JPCHAX
`
`
`
`The Journal of
`
`
`
`
`VOLUME 99
`‘* MAY11,1995
`
` ‘
`
`NUMBER19
`
`"'43.
`
`_..‘..”Lu "
`'IL‘
`(5‘. 2-
`
`
`
`PUBLISHED WEEKLY BY THE AMERICAN CHEMICAL SOCIETY
`
`NAN1016
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`1
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`NAN1016
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`

`
`
`activity relationships should be
`considered as a whole in quantitative
`terms, starting with physical organic
`chemistry and including all types of
`biochemical and biological processes.
`They give a unified view with
`extensive cross—referencing and show
`the interrelatedness of SAR from the
`ionization of acetic acid to the action
`of hallucinogens in humans.
`Throughout the book, QSAR in
`biological processes are related to
`those in physical organic chemistry.
`
`blame 2: Hydrophobic, Electronic, and
`Stert'c Constants contains comprehen—
`sive tables of physicochemical
`parameters (substituent constants and
`octanoI—water log P values) that are
`necessary for quantitative structure—
`activity relationships and qualitative
`SAR. These values were collected over
`25 years by two of the most re—
`nowned researchers in the field.
`
`Volume I by Corwin Hansch and
`Albert Leo
`
`
`
`
`
`
`
`
`Volume 2 by Albert Leo, Corwin
`
`Hansch. and David Hoekman
` ACS Professional Reference Book
`880 pages [1995) Clothbouricl
`ISBN 0-8412-2993- J"
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`T“°"°“'""' °' Physical Chemistry
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`Editor-in-Chief: MOSTAFA A. EL-SAYED. Georgia Institute of Technology
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`University of California. Berkeley
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`Massachusetts Institute of Technology
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`E. I. Du Pont de Nemours and Company
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`T“°"°""""‘"°" Physical Chemistry®
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`
`
`Registered in US. Patent and Trademark Ofllce
`Copyright 1995 by the American Chemical Society
`
`Vofume 99’ Number 19 May 11’ 1995
`JPCHAx 9909) 7197-7844 (1995)
`ISSN 0022-3654
`
`Mostafa A. El-Sayed Festschrift
`Photograph of Mostafa A. El-Sayed
`
`Scientific Co—workers
`
`Biography
`
`List of Publications
`
`John D. Simon. Alan Campion, and Malcolm F. Nicol
`
`ARTICLES
`
`SPECTROSCOPY
`
`Hierarchy of Spectroscopies and the Structure of Matter
`
`Raymond K. Sheline
`
`Luminescent GoldU) Complexes. Optical and ODMR Studies of Mononuclear Halo(triphenylphosphine)— and
`Haloltriphenylarsine)gold(l} Complexes
`L. J. Larson, E. M. McCauley, B. Weissbart, and D. S. Tinti“
`
`CASSCF Study of the Ground State and Lowest Lying 3s Rydberg States of ABCO
`R. Disselkamp, Q.-Y. Shang, and E. R. Bernstein“
`
`Threshold Photoelectron Spectroscopy of C12 and Br; up to 35 eV
`A. J. Yencha,* A. Hopkirk, A. Hiraya, R. J. Donovan, J. G. Geode, R. R. J. Maier, G. C. King, and A. Kvaran
`
`Phosphorescence and Zero-Field Optically Detected Magnetic Resonance Studies of (ndlm Transition-Metal Complexes. 2.
