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15 Dec 1972

Volume 57, Issue 12, pp. 5019-5623

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Classical S‐Matrix for Vibrational Excitation of H2 by Collision with He in Three Dimensions

Jimmie D. Doll and William H. Miller

J. Chem. Phys. 57, 5019 (1972); http://dx.doi.org/10.1063/1.1678182 (8 pages) | Cited 77 times

Online Publication Date: 4 September 2003

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Complex‐valued classical trajectories have been computed by direct numerical integration of the equations of motion for three‐dimensional collisions of He and H2, and from such trajectories classical S‐matrix elements for transitions between specific rotational‐vibrational states of H2 have been constructed. At the collision energies employed (∼1–2 eV) all vibrationally inelastic transitions are classically forbidden, thus the need for analytically continued, complex‐valued trajectories. Comparison with the quantum mechanical calculations of Eastes and Secrest shows excellent agreement between the quantum and uniform semiclassical transition probabilities. Since, however, for three‐dimensional collision systems one is seldom concerned with individual S‐matrix elements, but rather sums over many of them, an important practical feature is developed which shows how one can combine the usual Monte Carlo classical treatment of some of the internal degrees of freedom with a semiclassical state‐by‐state description of others; i.e., one can ``quantize'' only those degrees of freedom that are highly quantumlike (e.g., vibration). This ``partial averaging'' approach also greatly simplifies the practical aspects of applying classical S‐matrix theory to systems with several internal degrees of freedom.

Magnetic Field Dependence of I2 B‐State Lifetimes

Gene A. Capelle and H. P. Broida

J. Chem. Phys. 57, 5027 (1972); http://dx.doi.org/10.1063/1.1678183 (3 pages) | Cited 9 times

Online Publication Date: 4 September 2003

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A shortening of I2(B 3Π0u+) fluorescence lifetimes has been observed upon application of a magnetic field and is a function of the vibrational level of the upper electronic state and of magnetic field strengths. A suggested process is predissociation, due to mixing by the magnetic field of a repulsive Ou− state with the B state.

Structure of (KSO3)2NO in X‐Irradiated Single Crystals of (KSO3)2NOH

Phillip J. Hamrick, Howard Shields, and Thomas Gangwer

J. Chem. Phys. 57, 5029 (1972); http://dx.doi.org/10.1063/1.1678184 (4 pages) | Cited 5 times

Online Publication Date: 4 September 2003

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The nitrosyldisulfonate ion has been identified in x‐irradiated single crystals of potassium hydroxylaminedisulfonate. Principal values of the N14 hyperfine coupling constants are 27.5, 7.7, and 5.5 G. The principal g values are 2.0094, 2.0055, and 2.0026. Weak transitions due to hyperfine interactions with a proton from the host crystal are observed.

Microwave Dielectric Constant and Conductivity Measurements in the Phthalocyanines

M. A. Abkowitz and A. I. Lakatos

J. Chem. Phys. 57, 5033 (1972); http://dx.doi.org/10.1063/1.1678185 (4 pages) | Cited 17 times

Online Publication Date: 4 September 2003

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Dielectric constant and loss measurements have been made on α, β, and X metal free and copper phthalocyanine at microwave frequencies. Measurements were carried out on pressed pellets of polycrystalline material. Dielectric constant data is analyzed in terms of a powder dielectric model. The relative dielectric conductivities of these phthalocyanines are examined along with similar measurements on various β transition metal phthalocyanines. Dielectric conductivities of these metal phthalocyanines appear to be consistent with dc conductivities reported in the literature.

Exact Solutions for Dynamics of Finite, Semi‐Infinite, and Infinite Chains with General Boundary and Initial Conditions

Keum H. Lee and Hyunyong Kim

J. Chem. Phys. 57, 5037 (1972); http://dx.doi.org/10.1063/1.1678186 (8 pages) | Cited 4 times

Online Publication Date: 4 September 2003

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The exact analytic solutions in closed form for the dynamics of finite, semi‐infinite, and infinite linear chains of identical masses and ideal springs are presented. In addition to the harmonic interaction between nearest neighbors, each particle is harmonically bound to its equilibrium position and is subjected to frictional and other external time‐dependent forces. The motion of all the particles is expressed in terms of the given initial conditions and applied forces. In contrast with previous studies on the finite chains, very general (i.e., not necessarily ``periodic'') boundary conditions are used and the resulting solutions contain terms representing all the higher order multiple reflections from the two ends. The properties of the solutions are studied for all possible values of physical constants including the limiting values for uncoupled oscillators. By specializing some results of the present work, those of previous derivations on simpler systems by other authors are recovered. Some useful applications of the results are suggested.

