of the distance between ethylene and a behavior can be seen in the xx and yy components of the in-
duced quadrapole moment of the same system. However, the
Table 1. Dipole Moment of Ethylene + He zz component of the induced quadrapole moment cannot be-
come zero within 6 Å. It is interesting to see other systems
Ground state Excited state
like the ethylene+Ne and ethylene+Ar systems. The results
Distance x y z x y z
are listed in Tables 3-6. The middle and last panels of Fig. 2
1 0 0 1.0145 0 0 3.7543 show the in duced dipole and quadrapole mo ments of these
2 0 0 0.4721 0 0 0.541
systems. A quick change of the amplitude of the induced di-
3 0 0 0.0843 0 0 0.0888
4 0 0 0.0214 0 0 0.0133
5 0 0 0.0064 0 0 0.0022
6 0 0 0.0006 0 0 -0.0002 Table 2. Quadrapole Moment of Ethylene + He
0 0 0 0 0 0 Ground state Excited state
In units of Debye Distance xx yy zz xx yy zz

1 -13.751 -18.190 -18.037 -14.911 -13.605 -23.464

2 -13.558 -13.576 -16.993 -13.48 -13.342 -17.230
(A) 3 (B) 6
H
3 -13.543 -13.503 -16.879 -13.461 -13.262 -17.172
He
4 e 4 -13.532 -13.483 -16.893 -13.460 -13.250 -17.195
2 2 5 -13.526 -13.476 -16.95 -13.460 -13.249 -17.215
0
6 -13.524 -13.474 -16.982 -13.459 -13.248 -17.230
1 -15.903 -12.434 -12.389 -16.171 -12.404 -12.193
-2 ind
xx
ind
-4 yy
ind
In units of Debye-Angstrom; xy = xz = yz = 0.
zz
0
-6
1 2 3 4 5 6 1 2 3 4 5 6
Distance / Angstrom Distance / Angstrom
Table 3. Dipole Moment of Ethylene + Ne
Ne Ne
Ground state Excited state
0.0 0 Distance x y z x y z

1 0 0 -0.9472 0 0 -1.5365
ind
2 0 0 0.5848 0 0 0.7364
-0.5
-1
xx

yy
ind 3 0 0 0.0738 0 0 0.1172
zz
ind
4 0 0 0.004 0 0 0.0114
1 2 3 4 5 6 1 2 3 4 5 6
5 0 0 0.0014 0 0 0.0009
Distance / Angstrom Distance / Angstrom 6 0 0 0.0002 0 0 -0.0006
Ar Ar
0 0 0 0 0 0
0 In units of Debye
0.0
-1

Table 4. Quadrapole Moment of Ethylene + Ne

-0.5 -2 ind
xx

yy
ind
Ground state Excited state
ind
-3 zz
Distance xx yy zz xx yy zz
1 2 3 4 5 6 1 2 3 4 5 6
Distance / Angstrom Distance / Angstrom 1 -22.554 -21.290 -32.100 -23.800 -21.972 -35.013
2 -16.913 -17.063 -21.119 -16.723 -16.723 -21.334
Fig. 2. The cal cu lated in duced mo ments for eth yl- 3 -16.862 -16.840 -20.382 -16.637 -16.446 -20.519
ene+He, eth yl ene+Ne, and eth yl ene+Ar. The 4 -16.828 -16.785 -20.277 -16.618 -16.405 -20.402
results; (A) induced dipole moments and (B) in- 5 -16.825 -16.782 -20.280 -16.62 -16.408 -20.391
duced quadrapole mo ments, are shown as a 6 -16.824 -16.782 -20.283 -16.619 -16.409 -20.392
function of the distance between ethylene and a -15.903 -12.434 -12.389 -16.171 -12.404 -12.193
rare gas atom. In units of Debye-Angstrom; xy = xz = yz = 0.
802 J. Chin. Chem. Soc., Vol. 49, No. 5, 2002 Hayashi et al.