`CdX3(phen) [X = Cl. Br. and I: phen = LID-Phenanthrolinc)
`Seiya Kimachi, Shigeru Ikeda, and Tohru Azumi“
`
`Resonance Raman Characterization of the Triplet State of Zinc Tetraphenyichlorin
`S. E. Vitals. Shin-ichi Terashila, Milton E. Blackwood Jl'., Ranjit Kumble, Yukihiro Ozaki, and Thomas G. Spiro“
`
`Excited State Distortions in Ligand to Ligand Charge Transfer Excited States of Metal Diimlne Dithiolate Mixed Ligand
`Complexes
`Jefl'rey L. Wootton and Jeffrey I. Zink"
`
`S“ and 5: Electronic States of 2»Vinylnaphthalene. A Pseudo Polyene
`
`James F. Pfanstie] and David W. Pratt‘“
`
`Transient Phase Grating Spectroscopy of Nanosecond Relaxation Dynamics in Bacteriorhodopsin
`T. Renner, F. W. Deeg,* and C. Briiuchle
`
`Third-Order Nonlinearities Studied by Femtosecond Infrared Methods
`Tianquan Lian, Ym-iy Khoiodenko, Bruce Locke, and Robin M. Hochstrasser“
`
`Triplet State Potentials in the Competitive Excitation Mechanisms of Intramolecular Proton Transfer
`Michael Kasha.‘ Jozef Heldt, and David Gonnin
`
`Thermal Effects in Resonance Raman Scattering: Analysis of the Raman Intensities of Rhodopsin and of the Time-Resolved
`Raman Scattering of Bacteriorhodopsin
`Andrew P. Shreve and Richard A. Mathies“
`
`Hypcrquenched Glassy Films of Water: A Study by Hole Burning
`
`W.—H. Kim, T. Reinot, J. M. Hayes, and G. J. Small“
`
`Rotational Coherence Spectroscopy of Aromatic-(Ar). Clusters: Geometries of Anthracene-{Ar}...
`9.lU-Dichloroanthracene—Ar. and Tetracene—Ar
`Shane M. Ohline, Joann Romascan, and Peter M. Felker"
`
`MOLECULAR DYNAMICS
`
`Pushing Pyrazine to the (Statistical) Limit
`
`William R. Moomaitr,“l Te-Yang Lin, and Jonathan E. Kenny“
`
`5
`
`”H97
`
`7198
`
`7l99
`
`T200
`
`?211
`
`7218
`
`7227
`
`-.923]
`
`7242
`
`7246
`
`7251
`
`7258
`
`726?
`
`"£272
`
`7281
`
`7285
`
`7300
`
`731]
`
`7320
`
`5
`
`

`

`4A J. Phys. Chem., Vol. 99. No. I9. I995
`
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`

`J'. Phys. Chem, Vol. 99, N0. 19. [995 5A
`
`Temperature and Pressure Dependent Optical Dephasing of Pentacene in Triclinic and Monoclinic p-Terphenyl
`Bruce J. Beer and Eric L. Chronister"
`
`Subspace Method for Long Time Scale Molecular Dynamics
`
`Attila Askar, Brian Space, and Herschel Rabitz"
`
`Dissociation of Highly Excited N03 Induced by Collisions with Ar. CO. and O;
`
`A. Sanov, C. R. Bieler, and H. Reisler“
`
`Proton Transfer in Ground and Excited Electronic States of Glyoxalrnonohydrazine
`
`Karl Luth and Steve Scheiner“
`
`7324
`
`7330
`
`7339
`
`7352
`
`Solvent Effects on the Spectroscopy and Ultrafast Photochemistry of Chlorine Dioxide
`Robert C. Dunn, Bret N. Flanders. and John D. Simon“
`
`7360
`
`Collisional Flow of Vibrational Energy into Surrounding Vibrational Fields within S. p~Difluorobenzene Rate Constants for
`Initial Levels with High Vibrational Excitation
`
`David L. Catlett. .lr., Charles S. Parmenter,‘l and Christopher J. Pursell
`
`Experimental and Theoretical Velocity Profiles for Pure Rotational Scattering in Carbon Dioxide-Hot Hydrogen Atom
`Collisions
`C. K. Ni, T. G. Kreutz, and G. W. Flynn"
`
`Photoinduced Radical Cleavage of Iodobenzophenones
`
`Peter J. Wagner“ and Carol 1. Waite
`
`The Wavelength Dependence of the Rates of Internal Energy Redistribution during the Photodissociation of 3-lodopyridine
`John E. Freitas, Mostafa A. El-Sayed,* and Hyun Jin Hwang
`
`Collisional Alignment of Molecular Rotation: Simple Models and Trajectory Analysis
`David Pullman,‘ Bretislav Friedrich,‘ and Dudley Herschbach"
`
`7371
`
`738!
`
`7388
`
`7395
`
`7407
`
`Intramolecular Charge Transfer and Solvent-Polarity Dependence of Radiative Decay Rate in Photoexcited Dinaphthylamines
`Shtjie Wang. Jianiian Cai, Rovshan Sadygov, and Edward C. Lin)"
`
`7416
`
`Solvation Ultrafast Dynamics of Reactions. 8. Acid—Base Reactions in Finite-Sized Clusters of Naphthol in Ammonia. Water.