Near Hartree‐Fock Calculations on the Ground State of the Water Molecule: Energies, Ionization Potentials, Geometry, Force Constants, and One‐Electron Properties

Thom. H. Dunning, Russell M. Pitzer, and Soe Aung

J. Chem. Phys. 57, 5044 (1972); http://dx.doi.org/10.1063/1.1678187 (8 pages) | Cited 101 times

Online Publication Date: 4 September 2003

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Near Hartree‐Fock wavefunctions have been calculated for the ground state of the water molecule using both Slater and contracted Gaussian basis sets. Total energies of −76.063 hartree were obtained with a (5s4p1d∕3s1p) Slater basis and a [6s5p2d∕3s1p] contracted Gaussian basis derived from an (11s7p2d∕5s1p) primitive set; these energies are estimated to be within 0.003±0.002 hartree of the Hartree‐Fock limit. The Hartree‐Fock wavefunctions account for ∼70% of the dissociation energy of water. The Hartree‐Fock vertical ionization potentials (in electron volts), 11.1(2B1), 13.3(2A1), and 17.6(2B2), are too low by 1–1.5 eV as expected. With the Gaussian basis set a potential surface was computed and the equilibrium geometry and harmonic force constants were calculated. The calculated bond length, 0.941 Å, and bond angle 106.6°, are in good agreement with the experimental values, 0.957 Å and 104.52°. In spite of the rather good agreement for the geometry, the force constants are in error by 15%–20%. This is attributed to an inadequancy of the Hartree‐Fock model. A number of one‐electron properties were also computed; they differ only slightly from those reported in earlier work and are in satisfactory agreement with experiment. Plots of the valence (canonical) molecular orbitals are given.

Heat Capacity near the Consolute Point in Solid CH4�Ar

Sandra C. Greer, J. M. H. Levelt Sengers, and George T. Furukawa

J. Chem. Phys. 57, 5052 (1972); http://dx.doi.org/10.1063/1.1678188 (7 pages) | Cited 1 time

Online Publication Date: 4 September 2003

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Measurements are reported of the heat capacity at saturated vapor pressure (essentially Cp) of the system CH4�Ar near its solid‐solid consolute point (62°K, 65% Ar). In contrast to the behavior of the heat capacity at binary liquid consolute points, where there are striking anomalies, no large increase was observed for CH4�Ar. An abrupt increase of only about 13% occurred in the heat capacity near the transition. The possibility that the anomaly is suppressed by lattice strain effects is discussed.

Lifetimes of the A 2π and B 2Σ States of the CN Radical

Thomas J. Cook and Donald H. Levy

J. Chem. Phys. 57, 5059 (1972); http://dx.doi.org/10.1063/1.1678189 (7 pages) | Cited 24 times

Online Publication Date: 4 September 2003

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The lifetimes of the A 2Π(v = 10) and B 2Σ(v = 0) states of the CN radical have been measured from an analysis of the zero electric field limit linewidth of the level anticrossing spectrum. The measured value of τΣ = 39.4±9.3nsec was found to be in reasonable agreement with the most recent phase shift measurement. The value of τπ = 137±45nsec was in serious disagreement with previous direct decay measurements on v ≤ 9 vibrational levels, but in essential agreement with previous microwave and intensity measurements on the perturbed v=10 level.

Effect of H2 Pressure on Pulsed H2+F2 Laser. Experiment and Theory

S. N. Suchard, R. L. Kerber, G. Emanuel, and J. S. Whittier

J. Chem. Phys. 57, 5065 (1972); http://dx.doi.org/10.1063/1.1678190 (11 pages) | Cited 32 times

Online Publication Date: 4 September 2003

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Stimulated emission predictions and measurements for an H2+F2 laser are compared for H2 pressures from threshold to stoichiometric, a range of several orders of magnitude. Slowly flowing, helium‐diluted, 50 torr mixtures are initiated photolytically. Two dilution ratios and two output couplers are considered, and good agreement is found for time‐to‐threshold and pulse duration vs H2 pressure. Spiking, relaxation oscillations, and possibly mode beating, features not modeled, are observable in some pulses; however, predicted intensity vs time generally agrees in pulse shape with laser output. Observed and predicted peak intensities nearly match for low H2 pressure, and the predicted increase of peak intensity with low H2 is followed fairly well. For H2 in the vicinity of one‐tenth stoichiometric, the peak intensity data show an abrupt leveling off, while the calculations predict a continuing increase. This disagreement most probably cannot be attributed to uncertainties in the kinetic model. All rate modifications considered have proven incapable of producing a change sufficiently large or abrupt to explain this feature of the data. Experimental results are presented supporting the notion that parasitic oscillations cause this change in laser output.

