Simon et al.

Vol. 6, No. 5/May 1989/J. Opt. Soc. Am. B

1035

Material applications of the far-infrared free-electron laser

John D. Simon, John E. Crowell, and John H. Weare
Department of Chemistry, University of California, San Diego, La Jolla, California 92093

David R. Miller Department of Applied and Mechanical Engineering, University of California,San Diego,La Jolla, California
92093 Received November 3, 1988; accepted February 14, 1989

Our research program using the free-electron laser (FEL) to study structural and dynamical properties of materials is described. Initial experiments using the FEL facility at the University of California, Santa Barbara, focus on
understanding (1) low-energy processes in bulk and composite materials, (2) the intermolecular forces in van der Waal clusters, and (3) molecular interactions with surfaces. To support the interpretation of our experimental program we have developed the theory necessary to compute the dynamics of multicomponent systems that can interact through weak van der Waal forces or through formation of covalent and metallic bonds.

INTRODUCTION Understanding the chemistry of materials requires a detailed knowledge of the intermolecular interactions between the constituent atoms and molecules. These intermolecular (interatomic) forces determine the structure of the materials as well as the kinetics and mechanism of their chemical reactions. In order to understand these processes, one needs experimental probes that can examine intermolecular
properties of materials. Infrared (IR) light is a powerful

the far-IR spectral region.

However, there are several limi-

tool for studying the structural and dynamical properties of matter, as this spectral region encompasses the vibrational transitions of the aggregate system on the ground-state potential energy surface.' IR-light wavelengths are traditionally divided into three regions. The portion closest to the
visible region is called the near IR, X = 0.8-2.5 Aim,the mid IR extends from 2.5 to 20 ,um, and the far IR ranges from 20 to 1000 Am. The majority of commercial IR spectrometers

tations characteristic of these molecular-gas far-IR lasers. Poor beam structure (mode and pulse shape), large shot-toshot instability in power, and low repetition rate hinder their application to study properties of matter. Furthermore, these laser sources are not continuously tunable, providing radiation only on rovibrational transitions of the lasing medium. In addition to advances in providing narrow-bandwidth IR light for high-resolution spectral studies, there has been significant progress in the generation of time-resolved IR light. A variety of techniques have been explored, but the
majority focus on downconversion techniques that use a

operate in the mid IR. The potential uses of IR radiation for the study of chemical and physicial properties of molecules and materials has prompted an effort in the development of high-power light throughout the IR spectral region. Several types of IR-laser sources have been developed in the past
decade. All these sources have significant limitations; how-

ever, they offer a variety of both high spectral resolution as

well as short-time resolution (from microsecond to subpico-

variety of nonlinear-optical crystals. These frequency-mixing techniques generally involve using the fundamental of a Nd+3 :YAG laser and the output of a picosecond or subpicosecond dye laser to produce IR pulses over the spectral range 4 The wavelength of the IR light is from 4 to -11 ,um. determined by the frequency of the visible dye laser; thus, unlike molecular-gas lasers, this type of IR source is continuously tunable. The major limitation of the tuning range accessible results from the phase-matching conditions and optical absorption properties of the nonlinear optics. As exemplified in later sections of this paper, there are several important properties of molecules and matter whose
study requires light in the wavelength range from 10 to 1000 Am. As mentioned above, line-tunable far-IR gas lasers

second). The combination of these light sources now permit one to carry out experiments that examine both structural (high-resolution spectroscopy) and dynamical (time-resolved studies) properties of molecules and materials.
In our program we are interested in chemical processes in the mid- and far-IR spectral region (X = 2.5-1000 gim).

Both time-resolved and narrow spectral sources are required. A variety of high-resolution infrared lasers are cur-

rently available that cover a limited part of this wavelength region. For example, F-center lasers provide tunable, narrow-bandwidth radiation over the spectral region from 0.8 to
3.4 gm.2 CO2 lasers and far-IR gas lasers 3 (i.e., an optically

pumped CH3F laser) can provide line-tunable radiation over

0740-3224/89/051035-10$02.00

exist for this region of the spectrum. If the system of interest is accessible by one of the narrow bands generated by molecular-gas lasers, experiments can be carried out. However, as these lasers cannot be tuned, it is impossible to obtain a spectrum in this region, significantly limiting the information that can be obtained. Furthermore, ultrashortpulse generation is not possible, as the temporal properties of the molecular-gas lasers are determined by the pulse width of the pump CO2 laser. One desires optical sources of good stability (both frequency and time), mode structure, and tunability. Significant advances in this direction have been made using free 1989 Optical Society of America

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Simon et al.