Table 5. Dipole Moment of Ethylene + Ar work. MH and CHC would also like to thank the Na tional
Ground state Excited state Center for High-Performance Computing for Gaussian calcu-
Distance lation support. MH would like to thank NSC of the ROC for
x y z x y z
financial support (NSC-90-2113-M-002-024).
1 0 0 -3.4808 0 0 -4.242
2 0 0 0.6714 0 0 0.8180
3 0 0 0.053 0 0 0.1038
4 0 0 -0.0136 0 0 -0.0005 Received June 28, 2002.
5 0 0 -0.0058 0 0 -0.0066
6 0 0 0.0002 0 0 -0.0043 Key Words
0 0 -0.0031 0 0 0
Stark effect; Single molecular spectroscopy;
In units of Debye Polarizability; Dipole moment.

Table 6. Quadrapole Moment of Ethylene + Ar Appendix A. Matrix elements in atomic orbitals

Ground state Excited state We need to calculate the matrix elements e0 | V | 0g ,
r 0 r 0
1

Distance e2 | V |
0 0
g , e |V |
0 0
e ,
0
g | 2
| e and 0
g | | e . Let us 1 1
xx yy zz xx yy zz 2

1 -27.206 -45.262 -31.914 -27.482 -45.781 -32.954 start with calculation of e | V | g . Using Eqs. (5-9) and (5-
0 0
1

2 -24.057 -24.248 -31.566 -23.908 -23.936 -32.015 10), we have

3 -24.217 -24.199 -28.417 -24.100 -23.922 -28.771
4 -24.193 -24.149 -27.799 -24.087 -23.878 -28.041
0
e1
V 0
g

5 -24.186 -24.140 -27.700 -24.084 -23.872 -27.899

1
6 -24.186 -24.141 -27.682 -24.085 -23.874 -27.877 (| 1 1 2 3 | | 1 1 2 3 |)
-15.903 -12.434 -12.389 -16.171 -12.404 -12.193 2
In units of Debye-Angstrom; xy = xz = yz = 0. 1
| 1 1 2 3 | V | 1 1 2 2 |
2
1
pole moments can also be seen in these two systems, but it | 1 1 2 3 | V | 1 1 2 2 |
takes a lon ger dis tance to be come zero. The in duced qua- 2
drapole moments also show large changes within 2 Å and the 1
| 1 1 2 3 | V | 1 1 2 2 |
zz-components still keep large values even at 6 Å. 2
The above calculations indicate that a short range con- 1
figuration of hosts can affect the induced dipole moment of a | 1 1 2 3 | V | 1 1 2 2 |
2
guest mol e cule and rel a tively lon ger range con fig u ra tions
2
can affect the quadrapole of the guest molecule. 3 V 2 2 3 V 2 (A-1)
In sum mary, we have the o ret i cally shown, us ing the 2
perturbation method, a mechanism of the induced dipole mo- In similar fashion, we obtain
ment of a mol e cule im bed ded in po lar and non-polar host
molecules. To roughly estimate the effect of induced dipole 0
e2
V 0
g

moment, we have applied LCAO MO to a guest molecule. We 1

have also performed ab initio calculations to study how the (| 1 1 2 4 | | 1 1 2 4 |) V | 1 1 2 2 |
2
distance between a guest and a host molecule affects the in-
1
duced dipole and quadrapole moments. We have found that | 1 1 2 4 | V | 1 1 2 2 |
the in duced dipole mo ment is very sen si tive to short range 2
con fig u ra tions and, on the other hand, the in duced quadra- 1
| 1 1 2 4 | V | 1 1 2 2 |
pole moment can be affected by longer range configurations. 2
1
| 1 1 2 4 | V | 1 1 2 2 |
2
ACKNOWLEDGEMENTS 1
| 1 1 2 4 | V | 1 1 2 2 |
2
We wish to thank the National Science Council (NSC) (A-2)
of the ROC and Academia Sinica for financial support of this 2 4 V 2
Theory of the Stark Effect on Single Molecular Spectroscopy J. Chin. Chem. Soc., Vol. 49, No. 5, 2002 803

r
and No ticing that i | i| i 0 and ig nor ing two cen ter
integrals yields
0
e1
V 0
e2