Bond Order in LCAO Molecular Orbital Theory

Irwin Cohen

J. Chem. Phys. 57, 5076 (1972); http://dx.doi.org/10.1063/1.1678191 (9 pages) | Cited 8 times

Online Publication Date: 4 September 2003

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On the basis of LCAO theory, the following intrinsic definition of bond order is derived:
math
where i and j index basis functions on different centers, pij is the corresponding charge‐and‐bond‐order matrix element, Sij is the overlap integral, fij is a long range factor, and gij is an atomic hybridization and nonorthogonality factor. The term pijSij is the overlap population and the term pijfijgij is the associated net atomic population; the latter is defined by a reference homopolar bond constructed from normalized hybrids of compositions determined by the LCAO wavefunction. The bond order, Bij, reduces in the appropriate special cases to the Coulson, Mulliken, and Wiberg bond orders. However, Bij is not limited to these cases but is also valid for analysis of any LCAO wavefunction. It may also be combined with a Mulliken population analysis to resolve the total electron population into bonding terms and residual lone pair terms. Similarly, the valence electron population may be resolved into covalence, electrovalence, and free valence. Applications are given to HF, the Group I fluorides, and some organic molecules.

On the Energy Losses of Hot Atoms Colliding with Different Molecules

Zeev B. Alfassi and Saadia Amiel

J. Chem. Phys. 57, 5085 (1972); http://dx.doi.org/10.1063/1.1678192 (3 pages) | Cited 4 times

Online Publication Date: 4 September 2003

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Experimental α values for hot halogen atoms colliding with methyl halides disagree with the calculated values, assuming elastic collisions. This is attributed to the asymmetry of the target molecules which either render the interaction inelastic or are governed by a different scattering potential.

14N NQR Spectroscopy of Some Amino Acids and Nucleic Bases via Double Resonance in the Laboratory Frame

R. Blinc, M. Mali, R. Osredkar, A. Prelesnik, J. Seliger, I. Zupančič, and L. Ehrenberg

J. Chem. Phys. 57, 5087 (1972); http://dx.doi.org/10.1063/1.1678193 (7 pages) | Cited 40 times

Online Publication Date: 4 September 2003

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The 14N nuclear quadrupole resonance spectra and spin‐lattice relaxation times of the amino acids histidine, methionine, cystine, cysteine, and tyrosine as well as of the nucleic bases uracil, thymine, cytosine, and guanine have been determined by a 14N‐proton double resonance technique in the laboratory frame. The experiments were performed on polycrystalline samples at 77°K or above this temperature. A theoretical estimate of the sensitivity of this method for a variety of experimental conditions is as well presented. It is shown that in contrast to usual double resonance techniques the method works even in the case of a short proton spin‐lattice relaxation time if only the nitrogen relaxation time is long.

Theory of Fluorescence Depolarization by Anisotropic Rotational Diffusion

T. J. Chuang and K. B. Eisenthal

J. Chem. Phys. 57, 5094 (1972); http://dx.doi.org/10.1063/1.1678194 (4 pages) | Cited 180 times

Online Publication Date: 4 September 2003

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The general expressions for the time‐dependent fluorescence depolarization caused by anisotropic rotation diffusion have been obtained. It is shown that after an instantaneous exciting light pulse, the parallel and perpendicular components of fluorescence can have a maximum of six exponential decays and the difference of these two components a maximum of five decays. The present results differ from those of previous studies and the differences are discussed.