Table 1. Comparison of the Output Characteristics of the UCSB FEL with Those of a CH3F Molecular Gas Laser
Property Peak power Wavelength FEL (UCSB)a 10-40 kW 12 0-800,um
10-8

CH3Fb S250 kW 359.7 5 X 10-3

In the followingsections of this paper, the possible uses of this light for examining properties of molecular clusters and molecular interactions with surfaces are discussed. Specifically, we discuss examples of systems that are currently feasible for study at the UCSB FEL. EXPERIMENTAL STUDIES IN THE FAR INFRARED After a brief description of experimental considerations and instrumentation that we have developed for surface and cluster studies, we discuss three types of experiment that we are currently pursuing using the UCSB FEL: phonon-adsorbate dynamics following IR excitation of phonons and/or librational molecular modes of the adsorbate, rotational energy exchange in sticking/desorption at the gas-surface interface, and spectroscopy and bonding of composite clusters formed in molecular beams. Experimental Considerationsand Instrumentation Figure 1 is a schematic diagram of the ultrahigh-vacuum surface science chamber utilized for experiments at the UCSB FEL. Because of the low duty cycle of the FEL and because many future experiments will be operated at cryogenic temperatures, ultrahigh vacuum and proper surface characterization probes are a necessity in studying surface physics. This system is currently equipped with Auger electron spectroscopy, ion beam cleaning, helium-atom scattering, and thermal desorption mass spectrometry. Currently
all these techniques are present on a single level (as shown in Fig. 1) for our ongoing studies involving excitation of surface states (as described below).

Fraction frequency
Band width (single pulse)

Pulse length
Repetition rate Number of modes

0.5-50 usecc
1 Hz 1

:40 nsecd
<1 Hz >1

by the FEL. Data presented are for pumping the moleculargas laser with the 9(R)12line of a TEA CO2 laser.3 Smooth pulse shape. d Irregular spiked pulse shape, reflecting pump laser.

aData from Ref. 6. b There are several lines for the CH3F laser in the wavelengthregion covered

electron lasers5 (FEL's). FEL's have been demonstrated to work in various regions of the optical spectrum. In the region of the far IR and mid IR, the FEL's at the University of California, Santa Barbara (UCSB) and the Los Alamos National Laboratory, respectively, offer to be powerful light sources for experiments on the structure and dynamics of matter. As an example of the advantages of FEL light sources, the output characteristics of the UCSB laser system are compared in Table 1 with those observed for an intense line of a molecular CHF laser. As shown in this table, the FEL laser offers several significant advantages over the conventional molecular-gas laser. First, the FEL light is single mode. This property affects the focusing of the laser beam and is also important for the carrying out of a variety of nonlinearoptical experiments of interest. Second, the frequency bandwidth is extremely narrow. This, coupled with the continuous tunability of the laser (not possible with the molecular-gas laser) in the far IR, enables one to record optical spectra of the materials of interest. As mentioned above, the molecular-gas laser is only line tunable, depending on active rovibrational transitions in the lasing medium. Many condensed-matter phenomena (e.g., phonons, magnons, hindered rotations, librations, and vibrations) involve transitions in the IR. Most of these have at one time or another been probed with conventional light sources. As mentioned above, however, the FEL permits a much wider tunability and often much higher photon fluxes for these studies. The latter feature, high intensity, opens up the possibility for many nonlinear multiphoton experiments.
The tunability of a FEL is especially important in some of

the areas that we discuss below, such as the spectroscopy of solid surfaces and clusters, in which many-bodied interactions shift and broaden the spectra. For a source such as the UCSB FEL, which currently operates below 80 cm-' (0.01 eV or -100 K), it is obvious that molecular systems under investigation should be rotationally and vibrationally cold;
this can be accomplished

using free-jet expansions7 and for solid sample materials by utilizing low-temperature cold stages for sample manipulation. Furthermore, the molecular-beam species must be
properly chosen to match the energy range of the light

for molecular-beam

sources by

source. Similar considerations must be taken into account when excitation of the surface substrate is desired.

Other studies will utilize different configurations. The multilevel, multiport design of the surface facility will permit a variety of experiments to be performed, rather easily, including internal and external IR reflection studies, surface scattering with gas-phase excitation, and thin-film preparation and examination. Expansion ports are present for the addition of further surface diagnostic probes. The system is maintained at <1 X 10-10Torr, using a titanium sublimation pump and a 360-L/sec turbomolecular pump backed by a diffusion pump. Gases are introduced into the system by using a separate turbomolecular-pumped gas handling system at <1 X 10-8 Torr. Most of the instrumentation utilized to study the interaction of light generated by a FEL with condensed matter is somewhat conventional and not unique to use with FEL's.8 Owing to the low repetition rate common to many FEL's, a boxcar integrator or related gated detector, capable of signal averaging, must be employed. For molecular-beam or surface experiments, interfacing of the experimental vacuum system to the FEL light source is straightforward, but special considerations are sometimes required. For example, below 100cm-' the absorption by water vapor is serious, and light pipes must either be purged with dry nitrogen or evacuated. In addition, the window materials that permit the light to pass into the vacuum chamber depend on both the wavelength range and the desired vacuum in the experimental chamber. For example, near 60 cm-', either the plastic poly-4-methylpent-1-ene (TPX, available through Port Plastics) or single-crystalline quartz can be used with good transmission. TPX is easily machined, and adequate vacu-

Simon et al.