1 r e 2 ( 5 1) 2 r ( 5 1) 2 r r
(| 1 1 2 3 | | 1 1 2 3 |) V 2 23 [ Rba Rca Rda ]
2 5 5 4 4
1 e 2 ( 5 1) 2 r ( 5 1) 2 r r
(| 1 1 2 4 | | 1 1 2 4 |) [ Rba 2 Rba 3Rba ]
2 5 5 4 4
1
| | V
1
(| | | |) 3 5 r
2
1 1 2 3
2
1 1 2 4 1 1 2 4
(eRba ) (B-3)
2 (5 5)
1 1
| 1 1 2 3 | V (| 1 1 2 4 | | 1 1 2 4 |) In similar fashion, we have
2 2
1 0
r 0
r r
2 2
| 1 1 2 3 | V | 1 1 2 4 | g e2 4 2 42

2
1 ( 5 1) ( 5 1) r
1 2 [ a b c d ]
| 1 1 2 3 | V | 1 1 2 4 | 5 5 2 2
2
1 1 ( 5 1) ( 5 1)
| 1 1 2 3 | V | 1 1 2 4 | [ a b c d ] ,
2 5 5 2 2
1
| | V | | e (5 1) r (5 1) r r
2
1 1 2 3 1 1 2 4 [ Rba Rca Rda )]
20 4 4
e 2 (5 1) r (5 1) r r
1
| | V | |
2
1 1 2 3 1 1 2 4
[ Rba Rca Rda ] 0 (B-4)
20 4 4
1
| 1 1 2 3 | V | 1 1 2 4 |
2 and
V
3 4 (A-3)
0 r 0 r r
e1 e2 3 4 34
It is obvious from Eqs. (A-1)-(A-3) that
1 ( 5 1) ( 5 1) r
0 r 0 r r [ a b c d ]
g e1
2 2 3
2 23
(A-4) 5 5 2 2

0 r 0 r r 1 ( 5 1) ( 5 1)
g e2
2 4 2
2 42
(A-5) [ a b c d ]
5 5 2 2
and e (5 1) r (5 1) r r 2 r
[ Rba Rca Rda )] (eRba ) (B-5)
20 4 4 5
0 r 0 r r
e1 e2 3 4 34 (A-6)

Appendix C. Calculation of 3|V | 2 , 2 4|V | 2 and

r r r 3|V | 4
Appendix B. Calculation of , ,
r 23 42 34
We shall treat a non-polar molecule dissolved in polar
We begin with 23
molecules. In this case, we have
0
r 0
r r
g e1
2 2 3 2 23

0
V 0
2 V
r
g 3 2
1 ( 5 1) ( 5 1) e1

2 [ a b c d ]
r r r r r r
5 5 2 2 (m 2 32 ) 3( m R )( R 2 32 )

1 ( 5 1) ( 5 1)
R 3
R 5

[ a b c d ] , (B-1) r r r r r r
5 5 2 2 3 5 m ( eRba ) 3( m R ){R ( eRba )}
2 (5 5) R3 R5
where
3 5
r r r r r r r r Vmr ( R ) (C-1)
era e ( rb Rba ) e( rc Rca ) e( rd Rda ) (B-2) 2 (5 5)
804 J. Chin. Chem. Soc., Vol. 49, No. 5, 2002 Hayashi et al.

0
V 0
2 V REFERENCES
e2 g 4 2

r r r r r r
(m 2 42 ) 3( m R )( R 2 42 ) 1. Moerner, W. E.; Kador, L. Phys. Rev. Lett. 1989, 62, 2535.
0 (C-2) 2. Jung, J. A.; Schlittler, R. R.; Ginzawski, J. K.; Tang, H.;
R 3
R 5

Joachim, C. Science 1996, 271, 281.

