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Radiat. Phys. Chem. 51: 135–152.

445

Ionization of Solute

Molecules

at the Liquid

Water

Surface, Interfaces,

and

Self-Assembled Systems

Akira Harata

Kyushu University

Kasuga,

Japan

Miki Sato

Kyushu University

Kasuga,

Japan

Toshio Ishioka

Kyushu University

Kasuga,

Japan

Contents

17.1 General Comments ...............................................................................................................446

17.1.1 Introduction ..............................................................................................................446

17.1.2 Thermodynamic

View of the Water Surface............................................................446

17.1.3

Interface-Selective

Spectroscopic Methods...............................................................448

17.1.4

Photoionization

of Molecules at the Water Surface .................................................449

17.2

Experimental Setups............................................................................................................. 451

17.2.1 Photoionization-Current

Spectra of Molecules at the Water Surface ......................451

17.2.2

Laser

Multiphoton Ionization Current of Molecules at the Water Surface ..............451

17.2.3

Laser

Second Harmonic Generation and Surface Tension Measurements................ 452

17.3

Photoionization Spectra and Photoionization Threshold of Molecules

attheWater Surface ................................................................................................453

17.3.1 Photoionization-Current

Spectra of Molecules at the Water Surface ......................453

17.3.2

Determination

of the Photoionization Threshold.....................................................455

17.3.3

Photoionization

Thresholds of Molecules at the Water Surface...............................456

17.3.4

Photoionization of Rhodamine B at the Water Surface

underSelf-AssembledLayer ................................................................................ 457

17.4 Photoionization-Current

Dependence on the Surface Density of Solute Molecules

andEffect

of Incident Light Polarization ............................................................................. 458

17.4.1

Concentration

Dependence of Surface-Selective Signals of Rhodamine Dyes

the Water Surface: Laser Multiphoton Ionization and Second Harmonic

Generation Studies....................................................................................................458

17.4.2 Measurements

of Surface Tension and Ultraviolet-Visible AbsorptionSpectra ......460

446 Charged Particle and Photon Interactions with Matter

17.1 general Comments

17.1.1 introduction

Liquid interfaces are of fundamental and practical importance in science and technology (Birdi,

1997, 1999; Jungwirth etal., 2006). Understanding the molecular behavior at the interface involves

the fundamental sciences of molecular interaction and assists with the resolution of a variety of

problems related to chemistry, physics, and life and environmental sciences. Among liquid inter-

faces,

the air–water interface (water surface) is the most universal and may be the most important.

Many

studies have targeted the molecular behavior at liquid interfaces experimentally (Benjamin,

2006; Davidovits etal., 2006; Donaldson and Vaida, 2006; Gopalakrishnan etal., 2006; Shen and

Ostroverkhov, 2006; Winter and Faubel, 2006) and theoretically (Benjamin, 2006; Chang and Dang,

2006; Garret etal., 2006; Jungwirth and Tobias, 2006; Mundy and Kuo, 2006; Perry etal., 2006).

These studies have claried that molecules at a solution interface behave differently from those

of the same chemical species in a bulk solution. It is natural to consider that, primarily, the inho-

mogeneous and thermally uctuating structure in the vicinity of the top surface of the half-space

lled with solvent molecules dominates the interfacial properties of adsorbed solute molecules.

Additionally,

solute–solute interaction in the interface region inuences the molecular behavior.

Fundamental

interests in solute molecules at the liquid water surface include depth distribu-

tion, orientation, molecular interaction, adsorption–desorption dynamics, surface diffusion, and the

inuence of the bulk properties of solvent liquid on these from both the static (time-averaged) and

dynamic points of view. For applications to chemical processing and material fabrication using a liq-

uid surface, such as the Langmuir–Blodgett technique, the precise control of the molecular behavior

the interface might provide a novel way to control the properties of the materials produced.

precisely understand and control the molecular behavior at the interface, methodologies for

observing molecules at the interface play important roles. Interface-selective observation methods

are required because it is typical for a large amount of the same species of the target solute mol-

ecules to be in a bulk solution. Furthermore, a highly sensitive performance is preferable for this

method

because the absolute amount of the interface-adsorbed species is smaller than 1

nmol/cm

17.1.2 therModynaMic view of the water Surface

The water surface is thermally uctuating. Thermodynamic theory predicts a time-averaged view

of the liquid surface (Benjamin, 1996, 2006). As shown in Figure 17.1, the water surface has a tran-

sition region of mass density with a nite thickness. The density distribution along the surface nor-

mal is described as a co-error function with a parameter representing the half-width of the transition

region:

the thickness of the water surface can be dened as 2σ, which is given as

1 2

πγ

π ξ

kT l

l S

( / )

( ) /

(17.1)

17.4.3 Concentration-Dependent Orientation of Dye Molecule at the Water Surface........462

17.4.4 Effective Adsorption Equilibrium Constants ...........................................................463

17.4.5 Rhodamine

Dyes at the Water Surface......................................................................464

17.5

Detection

and Monitoring of Molecules at the Water Surface.............................................464

17.5.1

Detection Limit of Molecules at the Water Surface by Photoionization

Measurements...........................................................................................................464

17.5.2 Acid–Base Equilibrium Constant of Molecules at the Water Surface .....................465

17.5.3 Monitoring

of Volatile Molecules Spread on the Water Surface..............................467

17.6

Summary ..............................................................................................................................468

Acknowledgments..........................................................................................................................469

References......................................................................................................................................469

Ionization of Solute Molecules at the Liquid Water Surface 447

where

is the surface tension

S is the surface area of liquid

is the Boltzmann constant

T is the temperature

is the bulk correlation length (0.6–0.9nm)

Here l

is the capillary length equal to (γ/ρ

1/2

, with ρ

the mass density, and g the acceleration

due

to gravity

The

thickness of the pure water surface is estimated to be 0.8nm at 300K, which is comparable

to the size of an organic molecule. Surface tension has a strong inuence on the thickness. A smaller

surface tension, typically induced by the addition of organic molecules in the water, makes the tran-

sition region thicker. It is notable that these molecules are dynamically moving in, adsorbing to, and

desorbing

from the transition region.