`and Piperidine
`S. K. Kim. .I. J. Breen, D. M. Willberg, L. W. Pang, A. Heikal, J. A. Synge, and A. H. Zewail“
`
`742 I
`
`Femtosecond Transient Absorption Studies of Electrons in Liquid Alkanes
`Frederick H. Long, Hong Lu, and Kenneth B. Eisenthal“
`
`Transient Absorption and Vibrational Relaxation Dynamics of the Lowest Excited Singlet State of Pyrene in Solution
`Paolo Foggl,* Luca Pettini, Imre santa, Roberto Righinl, and Salvatore Califano
`
`HNCO + hv{l93.3 11m) -* H + NCO: Center-of—Mass Translational Energy Distribution. Reaction Dynamics. and
`DD(H~NC0}
`Jingsong Zhang, Michael Dulligan, and Curt Wittig“
`
`Femtosecond Many-Body Dynamics of Caging: Experiment and Simulation of l; Photodissociation—Recombination in Solid
`Ar
`Z. Li, R. Zadoyan, V. A. Apltarian,‘ and C. C. Martens‘
`
`Dynamics of Ultrahigh Molecular Rydbergs in Weak Electric Fields
`
`M. Bixon" and Joshua Jorhier"
`
`7436
`
`7439
`
`7446
`
`7453
`
`7466
`
`CHEMICAL KINETICS
`
`Kinetics and Product Branching Ratios for the Reaction HCO + N0;
`Yili Guo, Sean C. Smith, C. Bradley Moore,1R and Carl F. Melina
`
`7473
`
`Quenching Rate Constants of the Xe(5p56p and 6p’) States and the Energy-Pooling ionization Reaction of Xe(5p565) Atoms
`T. 0. Nelson, D. W. Setser,* and M. K. Richmann
`
`7482
`
`Four—Center Reactions: A Computational Study of Collisional Activation. Concerted Bond Switching. and Collisional
`Stabilization in Impact Heated Clusters
`Tamar R32 and R. D. Levine“
`
`7495
`
`The Mechanism of the Thermal Decomposition and the (n—rt“) Excited States of Azomethane
`Ching-Han Hu and Henry F. Schaefer 111*
`
`Molecular Architecture and Environmental Effects in Intramolecular Electron Transfer. An Electron Paramagnetic Resonance
`Study
`Kobi Hasharoni, Haim Levanon,‘ Jiirg Gatschmann, Heike Schubert. Harry Kurreck, and Klaus Miibius
`
`Influence of Atomic Fine Structure on Bimolecular Rate Constants: The CIGP) + HCl Reaction
`
`George C. Schatz
`
`Optogalvanic Effect as a Probe of Plasma Processes
`
`D. Kumar, R. R. Zinn. T. D. Armstrong, and S. P. McGlynn*
`
`Proton Transfers of Aqueous 7-Hydroxyquinoline in the First Excited Singlet. Lowest Triplet. and Ground States
`7
`Strong-In Lee and Dir-Jenn Jang‘
`
`7507
`
`7514
`
`7522
`
`7530
`
`7537
`
`7
`
`

`

`6A J'. Phys. Chem. Vol. 99. No. 1' 9. i 995
`
`Reaction—Diffusion Model for A + A Reaction
`
`Katja Lindenberg,‘ Panes Argyrakis, and Raoul Kopelman
`
`Nonequilibrium Free Energy Functions. Recombination Dynamics, and Vibrational Relaxation of If in Acetonitrile: Molecular
`Dynamics of Charge Flow in the Electronically Adiabatic Limit
`llan Beqiamin,‘ Paul F. Barbara, Bradley J. Genner, and James T. Hynes“
`
`Ultrafast Experiments on the Photodissociation. Recombination. and Vibrational Relaxation of If: Role of Solvent-Induced
`Solute Charge Flow
`Peter K. Walhoul, Joseph C. Alfano, Khalid A. M. Thakur, and Paul F. Barbara“
`
`Theoretical Study of Electron Transfer in Ferrocytochromes
`
`A. A. Stuchebrul-thov and R. A. Marcus“
`
`Beyond State-to—State Differential Cross Sections: Determination of Product Polarization in Photoinitiated Bimolecuiar
`Reactions
`Neil E. Shafer-Ray, Andrew J. Orr-Ewing. and Richard N. Zare“
`
`7557
`
`7563
`
`7581
`
`7591
`
`Molecular Adsorption—Desorption Reactions of Ammonia on Alkali Halide Clusters and Nanocrystals