3. Betzig, E.; Chichester, R. J. Science 1993, 262, 142.
0
V 0
V
4. Eiger, M.; Rigler, R. Proc. Natl. Acad. Sci. 1994, 91, 5740.
e1 e2 3 4

r r r r r r
(m 34 ) 3( m R )( R 2 34 ) 5. Orrit, M.; Bernhard, J. Phys. Rev. Lett. 1990, 65, 2716.
6. Wild, U. P.; Güttler, F.; Pirotta, M.; Renn, A. Chem. Phys.
R 3
R 5

Lett. 1992, 193, 451.

2 7. Basche, T.; Moerner, W. E.; Orrit, M.; Wild, U. P. eds.,
Vmr ( R )
5 (C-3) “Single Molecule Optical Detection, Imaging and Spectros-
copy” (VCH, Weinheim, 1997).
8. Moerner, W. E. Acct. Chem. Res. 1996, 29, 563.
where
9. Wild, W. P.; Güttler, F.; Pirotta, M.; Renn, A. J. Lumin. 1994,
r r r r r r
m (eRba ) 3( m R ){R (eRba )} 1003, 60-61.
Vmr ( R ) (C-4) 10. Orrit, M.; Ber nard, J.; Zumbusch, A.; Dersnor, R. Chem.
R R
3 5

Phys. Lett. 1992, 196, 595.

For a non-polar molecule dissolved in a non-polar crys- 11. Pirotta, M. PhD. Thesis, ETH Z ich, Diss. 1998, No. 11887.
tal, we have 12. Bach, H. PhD. Thesis, ETH Z ich, Diss. 1998, No. 12934.
13. Brunel, C.; Tamarat, P.; Louinis, B.; Woehl, J. C.; Orrit, M.
0
V 0
2 V J. Phys. Chem. 1999, A103, 2429.
e1 g 3 2

14. Gaussi an 98 (Re vi sion A.7), Frisch, M. J.; Trucks, G. W.;

r r Schlegel, H. B.; Scuseria, G. E.; Robb, M. A.; Cheeseman, J.
2 D
(R DA
2 32
)
R.; Zakrzewski, V. G.; Montgomery, Jr., J. A.; Stratmann, R.
D R 6
DA E.; Burant, J. C.; Dapprich, S.; Millam, J. M.; Daniels, A. D.;
r r Kudin, K. N.; Strain, M. C.; Farkas, O.; Tomasi, J.; Barone,
3 5 2 {R ( eR )}
D DA ba
V.; Cossi, M.; Cammi, R.; Mennucci, B.; Pomelli, C.;
2 (5 5) D R 6
DA
Adamo, C.; Clif ford, S.; Ochterski, J.; Petersson, G. A.;
Ayala, P. Y.; Cui, Q.; Morokuma, K.; Malick, D. K.; Rabuck,
3 5 r A. D.; Raghavachari, K.; Foresman, J. B.; Cioslowski, J.;
V (R ) D
DA
(C-5) Ortiz, J. V.; Baboul, A. G.; Stefanov, B. B.; Liu, G.;
2 (5 5) D
Liashenko, A.; Piskorz, P.; Komaromi, I.; Gomperts, R.;
Martin, R. L.; Fox, D. J.; Keith, T.; Al-Laham, M. A.; Peng,
0
e2 V 0
g 2 4 V 2 0 (C-6) C. Y.; Nanayakkara, A.; Gon za lez, C.; Challacombe, M.;
Gill, P. M. W.; John son, B. G.; Chen, W.; Wong, M. W.;
2 r Andres, J. L.; Head-Gordon, M.; Replogle E. S. and Pople, J.
0
e1
V 0
e2 3 V 4 V ( RDA ) (C-7)
D

5 A. Gaussian, Inc., Pittsburgh PA, 1998.

where
r r
r 2 D {RDA (eRba )}
V D ( RDA ) (C-8)
RDA
6