Traditionally,

surface tension measurements have been made to thermodynamically understand a

state of solute molecules adsorbed at the water surface. Surface excess Γ is a function of the surface

tension and the solute concentration C in a bulk solution as (Motomura, 1978; Motomura etal., 1981)

Γ = −

∂













vRT C

T P

(17.2)

where

is the universal gas constant

P is the pressure

represents the number of ions contributing to the surface tension decrease per single solute molecule

The surface density of solute molecules N is equal to Γ for most organic molecules because most

of the excess molecules are expected to be in a nanometer region of the surface although, strictly

speaking, the denitions of N and Γ differ. Generally, for water-soluble molecules, the Langmuir

isotherm

given as

= +

K C

(17.3)

–1

–2

Time-averaged density

Depth under the surface (nm)

Figure 17.1 Time-average mass density distribution at the pure water surface at 300 K.

448 Charged Particle and Photon Interactions with Matter

provides a good approximation for the relation between N = N

max

θ and C, where θ is the surface cov-

erage, K

is the adsorption constant, and N

max

is the maximum value of surface density. Assuming

the

Langmuir adsorption isotherm, we get

γ γ= − +

w max ad

vRTN K Cln( ),1 (17.4)

where

is the surface tension of pure water.

The typical relation between the concentration and surface density is shown in Figure 17.2 for

two types of rhodamine dyes estimated from the surface tension-dependence on the bulk concen-

tration using Equation 17.4. It is evident that the surface density of an adsorbed solute molecule

saturates at a specic concentration. The applicable concentration ranges of a variety of methods

are also indicated (vide infra).

Surface tension measurements are valuable because the surface density of adsorbed solute mol-

ecules can be estimated through them. However, a molecular-scale view of the interface is, unfortu-

nately,

not easy to obtain; this is especially true for a condition with low adsorption coverage.

17.1.3 interface-Selective SpectroScopic MethodS

Interface-selective spectroscopic methods have been applied to provide a variety of information

on the solute molecules adsorbed at the water surface. Every interaction between light and surface

molecules

can be utilized to observe molecules at the interface, as shown in Figure 17.3.

Linear

spectroscopic methods, such as reection spectroscopy, including Brewster angle

microscopy (Hoenig and Moebius, 1991; Lheveder et al., 2000), and uorescence spectros-

copy, including confocal uorescence microscopy (Li etal., 1998a,b; Zheng etal., 2000, 2001,

2004; Zheng and Harata, 2001), are general and powerful. Nonlinear spectroscopic methods,

such as resonance optical second harmonic generation (SHG) (Shen, 1989; Zhao etal., 1990;

Eisenthal, 1992; Slyadneva et al., 1999, 2003; Tsukanova etal., 2000; Benjamin, 2006) and

vibrational sum-frequency generation (Gopalakrishnan etal., 2006; Perry etal., 2006; Shen

and Ostroverkhov, 2006), are powerful tools for the surface selective observation of molecular

electronic and vibrational states, respectively. However, it is often the case that their sensitivity

–12 –11 –10 –9 –8 –7 –6 –5 –4 –3

Log (concentration/M)

Log (surface density/cm

)

Confocal fluorescence

Surface tension

Laser multiphoton

ionization

Synchrotron

photoionization

Surface SHG

Rhodamine 6G

Rhodamine B

Figure 17.2 Relationship between concentration and surface density for rhodamine dyes. The concentra-

tion ranges for an observation with a variety of methods are shown. The surface density ranges should be

calculated from the concentration range with the relationship between the concentration and surface density

(solid

curves).

Ionization of Solute Molecules at the Liquid Water Surface 449

to detect solute molecules adsorbed at the water surface is not sufcient, especially when the

surface coverage is less than 5% of the monolayer coverage.

The applicable concentration ranges of a variety of methods are summarized in Figure 17.2; the

ndings in this gure are based solely on our experience and are one of the guidelines. Of course,

the range depends on the target molecules and experimental conditions. However, among a variety

of spectroscopic methods for observing molecules at the air–water interface, the photoionization

method surely has good potential to detect adsorbed solute molecules with surface selectivity and

sensitivity. Only the uorescence detection of the surface-adsorbed molecules is highly sensitive.

When confocal uorescence microscopy is used, the surface-selective detection of adsorbed dye

molecules is possible up to a surface coverage of 10

−6

level even if the dye molecule is water-soluble.

However, under a high-concentration condition, surface selectivity is lost because the ratio of sur-

face-adsorbed

to bulk molecules decreases.

17.1.4 photoionization of MoleculeS at the water Surface

When photo-emitted electrons from the molecules at the water surface are collected in the upper gas

phase, as in the total current yield detection method used in x-ray spectroscopy, the photoionization

current owing from the solution to the ground reects the photoionization of molecules only at the

surface

(Figure 17.4).

Absorption

–

Ionization

Harmonic

generation

Heat generation

Fluorescence

2hν

hν

ΔH

hν

Reflection

Figure 17.3 Interactions of laser light with molecules at an interface.

–

hν

–

Figure 17.4 Schematic illustration for the detection of photoionization current from molecules adsorbed

the water surface.