Vol. 6, No. 5/May 1989/J. Opt. Soc. Am. B

Quadrupole Mass

1037

_ Spectrometer
Electron

ITY

Metal Deposition Source

Level I
Auger Electron Spectrometer

X,YZ,0 Crystal
Manipulator

Sputter

\\Ion Gun
FEL Radiation (Entrance)

/UDetector

Level I
Shielded Quadrupole Mass Spectrometer

Helium Beam Source

Level II

Level I Level III

360 Liter/sec Turbomolecular Pump Titanium Sublimation Pump Optical Ports

Level III
Fig. 1. Schematic diagram of the experimental ultrahigh-vacuum configuration used to study the excitation of surface modes or those of gases incident upon a surface using FIR radiation. The crystal surface can be cleaned by ion beam sputtering and characterized by Auger electron

spectroscopy, helium-atom scattering, and temperature-programmed desorption. um seals can be made with compression 0-ring seals. How-

ever, this material cannot be baked and is therefore not suitable for the ultrahigh-vacuum conditions required for high-purity surface characterization. In this case singlecrystalline quartz (which transmits between 30 and 250 cm-') is used. The quartz windows are vacuum sealed with
differentially pumped viton 0-ring seals. We have used

Figure 2 is a schematic of the experimental apparatus that we have constructed for cluster studies using the UCSB FEL. For these experiments we have found that TPX is the
window material of choice. Because of the pulsed nature of

such a design in the system constructed for studies at the UCSB FEL user center. After the chamber is baked at 1500C,this system maintains a base pressure of 10-10Torr.

the laser it is desirable, though not necessary, to utilize a pulsed-nozzle free-jet beam source. Several are commercially available, and the upper half of Fig. 2 depicts one such design (by Laser Technics) that uses a piezoelectric crystal
to pull a plunger and permit gas flow. A solenoid valve (e.g.,

those available through General Valve Corporation) will do

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Fig. 2. Schematic of the experimental setup for cluster beam photon-interaction studies. A detailed drawing of the pulsed valve and the interaction of a composite cluster with the laser radiation are shown in the upper and lower halves, respectively, of the figure.

equally well. The advantage of the pulsed valve is that highpressure sources can be used with small diffusion-pumped vacuum chambers. High source pressures are desirable to
achieve a considerable density of large clusters or to cool

internal molecular rotation states. The size distribution of clusters is qualitatively controlled by the source pressure and temperature but is rarely better than 10% FWHM. Also indicated in the figure is a composite cluster made of a solvent speciesB and a solute chromophore A, which absorbs the photon. The energy deposited in the chromophore may be exchanged with the host and subsequently sublime and/ or melt and evaporate a fragment. Gough et al.9 have been able to adjust the source such that the chromophore is initially either inside the cluster (by mixing the gases in the nozzle) or attached to the surface of the cluster (by using a pure solvent expansion into a background of solute molecules). Of course, two of the interesting questions are

whether, in fact, the solute chromophore will diffuse within the cluster and how long it takes for such an adjustment. This is a function of the AA, AB, and BB interaction potentials and the dynamics of the cluster.
Excitation of Surface States

The far-IR light at the UCSB FEL is probably most well suited for studies involving condensed-matter excitons, such as phonons and magnons, in the bulk and at interfaces. Such studies in the bulk have a substantial history covering

the past 30 years,la and many experiments will be enhanced by the tunability and intensity of the FEL. We are particularly interested in surface modes and the dynamical interaction of surface modes with adsorbates. There are two types of experiment that are of interest: direct excitation of an adsorbate mode, followed by desorption into a mass spectrometer detector, as suggested by the experimental schematic shown in Fig. 1 above; and indirect excitation through excitation of a surface phonon, followed by dynamical coupling to an adsorbate and subsequent desorption and detection by a mass spectrometer. In both cases, the photon absorption can also be followed by reflection attenuation measurements. The interaction of light with surfaces and adsorbates has been a subject of intense research during the past decade, and several examples of the type of experiment that we are discussing are available, most of which use metal surfaces and irradiation by UV light from intense laser sources. For example, Hoheisel et al." pumped surface plasmons in sodium clusters to stimulate desorption. Budde and co-workers' 2 have pumped electronic states of NO and then characterized the translational and internal states of the desorbed species for dynamical information. They were able to resolve both thermal and nonthermal channels for desorption. Most recently Tro et al.13 used the Stanford FEL at 3.3 m to examine the dynamics of adsorbed C4H1a. They were able to distinguish a greater desorption yield on excitation of

Simon et al.

Vol. 6, No. 5/May 1989/J. Opt. Soc. Am. B

1039

the asymmetric C-H stretch as compared with the symmetric C-H stretch, attributable to orientation affects in the adsorbed butane layer. The vibrational excitation leads to resonant heating and thermal desorption of the butane ad4 layer. Related investigations are those of Avouris et al.' 5 and Andersson and Harris,' who used electron-energy-loss spectroscopy to probe hydrogen physisorbed on metals. It
is observed that hydrogen is in an unhindered rotational

effects owingto the large polarization of the lattice atoms. r is the surface Brillouin zone center, while X and Mare the high-symmetry points at the zone edges along the [110] and [100] directions, respectively. The most pronounced relaxation effect is the separation of a new surface optical mode,
SP , near 115 cm-' (2.2 X 1013sec'1), which is raised out of

state on the surface and that the surface plays a role, not yet understood, in the ortho-para spin conversion. When one is considering the UCSB FEL, good candidates for substrates include the alkali halides, such as CsI and RbBr, which have well-defined optical and acoustical phonons at the surface in the frequency range accessible with

the transverse optical band when the surface is allowed to relax. This sagittal plane (SP) mode vibrates perpendicular to the surface, has not been confirmed experimentally, and would be a sensitive probe of the lattice dynamics calculation and force model. It is an obvious candidate for the

the FEL. These surfaces, as we have found, can be prepared, cleaned, and maintained in the ultrahigh vacuum rather easily. Since the optical phonon dispersion, c(k),
crosses the photon dispersion curve, w = ck, coupling of the

light to the surface must be done to the resulting surface polariton.' 6"7 This requires that the incident light wave
vector be altered by using a prism or a grating. However, such an arrangement
6 is the basis of the attenuated total reflection method.'