Determination of a Three Parameter Pair Potential from Second Virial Coefficients: Ar, Kr, and Xe

Bruce W. Davis

J. Chem. Phys. 57, 5098 (1972); http://dx.doi.org/10.1063/1.1678195 (10 pages) | Cited 3 times

Online Publication Date: 4 September 2003

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To prepare second virial coefficient data for use in determining the Ar, Kr, and Xe pair potentials, random errors in B(T) data are initially eliminated by least square fitting to a polynomial in T−1. After choosing an analytical form for the potential, optimum values for the potential parameters are obtained using a modified version of the method of selected points. This procedure permits rapid testing of three parameter model potentials without having extensive tables of reduced second virial coefficients. A piecewise potential (RMMV for rigid, Morse, Mie, and van der Waals) was selected and extensively compared with existing theoretical and experimental determinations of the pair potential for Ar, Kr, and Xe. The RMMV potential was found to be satisfactory, not only in the well region, but also in the short and long range limits.

Singlet‐Triplet Splitting in Diffusing Radical Pairs and the Magnitude of Chemically Induced Electron Spin Polarization

Frank J. Adrian

J. Chem. Phys. 57, 5107 (1972); http://dx.doi.org/10.1063/1.1678196 (7 pages) | Cited 52 times

Online Publication Date: 4 September 2003

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A previous theory of anomalous electron spin resonance spectra of free radicals in solution attributes the electron spin polarizations to the combined effects of singlet‐triplet mixing by magnetic interactions in a diffusing radical pair and singlet‐triplet splitting by the exchange interaction when, and if, the diffusing radicals reencounter each other. This theory is studied in more detail by considering the exchange interaction at all times during the diffusive trajectory of the radical pair, in contrast to the original treatment of approximating it as a rectangular pulse which is nonzero only briefly during the second encounter of the radicals. Time dependent perturbation theory is used to calculate the radical pair wavefunction and the corresponding electron spin polarization to first order in the exchange interaction. The polarization is averaged over all possible diffusion paths of the radicals by averaging the exchange interaction over the distribution of radical pair separations obtained by solution of the diffusion equation with appropriate boundary conditions. These boundary conditions take into account the facts that polarization begins when the radicals separate to a point where the magnetic and exchange interactions are roughly equal, and that the developing polarization is destroyed by spin exchange if the radicals subsequently come too close together. The calculated polarizations are of the right order of magnitude to account for the experimental results, and the dependence of the polarization on the magnetic interactions and the diffusion parameters is essentially the same as predicted by the earlier simpler theory.

On the O2+�C2D2 Reaction: An Endoergic Stripping Process

M. M. Chiang, Bruce H. Mahan, and Charles Maltz

J. Chem. Phys. 57, 5114 (1972); http://dx.doi.org/10.1063/1.1678197 (3 pages) | Cited 8 times

Online Publication Date: 4 September 2003

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We have determined the product velocity vector distributions for the endoergic (ΔE0°=2.23 eV) atom abstraction reaction O2+(C2D2,C2D)O2D+ at a number of values of the initial relative energy. Deuterium atom abstraction occurs at higher energies by a spectator stripping process. An energy threshold for the zero angle reactive scattering process is observed when the energy of the O2+ projectile relative to the abstracted atom is equal to the endoergicity of the reaction. The results show that the spectator stripping process is not to be uniquely associated with exoergic reactions or those which proceed along monotonically decreasing potential energy surfaces.

Self‐Diffusion in Liquid Water to −31°C

Kenneth T. Gillen, D. C. Douglass, and M. J. R. Hoch

J. Chem. Phys. 57, 5117 (1972); http://dx.doi.org/10.1063/1.1678198 (3 pages) | Cited 111 times

Online Publication Date: 4 September 2003

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The self‐diffusion coefficient of water is reported to −31°C, where the activation energy reaches 11 kcal∕mole compared with 4.5 kcal∕mole at 25°C. The similarity of the temperature dependence of the fraction of broken hydrogen bonds, as inferred from Raman and infrared data, and the diffusion coefficient over the entire liquid range forms the basis of empirical support of the dominant role of hydrogen bonding in the fundamental diffusion mechanism.

Strengths and Collision Broadened Widths in the Second Overtone Band of Hydrogen Fluoride

R. L. Spellicy, R. E. Meredith, and F. G. Smith

J. Chem. Phys. 57, 5119 (1972); http://dx.doi.org/10.1063/1.1678199 (5 pages) | Cited 35 times

Online Publication Date: 4 September 2003

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Individual line strengths and self‐broadened half‐widths have been measured in the second overtone band of hydrogen fluoride. The electric dipole matrix element for the band has been determined from the measured strengths. Its value is:
math
The m dependence of the measured half‐widths agree with the Anderson theory of collision broadening if off resonant collisions are taken into account.