`Margie L. Homer. Frank E. Livingston, and Robert L. Whetten“
`
`7604
`
`PHYSICAL CHEMISTRY OF MATERIALS
`
`Chemical Affinity of iii—Sim Phosphatizing Reagents on Cold-Rolled Steel
`
`T. Yu, L. Li, and C. T. Lin“
`
`Laser-Induced Polymeric Film and Particle Formation from a Gaseous Mixture of Methyl Acryiate and Acrolein
`Htroshi Morita" and Makoto Shimizu
`
`Photooxidation of CH3C] on TiOfil [0}: A Mechanism Not Involving H20
`
`G. Lu, A. Linsebigler, and J. T. Yates, Jr.‘l
`
`Effect of Structural Order on the Dark Current and Photocurrent in Zinc Octakisw-decosyethylmorphyfin Thin-Layer Cells
`Chong-Yang Liu, Horng-Long Pan, Huaiun Tang, Mal-ye Anne Fox,* and Allen J. Bard“
`
`Structures and Growth Mechanisms for Heteroepitaxial fcc(l ll) Thin Metal Films
`
`Tsun-Mei Chang and Emily A. Carter“
`
`Quantum Confinement Effects in CdSe Quantum Dots
`
`B. Zorn'lan,‘= M. V. Ramakrishna, and R. A. Friesner“
`
`7613
`
`7621
`
`7626
`
`7632
`
`7637
`
`7649
`
`Time Resolved Electron Spin Resonance and Laser Flash Spectroscopy Investigation of the Photoreduction of
`Anthraquinone-2.6—disulfonic Acid. Disodium Salt by Sodium Sulfite in Aerosol OT Reverse Micelles
`Nicholas J. Turro* and Igor V. Khudyaltov
`
`7654
`
`Structure and Wetting Properties of w—Alkoxy—n-alkanethiolate Monolayers on Gold and Silver
`Paul E. Laihinis,‘I Colin D. Bain,‘ Ralph G. Nuzzo,* and George M. Whitesides“
`
`7663
`
`Infrared Spectroscopy of Model Electrochemical Interfaces in Ultrahigh Vacuum: Roles of Adsorbate and Cation Double-Layer
`Hydration in the Pt( I i 1)-Carbon Monoxide Aqueous System
`Naushad Kizhakevariam, Ignacio Villegas, and Michael J. Weaver“
`
`Charge-Transfer—to—Solvent Photochemisz of Electrode-Confined Ferrocene- and Cobaltocene—Based Polymers:
`Photoelectrochcmical Reduction of Halocarbons Helen B. Tatistchefi', Lawrence F. Hancock, and Mark S. Wrighton“
`
`7677
`
`7689
`
`Effect of Tension on Pore Formation in Drug-Containing Vesicles
`Cheryl Li Weakliem,‘ Gary Fujii, Joan-En Chang, Avinoam Ben-Shaul, and William M. Gelhart
`
`7694
`
`Density Functional Theory Prediction of the Second—Order Hyperpolarizability of Metalloporphines
`Nohuyulti Matsuzawa,‘ Masafunti Ate, and David A. Dixon“
`
`7698
`
`Investigations of ClzClJ.+ (x- = 0*— 10) Using the lon
`Structures of Carbon Clusters from Polychlorinated Graphitic Precursors:
`Chromatography Method
`Gert von Helden, Edwart Porter, Nigel G. Gotts, and Michael T. Bowers“
`
`Influence of Doping on the Third~0rder Optical Nonlinearity in Poly(bithiophcne): First Observation of
`ChargevTransfer-lnduced Scattering
`Klaus Meerholz, Jacek Swiatkiewiez, and Paras N. Prasad*
`
`Enhancement of Metallic Silver Monomer Evaporation by the Adhesion of Poiar Molecules to Silver Nanocluster Ions
`Clifton K. Fagerquist, Dilip K. Sensharma. Mostafa A. El-Sayed,* Angel Rubin. and Marvin L. Cohen
`
`Studies of Excess Electrons in Sodium Chloride Clusters and of Excess Protons in Water Clusters
`R. g. Barnett, H.—P. Cheng, H. Hakkinen, and Uzi Laudman“
`
`7707
`
`7715
`
`7723
`
`773l
`
`8
`
`

`

`J. Phys. Chem. Vol. 99. No. 19. 1995
`
`7A
`
`Synthesis and Characterization of InP. GaP, and GalnPg Quantum Dots
`O. I. Mieie.‘ J. R. Sprague. C. J. Curtis,* K. M. Jones, J. L Machol, A. J. Nozik,‘ H. GieSsen, B. Flue-gel.