The former

that uses a prism to couple to

surface polariton experiment, although the UCSB FEL is not currently extended to this energy. Of further interest in Fig. 3 are the surface modes 8, and Sl' of RbBr. Sl' is an optical (or second) Rayleigh mode. It has a transverse-optical vibration pattern, and since its relative motion cannot be distinguished from the Rayleigh acoustic mode S1, there should be a large apparent enhance8 ment of Si expected at both the X and M points.' Therefore a two-phonon (TA + TO) experiment should be possible with adsorbates, using both reflection intensity and desorption as monitors of the phonon coupling. The sum of S, and Sj' at X and M is 78 and 66 cm-, respectively.
At low temperatures, adsorbates can be weakly physi-

the surface polariton is not suitable for examining the surface and the interaction of adsorbates under ultrahigh vacuum. Therefore we are using a grating on the surface for such

optical phonon experiments. The grating that we have put

into a CsI(100) crystal surface is spaced at 2-mm intervals,

permitting coupling to the FEL light along the [110] direction at -67 cm'. While coupling to acoustic phonons such
as the surface localized Rayleigh phonon does not involve a

polariton, it does require a two-phonon excitation in order to conserve momentum.

As another example of a system that we are currently

examining, consider the RbBr surface. Figure 3 shows the phonon dispersion curves, recently calculated by de Wette et
al.18 which are influenced by substantial surface relaxation

sorbed to the substrate sothat such excitation by the electric field or by phonon coupling may desorb them into the mass spectrometer for detection. For mass spectrometric detection it is desirable to use a molecule that has a small background concentration in the UHV chamber. It is possible to select a frequency where the substrate will not absorb strongly, i.e., a polariton is not excited, so that direct excitation of the adsorbate can be examined together with the effect of relaxation from the adsorbate to the lattice. In this case, an adsorbate such as HCl and D20 might be examined with the UCSB FEL. Conversely, an arrangement is possible to permit excitation of optically coupled phonons (polaritons) or multiple acoustic phonons, which then couple dy-

RbBr relaxed

U) Ln

Fig. 3.

Angular distribution
-

of the reflected number density for HD scattering from Ag(111) along the (112) direction.

Rotationally inelastic

transitions are labeled J

J. Adapted from Ref. 19.

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Simon et al.
9 ments are those of Whaley et al. for HD on Ag(111).1 Light species such as HD exhibit strong quantum-mechanical features such as diffraction, which are greatly influenced by the nature of the gas-surface interaction potential, especially the attractive portion. The bound states in the attractive potential well can significantly alter the intensity of elastic, 25 and inelastic, scattering. Rotational to translational energy exchange opens up well-defined inelastic channels, which do not involve exchange of energy with the surface, and provides strong resonant features in the scattered differen-

namically to the adsorbate and induce desorption. Such an experiment, using polariton-induced desorption, has been discussed theoretically by Reyes et al.20 Candidates for the
UCSB FEL would be physisorbed krypton or HD, for example, on CsI or RbBr. Naturally the lattice absorption can be

followed by reflection intensity, while the coupling to the adsorbate is followed by mass spectrometric analysis of the desorption rate. Again, the mass spectrometer indicates not only what desorbs but, by time-of-flight analysis, the translational energy with which the species desorbs, providing additional dynamical information. More detailed considerations will likely be necessary to separate clearly the effects

tial cross section.

An example is shown in Fig. 4 for the HD/

of enhanced electric field from mechanical coupling to the phonon motion.

Rotational Exchange with Surfaces Molecules can be prepared in low-rotational-state popula-

tion in a high-pressure free-jet molecular-beam expan72 sion. , 1 This is accomplished, for example, by mixing the molecular species of interest into a carrier gas such as helium and then expanding the mixture from high pressure, through a nozzle or an aperture, into high vacuum. The carrier gas serves to prevent condensation or clustering but provides the rapidly cooled bath of background atoms that cools the molecular species. Rotational temperatures can be varied between 5 and 30 K, and the velocity distribution translational temperature can be varied from well below 1 to 10 K.

Ag system. In this case the HD molecules were cooled to the J = 0 state in a free-jet expansion and the rotational-translational transitions followed by measuring scattered intensity as a function of angle from the surface normal, using a mass spectrometer. It is seen that most of the scattering is not coupled to a diffraction channel, AG = 0, and involves the J = 0 initial state. Both Ag(111) and Au(111) are good candidates for the experiment because they can be maintained clean in ultrahigh vacuum, and they are smooth surfaces so that the AG = 0 channels are favored. Analysis of

such data provides insight regarding the gas-surface potential and the collision dynamics. By using the UCSB FEL for the beam excitation, and the
rotationally mediated selective adsorption process as a de-