Further Considerations on the Theory of Intermolecular Obstruction in Rubber Elasticity

Julius L. Jackson

J. Chem. Phys. 57, 5124 (1972); http://dx.doi.org/10.1063/1.1678200 (4 pages) | Cited 3 times

Online Publication Date: 4 September 2003

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An earlier theory which took into account intermolecular obstruction in rubber is reconsidered. On the basis of a revised procedure for counting configurations of polymer chains, a new equation of state is obtained relating stress to strain in uniaxial extension. The new relationship has the same from as a function of the strain but differs in its dependence on f, the fraction of the rubber volume occupied by the polymer chains. When applied to experiments, it leads to higher values of f. In addition, results presented previously only for uniaxial extension are generalized for arbitrary strains.

Formation of HeH+ from Low‐Energy Collisions of Metastable Helium and Molecular Hydrogen

R. H. Neynaber, G. D. Magnuson, and J. K. Layton

J. Chem. Phys. 57, 5128 (1972); http://dx.doi.org/10.1063/1.1678201 (10 pages) | Cited 30 times

Online Publication Date: 4 September 2003

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A merging‐beams technique has been used to study HeH+ formation resulting from the interaction of a composite beam of He(21S) and He (23S) with a beam of H2. The experiments were conducted over a range of interaction energy W from 0.05 to 10 eV. It was learned that the dominant process for producing HeH+ is the rearrangement ionization reaction He*+H2→HeH++H+e, where He* represents the metastable helium. The experiment consisted of measuring the lab‐energy distributions of HeH+. Relative and absolute cross sections were obtained from these distributions. The distributions indicate that, in the center‐of‐mass system, most of the HeH+ is scattered in the direction of the incident He*. The energies associated with the HeH+ at the peaks of these distributions are very close to those expected for spectator stripping. Conservation of energy for the reaction can only be achieved by assuming that the electron carries away a substantial portion of the available energy. It is shown that the two‐step model He*+H2→He+H2+†+e→HeH++H+e (where † indicates ground‐state or vibrationally excited H2+) satisfactorily explains the measured lab‐energy distributions near W=0.05 eV but does not agree completely with the results for W ≥ 2 eV.

Infrared Study of Matrix‐Isolated Lithium Isocyanide

Zakya K. Ismail, Robert H. Hauge, and John L. Margrave

J. Chem. Phys. 57, 5137 (1972); http://dx.doi.org/10.1063/1.1678202 (6 pages) | Cited 29 times

Online Publication Date: 4 September 2003

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The infrared spectrum of lithium isocyanide trapped in solid matrices of neon, argon, and nitrogen was examined over the range 4000–33 cm−1. The effect of temperature cycling, which results in migration of trapped molecules to generate polymeric species, has been pursued. A careful study of the effect on the spectra of superheating the vapor species has been carried out. By these means it has been possible to identify the bands in the spectrum due to monomeric and to polymeric species. This paper is only concerned with the monomeric species. Isotope frequency shifts were measured for carbon‐13, nitrogen‐15, and lithium‐6 enriched samples of lithium isocyanide. From the measured isotopic shifts it was possible to determine the structure of the monomer of the lithium compound as being linear LiNC. Accurate force constants were calculated using the measured frequency values of the three fundamental vibrational modes of the different isotopic molecules of LiNC.

Scattering of Diatomic and Polyatomic Molecules from the (100) Crystal Face of Platinum

L. A. West and G. A. Somorjai

J. Chem. Phys. 57, 5143 (1972); http://dx.doi.org/10.1063/1.1678203 (11 pages) | Cited 19 times

Online Publication Date: 4 September 2003

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The angular distributions of thermal energy molecular beams of diatomic (CO, N2, O2, NO, H2, D2) and polyatomic (CO2, N2O, C2H2, NO2, NH3, and methylene cyclobutane) molecules were monitored following scattering from the (100) crystal face of platinum. All of the gases studied (with the exception of ammonia) yielded directed scattering patterns with the maximum intensity peaked at or near the specular angle for scattering from a clean platinum surface or from a platinum surface covered by a layer of ordered graphite. Broad, cosinelike angular distributions which were independent of incident angle were observed, however, for the cases of C2H2 scattered from an adsorbed layer of C2H2 and CO scattered from adsorbed CO. These results seem to indicate that efficient energy transfer between the surface atoms and gas molecules, as indicated by angular distributions, occurs only in specific instances. Apparently, the incident particles are reflected whenever the nonlocalized vibrational energy modes of surface atoms and the translational energy of the incident molecules are of similar magnitude. The adsorption of gases may lead to the formation of additional low frequency localized surface modes that can be excited by the incident molecules. The efficient transfer of energy via localized surface modes would increase the residence time of the incident molecules and could thus account for the cosinelike angular distributions observed for C2H2 and CO.