`G. Mobs, and N. Peyghambarian
`
`7754
`
`BIOPHYSICAL CHEMISTRY
`
`Influence of Membrane Microstructure on the Diffusion Ban‘ier of Supported Liquid Crystalline Membranes
`R. van den Berg,‘ D. Schulze, J. A. Bolt-Westerhoff, F. de Jong. D. N. Reinhoudt, D. Velinova. and L. Buitenhuis
`
`Time-Resolved Resonance Raman Study of Free-Base Octaethylporphyrins in the Sn. 8:. and T1 States
`S. Sato, K. Aoyagi, T. Haya, and T. Kitagawa"
`
`Fourier Transform Infrared Spectroscopic Studies of the Effect of Ca2+ Binding on the States of Aspartic Acid Side Chains in
`Bacteriorhodopsin
`Satoshi Masuda, Masayuki Nara, Mitsuo Tasumi", Mostafa A. El-Sayed*, and Janos K. Lanyi
`
`Electrostatic Potentials near the Surface of DNA: Comparing Theory and Experiment
`Jonathan L. Hecht, Barry Honig,‘ Yeon-Kyun Shin, and Wayne L. Hubbell
`
`Electrostatic and Conformational Effects on the Proton Translocation Steps in Bacteriorhodopsin: Analysis of Multiple M
`Structures
`Christina Schamaglg“ Johannes Hettenkofer, and Sighart F. Fischer
`
`Picosecond Time-Resolved Absorption Dynamics in the Artificial Bacteriorhodopsin Pigment BR6.9
`J. K. Delaney, G. H. Atkinson,“l M. Shows} and M. Ottolenghi“
`
`Time- and Space-Resolved Studies of the Physics and Chemistry of Liquid Water near a Biologically Relevant Interface
`C. H. Cho, Mary Chung, J. Lee, Tom Nguyen, Surjit Singh, Mary Vedamuthu. Shihua Yao, J.—B. Zhu, and
`G. Wilse Robinson“
`
`TI-{ERMODYNAMJCS
`
`Griineisen Ratios of M g0 from the Calculation of Entropy
`Hyunchae Cyan, Orson L. Anderson. Donald G. Isaak, and Malcolm Nicol“
`
`Ligand Effects in Organometallic Therrnochemistry: The Sequential Bond Energies of Ni(CO),"' and Ni(N2),+ {x = 144) and
`1"~1i(1\10).+ (x = 1-3)
`Farooq A. Khan, Dale L. Steele, and P. B. Armentront“
`
`Mass Spectral and Computational Free Energy Studies of Alkali Metal Ion-Containing Water Clusters
`E. A. Steel, Kenneth M. MEI‘Z, Jr., A. Selinger, and A. W. Castleman, Jr.‘
`
`The Kelvin Relation: Stability. Fluctuation. and Factors Involved in Measurement
`
`Howard Reiss“ and Ger J. M. Koper
`
`7760
`
`7766
`
`7776
`
`7782
`
`7787
`
`7301
`
`7806
`
`7813
`
`7819
`
`7329
`
`7837
`
`I Supplementary material for this paper is available separately (consult the masthead page for ordering
`information); all supplementary material except structure factor tables will also appear following the
`paper in the microfilm edition of this journal.
`
`* 111 papers with more than one author, the asterisk indicates the name of the author to whom inquiries
`about the paper should be addressed.