Both nozzle source temperature and pressure are used to adjust the beam properties. As an example, if HF (with
rotational constant B = 21 cm-') were cooled rotationally to 5 K, then essentially all molecules would be in the J = 0 state Nj=l/Nj=o = (2 X 10-5), while at 30 K the ratios are approximately Nj=l/Nj=O = 0.4 and Nj= 2 /Nj=o = 0.01. The FEL

tector, it is possible to examine rotational excitation in the beam, including multiphoton processes, and the effect of rotational excitation on the gas-surface interaction. The molecular species must be light enough to exhibit quantummechanical scattering and to scatter preferentially without interactions with phonons at the surface. One such candidate, whose states are accessible with the UCSB FEL, is HF, although its sticking probability on metals is not yet known.
Structure and Dynamics of Clusters

can then be used to prepare a rotationally excited beam for further interaction studies with other gases, photons, or solid surfaces. In particular, we will be interested in the effects

of rotational states in the sticking and scattering from welldefined single-crystal surfaces. Recently a great deal of progress has been made in using laser spectroscopies to examine the rotational states of desorbing species, especially NO, from smooth metals. 22 One of

the interesting results is the underpopulation of high rotational states in the desorbing species compared with the lowJ states. This is now understood in terms of straighforward collision dynamics. The reverse process, sticking of prescribed rotational states, has not been examined. The two processes would be coupled by detailed balancing, provided that the states of the solid surface with which the molecules interact represent an equilibrium distribution of states. Therefore such studies are affected by the relaxation rates of the lattice and the dynamics of the interaction. While sticking probabilities can be studied by mass spectrometric analysis of scattered molecules, a more direct measure is to use helium-atom scattering as a monitor of surface coverage.

Adsorbates attenuate the intensity of coherent helium-atom 23 scattering. Comsa and Poelsema have used this technique to examine adsorbates and defects on several surfaces, and Elliot and Miller24 have investigated the sticking coefficient
of CO on Au(111). This probe is especially sensitive for surface coverages below 10%.

Another type of experiment is rotationally mediated selective adsorption processes. Here the prototype experi-

Experimental Studies As discussed further below, there is considerable interest in understanding the dynamics of small condensed systems or clusters. Molecular beams provide a means of probing such systems in a free state, as compared with examining clusters on surfaces where the interaction of the substrate can be significant. During the past decade many studies involving lasers using pulse-probe techniques have been applied to condensed phase systems to investigate energy transfer. Most of these have been in the UV portion of the spectrum and have used electronic state spectroscopy. A few near-IR experiments have been reported that probe the dynamics of vibrational energy transfer in clusters. Two studies that are closely related to our interests in the far IR are those of Gough et al.,9 who examined SF6/Ar composite clusters, and those of Vernon et al.,2 6 who studied small water clusters. Using far-IR FEL radiation, we intend to pump energy into composite clusters and then to examine the heating and fragmentation of the small clusters. Molecular systems that can be probed include HCl and HF as chromophores in Ar or D20 clusters. Figure 2 indicates two geometries for studying the interaction of far-IR photons with the molecular beam. In the first geometry the photons cross the beam in the nozzle chamber and may make multiple passes with properly arranged reflecting surfaces. The beams and associated fragments are then monitored in the mass spectrometer chamber. Detec-

Simon et al.

Vol. 6, No. 5/May 1989/J. Opt. Soc. Am. B

1041

C\

2
Can

01 !

I
30

II

60

90

Fig. 4. Phonon dispersion curves for 15-layer unrelaxed and relaxed slabs of RbBr with free (001) surfaces: S1 and S1' indicate the acoustical and optical Rayleigh modes, respectively. SP11 and SP 1 indicate longitudinal and transverse sagittal-plane vibrations. Only surface modes with vibrations perpendicular to the surface have been identified. Adapted from Ref. 18.

tion can be either on the beam center line, so that a decrease in intensity is observed as the cluster fragments, or off the

axis of the primary molecular beam, where the fragments

give an increase in signal and the noise of the primary beam is avoided. In the second geometry the photon flux is brought in along the axis of the molecular beam, to increase

the interaction density substantially and thereby favor multiphoton processes. Doppler broadening is larger in this geometry. For a velocity distribution translational temperature of 10 K, Av/v0 = 3 X 10-7, compared with the 10-8 mode purity per pulse of the FEL (see Table 1). Since both

beams are pulsed it is straightforward to arrange the appropriate timing. In both cases it is possible to obtain dynamical information by measuring the time of flight of the fragments to the detector, which provides a measure of their
translational energy as they leave the parent cluster. Such a measurement is obviously much more precise in the crossed-

beam geometry. Theoretical Studies

A primary objective of our FEL research program is the

study of the structural and dynamic properties of condensed-matter systems. The dynamical behavior of these systems is considerably more complicated than that of the molecular systems that are more commonly studied by chemists. However,with the availability of large computers it is now possible to simulate complicated dynamical processes theoretically with considerable accuracy. These simulations can be used to support interpretations of experi-

does not appear to provide a viable improvement. In order to simulate such systems we have developed software to implement an ab initio molecular dynamics approach similar to that recently suggested by Car and Parrinello.2 8 In this approach the potential interactions are calculated from an approximate solution to the many-electron Hamiltonian for the system. The method requires no empirical information other than the nuclear charges of the constituent atoms and therefore can provide predictions about systems with unknown chemistry. At present our programs are fully operational, and we are using them to calculate the dynamics of systems of interest to the experimental program. The generality of the programs that we have developed is such that the programs can be used in other studies of direct interest to the development of the FEL. For example, simulations of melting in mixed and pure thin films may be of value to the development of damage-resistant materials for laser mirrors. In what follows we briefly describe our progress with our simulation programs. Simulations of Energy Transfer in Doped van der Waals Clusters: The spectroscopy of molecular and atomic clusters is currently an area of intense experimental and theoretical investigation. 2 9 From a theoretical point of view, clus-