Effect of Thickness on the Layer Structure of Grandjean Texture in a Sheared Cholesteric Liquid Crystal

J. M. Pochan and D. G. Marsh

J. Chem. Phys. 57, 5154 (1972); http://dx.doi.org/10.1063/1.1678204 (3 pages) | Cited 3 times

Online Publication Date: 4 September 2003

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Reflection spectra of the sheared (1.32×102sec−1) Grandjean texture of the cholesteric mesophase have been obtained as a function of sample thickness in the visible wavelength region. These studies substantiate a model of the sheared mesophase composed of layers consisting of normal Grandjean, perturbed Grandjean, and dynamic focal conic textures. Changes in sample thickness affect principally the perturbed Grandjean layers. The central dynamic focal conic layer is shown to be relatively thin (<7 μ).

Drift Velocities and Interactions of Cs+ Ions with Atmospheric Gases

L. G. McKnight and J. M. Sawina

J. Chem. Phys. 57, 5156 (1972); http://dx.doi.org/10.1063/1.1678205 (7 pages) | Cited 11 times

Online Publication Date: 4 September 2003

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The drift velocities and interactions of the Cs+ ion in atmospheric gases have been measured at 300°K using an ion drift apparatus. Cs+ was found not to form clusters with N2, O2, and Ar at 300°K, implying a reaction rate less than 10−24 cm6∕sec or an equilibrium constant less than 10−2 torr−1. Low field mobilities (μN) for the ion were 6.0, 5.9, and 5.6×1019(V⋅sec⋅cm)−1 in O2, N2, and Ar, respectively. Cs+ was found to form clusters with water by the three‐body reaction Cs++H2O+N2→(Cs⋅H2O)++N2, with a forward rate constant 9×10−30cm6/sec and a reverse rate constant of 1×10−15cm3/sec at 306°K. Ion clusters as large as (Cs⋅4H2O)+ were observed and, by measuring the equilibrium constants between 300 and 650°K, the entropy and enthalpy of formation of the first, second, and third water clusters were determined. With SO2, Cs+ was found to cluster by the reaction Cs++SO2+M↔(Cs⋅SO2)++M, with ΔH°= − 11 kcal∕mole and ΔS°= − 19 eu. The forward rate constant for the formation of (Cs⋅SO2)+ was 3×10−20 cm6/sec and the reverse rate constant 1×10−13cm3/sec. The rates were the same with either SO2 or N2 as the third body. In CO2 the equilibrium amount of the clustered ion was too small to enable the measurement of the rate of formation, but the equilibrium constant measured between 200 and 400°K allowed the ΔH° and ΔS° values to be determined as −6 kcal∕mol and − 14 eu, respectively. The low field mobility of Cs+ in CO2 was found to be 3.1×1019(V⋅sec⋅cm)−1. The interactions of the Cs+ ion with its large radius, low ionization potential, and almost inert electronic structure should be the minimum ion‐molecule interaction for an ion of this size. The interactions of smaller and more reactive ions should be at least as great as that of Cs+. Evidently the formation of ion‐molecule clusters with polar and polarizable molecules is a nearly universal property of small ions.

Charge Transfer States of Molecular Crystals in Contact with a Metal

Joong‐Woong Pak and Sang‐il Choi

J. Chem. Phys. 57, 5163 (1972); http://dx.doi.org/10.1063/1.1678206 (8 pages)

Online Publication Date: 4 September 2003

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A quantum mechanical model study of electronic states of a molecular crystal in contact with a metal is made. A molecular crystal is represented by the parameters: intermolecular spacing, electron affinity of a constituent molecule, dielectric constant, charge transfer matrix, and polarization energy of the molecular crystal. A set of difference equations is established and solved for the energy eigenvalues and eigenfunctions under the assumption that the interaction between a transferred electron and a metal is that of electrostatic image potential. Appearance of lower energy bands corresponding to an electron localized in the x direction and one continuum energy spectrum representing the conducting state of an excess electron in the molecular crystal is noted. Also, the transferred electron density is calculated for each energy band.
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