`
`9
`
`

`

`
`This material may be protected by Copyright law (Title 17 us. Code)
`
`
`
`
`7754
`
`J. Phys. Chem. 1995, 99. 7754—7759
`
`Synthesis and Characterization of InP, GaP, and GaIan Quantum Dots
`
`0. I. Miéié,* J. R. Sprague, C. J. Curtis? K. M. Jones, J. L Machol, and A. J. Nozik*
`
`National Renewable Energy Laboratory. 1’6}? Cole Blvd, Golden. Colorado 80401
`
`H. Giessen, B. Fluegel, G. Mobs, and N. Peyghambarian
`
`Optical Sciences Center, University of Arizona, Tucson. Arizona 85721
`
`Received: October 6. 1994; In Final Form: January 26.
`
`l995®
`
`Quantum dots (QDs) of InP, GaP, and GalnP: with diameters ranging from 20 to 65 (it were synthesized as
`well-crystallized nanoparticles with bulk zinc blende structure. The synthesis of InP, GaP. and GalnP; QDgJ
`was achieved by heating appropriate organometallic precursors with stabilizers in high boiling solvents f0;
`several days to produce QDs which can be dissolved in nonpolar organic solvents. forming transparent colloids?
`QD dispersions. The high sample quality of the In? and GaP (203 results in excitonic features in the absorptirmr
`spectra. Ternary QDs of GalnPg were synthesized with a well~crystallized zinc blende structure and lattice:
`spacing between InP and GaP The QDs were characterized by TEM, powder x--ray diffraction. steady state-
`optical absorption and photoluminescence spectroscopy, transient photoluminescence spectroscopy, and fit toil
`ps pumpprobe absorption (i. e., hole-b-urning) spectroscopy
`
`prepared by mixing anhydrous InCl; or GaCl; with Na3C204
`in CH3CN in a 1:] molar ratio. and heating the solution of 70
`°C under N2 for 15 h. The resulting suspension at white material"
`was filtered and the solvent removed from the clear filtrate to.
`give the chlorometal oxalate complex. The complex appears
`to contain two metal atoms per oxalate and three chloride ligands
`per metal atom. but the mode of oxalate binding and the number:
`of CH3CN ligands present have not yet been established. All
`synthetic procedures were carried out using standard airless 1
`techniques.
`Synthesis of Colloidal InP QDs. Quantum dots of InP were
`synthesized by mixing the chloroindium oxalate complex and'
`P(SiMe3}3 in a molar ratio of In:P of l.6:l in CH3CN at room.
`temperature to form a soluble orange InP precursor species. and
`then heating this precursor solution with a mixture of trl-'
`octylphosphine oxide (TOPO) and nioctylphosphine (TOP). Use,
`of TOPOFTOP as a colloidal stabilizer was based on the recent
`
`
`
`
`Introduction
`
`The unique size-dependent, optical. photocatalytic. and
`nonlinear optical properties of colloidal nanocrystalline semi~
`conductor particles (called quantum dots (QDs)) continue to
`attract considerable interest] Excellent progress has been made
`in the preparation and characterization of 0135 made from II—
`VI compounds, oxides (Ti. In, Cu, W) and iodides (Hg. Pb.
`Bi}; the preparation and properties of Si QDs have also been
`reported.2 However. the preparation of high-quality QDs of
`III—V semiconductors has proven to be problematic-"'1" Here.
`we report the synthesis and properties of excellent quality binary
`III‘V InP and Ge? ODS, and the ternary Ill—V QD, Galan.
`It is interesting to compare the properties of InP and GaP
`0135 because the former is a direct gap semiconductor. while
`the latter is an indirect gap semiconductor; the effects of size
`quantization on the optical properties of the indirect semi-
`conductor GaP are explored here. Galan is of interest because
`its band gap depends on the degree of atomic ordering in the
`material, and the effect of quantization on this behavior has
`not been investigated.
`The preparation of well-crystallized QDs of Ill—V com-
`pounds requires high temperature. and the relevant solution
`chemistry is not well-developed. At high temperatures, quantum
`dots tend to aggregate irreversibly. and the resulting precipitate
`cannot be redissolved to form colloidal solutions; also. at high
`temperatures the particles tend to grow and lose their quantum
`confinement. However. using high~boiling solvents (t >300
`°C) and certain stabilizers. we have recently succeeded in
`preparing well-crystallized InP QDs” with diameters ~25 A.
`In this work. we report on additional characterization studies
`of InP QDs. and the successful synthesis of colloidal dispersion