mental data. For this reason our group has developed the theoretical tools and software to simulate accurately systems
of complex chemistry. For systems interacting by means of van der Waals forces

ters of rare-gas atoms are certainly the most studied. The pairwise additivity of the interaction potential between atoms in van der Waals bonded systems, together with the spherical symmetry of the potential for rare gases, makes these systems easily simulated. These studies have shown that certain size clusters are especially stable, most notably those derived from the symmetry of the icosahedral point
group (Mn, n = 13, 55, 147, .. ).

the methods of simulation are straightforward. However, for systems with metallic and covalent bonding, which display more interesting chemistry, the problems of simulation 27 The interactions in these become much more complex. systems are not satisfactorily described by two-body interactions. Adding higher-body phenomenologicalcontributions

The study of the dynamics of these systems has led to some interesting results. For example, constant energy simulations have identified a sharp liquid-solidlike phase
change in clusters as small as seven atoms. Because of the

possible relationship of this phenomenon to bulk transitions it has become a topic of considerable theoretical interest.
Unfortunately, because of the lack of a dipole moment in a

pure van der Waals cluster, experimental data for these

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Simon et al.

0 E

2.4 0

(n.6

c08 E

0
Fig. 5.

0.1

0.2 0.3 temperature

0.4

the MSD of the motion within the solvation shell. The open circles are the MSD of the motion perpendicular to the shell.

Calculated MSD of an A12B cluster.

The filled circles are

systems are not available. In order to circumvent this difficulty, Gough et al.9 studied argon clusters doped with IRactive SF6 . By studying the shifts from the gas-phase IR spectra with the addition of argon atoms, these workers hoped to obtain information about the dynamics of the cluster system. Other experiments with a similar objective have been published by Hahn and Whetten3 0 and Bosiger and Leutwyler.3 1 Superficially, these experiments appear to support an interpretation in terms of the sharp three-dimensional transition apparent in the simulations of pure clusters. However, our more recent simulations suggest that the situation in the mixed systems is considerably more complicated.32 For example, in systems meant to simulate the IR
experiments of Gough et al.,9 we have found a sharp two-

dimensional phase transition at a temperature considerably

50.0

lower than the predicted three-dimensional transition. The structure of this system is dominated by the strong interactions between the impurity atom and the pure atoms. The impurity forms a spherical surface on which the pure atoms form a solidlike ordered phase at low temperatures and a liquidlike phase at higher temperatures. Because there are not enough atoms the impurity is incompletely solvated. The best evidence for this abrupt change in the dynamics of this system is given by the calculated mean-square displacements (MSD's) as shown in Fig. 5. In this figure the open circles show the MSD's for the bond length from the impurity atom (SF6) to the solvating argon atoms. The filled circles show angular MSD's for the same bonds. As the temperature is raised the bond-length MSD remains roughly constant, indicating solidlike vibration in the solvation shell. On the other hand the bond-angle MSD shows a sharp change with temperature, indicating a two-dimensional melting in the incomplete solvent shell of the SF6. Other supporting evidence for this transition can be obtained from 32 the simulations. Even less is known about either energy transfer in clusters or the dynamics of simple chemical reactions in clusters. We have begun research along these directions, also using molecular dynamics simulations. Extensions to experimental studies using the FEL light at UCSB are planned. The goals of this aspect of our research are to understand (1) vibrational relaxation in clusters and (2) the dynamics of photodissociative systems in rare-gas clusters. Our calculations on vibrational relaxation have focused on rare-gas clusters (xenon and argon) doped with molecular nitrogen. Clusters of this type are easily formed by using molecularbeam techniques. By monitoring the potential and kinetic energy of the nitrogen and argon atoms followingvibrational excitation of the diatomic, the flow of vibrational energy from the excited molecule into the cluster can be examined. We have studied the energy transfer dynamics in the three smallest icosohedral structures, N2Ar 2 , N2Ar5 4, and N2Ar 46 , using various

40.0

X
30.0
CU

E Ca2 d) 20.0 a) 10.0

0.0

0.0

1.0

2.0

3.0

4.0

5.0

Time (psec)
Fig. 6. Temperature dependence of various shells of the Ar 54N2 cluster after excitation of the embedded nitrogen molecule. First shell,
second shell, . ; third shell, -----.

--

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Vol. 6, No. 5/May 1989/J. Opt. Soc. Am. B

1043

excitation energies of the nitrogen.33 Although this particular system cannot be experimentally probed by using the UCSB FEL, the dynamical information is important and applicable to understanding other systems. Results for our simulation of vibrationally excited nitrogen in the rare-gas cluster of Ar 54 are presented in Fig. 6.

and density as the original many-electron problem. Unfortunately, the potential for the equivalent problem is known only in principle. A possible solution to this dilemma, which provides a highly accurate and practical approximation, was suggested by Kohn and Sham. In the LDA, the exact exchange correlation potential for a particular problem is replaced by the exchange correlation potential for a homoge-

The data in this figure correspond to an excitation equal to 35 quanta of the stretching vibration. In this plot the time
dependence of the temperature of various shells of the clus-

ter is plotted. The shells are defined by peaks in the N2 -Ar pairwise distribution function, g(r)N 2 -Ar. The melting temperature of the Ar55cluster is 40 K.34 These data indicate that immediately following the excitation of the diatomic, the first shell temperature increases rapidly. Changes are also observed in the pairwise radial distribution functions,
g(r)ArAr and g(r)N2 Ar. The temperature data also show that

neous electron gas. This potential is also not exactly known, but it has been calculated to a high approximation by numerical methods. Although they are approximate, numerous calculations have shown that the results approach the
accuracy of configuration interaction calculations.
32

Since

energy propagates from the inner shell to the outer shells in a wavelike manner. By using the maxima in the temperature curves for the first and outer shells, an estimate of the propagation velocity of the thermal wave is found to be -2000 m/

sec. This is in excellent agreement with the speed of sound

in solid argon, 1800-2400 m/sec.
35

the only approximation in the theory is the replacement of the potential with the homogeneous electron gas potential, the method can be applied to an arbitrary system simply by specifying the number of electrons and the nuclear charges of the constituent atoms. This coupled with the proven accuracy and efficiency of the LDA approach is proving to be a powerful and effective tool for predicting properties of quite large systems. Recently Car and Parrinello2 8 showed that the LDA method can be implemented in a way that improves its efficiency

Simulations of Covalently and Metallically Bound Systems: As mentioned above, for covalent and metallically bound systems the usual approach to simulation in which the interactions between molecules are described by analytical potentials such as the Lennard-Jones potential is no

to the extent that limited dynamical simulations are now possible. In this ab initio molecular dynamics approach the electronic states and atomic motions are computed simultaneously. An effective method of updating the LDA wave

longer sufficiently accurate. Furthermore, for studies of systems of more than a few metal atoms, the experimental data are more complicated than those found for rare-gas
clusters because of the presence of a number of nearly degenput becomes even more important for interpretation. use of three-body
27 Therefore theoretical inerate electronic configurations.

Vari-

ous efforts have been made to simulate these systems by the

potentials to improve the force calcula-

tions. This work, however, has not been successful. The structures and dynamics predicted from such approaches disagree strongly with accurate calculations. The data required, either computed or measured, to parameterize such an approach are also quite extensive and are not generally available for systems that exhibit interesting chemistry. For most systems the forces between atoms can be calculated from a single solution to the time-dependent manyelectron Schrodinger equation. In this case, the dynamics
of the system can be adequately described by interactions on

one Born-Oppenheimer surface. Unfortunately, calculating the solution to the full Schrodinger equation for a single potential energy, even for a diatomic by a configuration

interaction approach, is a difficult computational task. On the other hand, approximate approaches such as that of
Hartree-Fock are seldom accurate enough to be relied on to

predict chemical behavior. Recently there has been considerable interest in an alternative approximate approach to the quantum-mechanical problem, the local density approximation (LDA). In this method the many-electron quantum mechanical problem is replaced by an equivalent one-electron problem. The Hamiltonian for the equivalent problem contains a potential, the exchange correlation potential, that is a function of the electron density in a way similar to the Hartree-Fock potential. In this case, however,Kohn and Sham36 have shown that the solution to the equivalent problem will have the same energy

Fig. 7. Calculated structure of the Be 13 cluster. The average bond length is 3.1 A. The length varies strongly with bond coordination, as illustrated.

1044

J. Opt. Soc. Am. B/Vol. 6, No. 5/May 1989

Simon et al.

functions as the atomic positions are updated in the simulation further increases the efficiency of the LDA calculation in the Car-Parrinello approach. We have developed the theory and software necessary to implement such an algorithm. To illustrate some of our
results we show in Fig. 7 the calculated structure of the Be13 system. 3 7 Because of its closed s2 atomic configuration,

6. L. R. Elias, IEEE J. Quantum Electron. QE-23, 1470(1987). 7. D. R. Miller, in Atomic and Molecular Beam Methods, G.
Scoles, ed. (Oxford U. Press, New York, 1988).

8. K. Moller and W. Rothschild, Far-Infrared Spectroscopy (Wiley-Interscience, New York, 1971). 9. T. Gough, R. Miller, and G. Scoles, J. Chem. Phys. 69, 1588 (1978); T. Gough, M. Mengel, P. Roundtree, and G. Scoles,

"Infrared spectroscopy at the surface of clusters-a new type of

surface spectroscopy:

small clusters of beryllium are weakly bound. For example,

the bond energy of the dimer is 0.11 eV. As the size of the

(University of Waterloo, Waterloo, Ontario, Canada, 1985); T.

E. Gough, D. G. Knight, and G. Scoles, Chem. Phys. Lett. 97, 155 (1983); T. E. Gough, M. Mengel, P. A. Roundtree, and G. Scoles, J. Chem. Phys. 83, 4958 (1985).

SF6 on Ar," Chem. Phys. Rep. CP-2716

system is increased the bonding changes from van der Waals to metallic. Recently several attempts to quantify this progression of behavior as a function of system size have been published. Our calculated results suggest that there is considerable sp interaction in quite small cluster sizes. Metallic behavior is present even in systems as small as five atoms.

10. S. Mitra and S. Nudelman, Far-Infrared Properties of Solids

(Plenum, New York, 1970). 11. W. Hoheisel, K. Jungmann, M. Vollmer, R. Weidenauer, and F. Trager, Phys. Rev. Lett. 60, 1649 (1988). 12. F. Budde, A. Hanza, P. Fenn, G. Ertl, D. Weide, P. Andresen, and H. Freund, Phys. Rev. Lett. 60, 1518 (1988). 13. N. J. Tro, D. A. Arthur, and S. George, "Infrared resonant desorption of butane from A1 2 0 3 (1120): evidence for an ordered adlayer from vibrational mode selectivity," J. Chem. Phys. (to be published). 14. Ph. Avouris, D. Schmeisser, and J. Demuth, Phys. Rev. Lett. 48, 199 (1982). 15. S. Andersson and J. Harris, Phys. Rev. Lett. 48, 545 (1982). 16. V. M. Agranevich and D. L. Mills, Surface Polaritons (NorthHolland, New York, 1982). 17. R. F. Wallis and G. I. Stegeman, Electromagnetic Surface Excitations (Springer-Verlag, New York, 1986). 18. F. deWette, A. Kulkarni, U. Schroder, and W. Kress, Phys. Rev. B 35, 2476, 5783 (1987). 19. K. Whaley, C. Yu, C. Hogg, J. Light, and S. Sibener, J. Chem. Phys. 83, 4235 (1985). 20. J. Reyes, F. Goodman, and M. Cole, Surf. Sci. 151, 221 (1985). 21. D. Levy, L. Wharton, R. Smalley, "Laser spectroscopy in super-

The complexity of the structure in Fig. 7 illustrates the expected difficulty of describing such a system with phenomenological force equations. The structure in this figure is fully optimized with respect to bond angle and lengths. The size of the largest beryllium cluster calculated by other
authors is five atoms. As noted above, it is well known that

systems interacting through van der Waals forces adopt a highly stable 13-atom icosahedral structure. The stable structures for small metallic systems are essentially unknown. Bulk beryllium adopts a hexagonal close-packed structure. Additional calculations that we have done have
shown that for Be13 the hp structure is already close in

energy to the icosahedral structure. ACKNOWLEDGMENTS The ongoing studies reviewed in this paper represent the
work of a number of students and research associates, in-

sonicjets, in Chemical and Biochemical Applications of Lasers,

22. 23. 24. 25. 26. 27. C. B. Moore, ed. (Academic, New York, 1977), Vol. II; R. Smalley, D. Levy, and L. Wharton, J. Chem. Phys. 64, 3266 (1976). J. Barker and D. Auerbach, Surf. Sci. Rep. 4, 1 (1984). G. Comsa and B. Poelsema, Appl. Phys. A 38, 153 (1985). G. Elliot and D. R. Miller, in Rarified Gas Dynamics, H. Oguchi, ed., Proceedings of the 14th International Symposium on Rarified Gas Dynamics (U. Tokyo Press, Tokyo, 1984), p. 349. T. Engel and K. H. Rieder, in Structural Studies of Surfaces, G. Hohler, ed., Vol. 91 of Springer Tracts in Modern Physics (Springer-Verlag, Berlin, 1982), p. 1. M. Vernon, D. Krajnovich, H. Kwok, J. Lisy, Y. Shen, and Y. Lee, J. Chem. Phys. 77, 47 (1982). P. Jena, B. K. Rao, and S. N. Khana, eds., Proceedings of the

cluding Shyh-Gang Su, Bob Ning, David Smith, Bruce Andrein, Ryoichi Kawai, and Xiping Long. We thank Vincent Jaccarino and the UCSB FEL Group for their help in carrying out experiments. This research is supported by a grant from the Strategic Defense Initiative Material and Medical Free Electron Laser Program.
J. D. Simon is a National Science Foundation Young In-

vestigator (1985-1990) and an Alfred P. Sloan Fellow (19881990).

International Symposium of the Physics and Chemistry of

Small Clusters (Plenum, New York, 1987); M. R. Hoare, Adv. Chem. Phys. 40, 49 (1979); M. D. Morse, Chem. Rev. 86, 1049 (1986); M. Kappas, Chem. Rev. 88, 369 (1988). 28. R. Car and M. Parrinello, Phys. Rev. Lett. 55, 2471 (1985). 29. D. J. McGinty, J. Chem. Phys. 58,4733 (1973); C. L. Briant and J. J. Burton, J. Chem. Phys. 63,2045, 1975; T. L. Beck and R. S. Berry, J. Chem. Phys. 84,,2783 (1986); R. S. Berry, T. L. Beck, and H. L. Davis, in Evolution of Size Effects in Chemical Dynamics, I. Prigogine and S. A. Rice, eds., Vol. 70 of Advances in Chemical Physics (Wiley, New York, 1988); T. L. Beck and R. S. Berry, J. Chem. Phys. 88, 3910 (1988). 30. M. V. Hahn and R. L. Whetten, Phys. Rev. Lett. 61,1190 (1988). 31. J. Bosinger and S. Leutwyler, Phys. Rev. Lett. 59, 1895 (1987). 32. R. Kawai, I. L. Garzone, X. P. Long, and J. H. Weare, in The

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