Geminate recombination and relaxation of molecular iodine (English)

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In: The Journal of Chemical Physics   ;  84 ,  3  ;  1335-1344  ;  1986

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Picosecond absorption kinetics of I2 in several room temperature solvents have been obtained. Probe wavelengths of 500, 580, and 640 nm were used following excitation with 30 ps pulses of 532, 630, or 683 nm light. The results indicate that population of the electronically excited A(3π1u) and A’(3π2u) states occurs rapidly (<30 ps) following dissociation. Analysis of transient absorption intensities indicates that repopulation of the ground electronic state requires about 30–50 ps. We propose that the difference in population times may be understood in terms of trapping in weakly bound electronic states (perhaps 3π0−u) which relax to populate the ground electronic state, or in terms of slow atom recombination into the ground state. The results show that for I2 in CCl4, X state repopulation and vibrational relaxation occur on roughly comparable time scales. The results also show that the recombination dynamics are determined primarily by the nature of dissociative state, not the recoil energy. Vibrational relaxation rates through the ground state mainfold were interpreted in terms of vibration to translation energy transfer as given by the Schwartz, Slawsky, Herzfeld theory. This was found to work quite well for weakly interacting solvents such as CFCl3, C2Cl3F3, and CCl4. This simple theory breaks down for more strongly interacting solvents such as CH2Cl2 and CHCl3.

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Laser photoelectron spectroscopic determination of electronic states of Fe atoms produced in multiphoton dissociation of Fe(CO)5 in the gas phase
Nagano, Yatsuhisa / Achiba, Yohji / Kimura, Katsumi | 1986
Resonance Raman overtone intensity calculations of a matrix‐isolated I2 molecule by the symmetrized split operator fast Fourier transform method
Kono, H. / Lin, S. H. | 1986
High pressure study of associated media: Raman scattering of pyridine complexes in aqueous solution
Zakin, M. R. / Grubb, S. G. / King, H. E. / Herschbach, D. R. | 1986
Nuclear spin‐lattice relaxation in the sodium anion, Na−
Holton, Dolores M. / Ellaboudy, Ahmed / Pyper, Nicholas C. / Edwards, Peter P. | 1986
Chemical timing 3. The picosecond dynamics of intramolecular vibrational redistribution from 11 levels in S1 p‐difluorobenzene vapor
Holtzclaw, Karl W. / Parmenter, Charles S. | 1986
Chemical timing 4. The rovibronic level structure associated with intramolecular vibrational redistribution in S1 p‐difluorobenzene
Dolson, D. A. / Holtzclaw, K. W. / Moss, D. B. / Parmenter, C. S. | 1986
A problem of gauge for matter–radiation interaction in calculations of intensities of vibrational transitions
Sobolewski, A. L. | 1986
Proton magnetic resonance study of the H2–Ne potential energy surface
Wagner, Robert S. / Armstrong, Robin L. / Lemaire, Claude / McCourt, Frederick R. | 1986
Photoionization studies of HgKr and HgXe
Liao, C. L. / Ng, C. Y. | 1986
Magnetic field modulated infrared laser spectroscopy of molecular ions: The ν1 band of DCO+
Kawaguchi, Kentarou / McKellar, A. R. W. / Hirota, Eizi | 1986
Rotational collisional narrowing in an infrared CO2 Q branch studied with a tunable‐diode laser
Strow, L. Larrabee / Gentry, Bruce M. | 1986
The microwave spectrum of an unstable molecule, HPO
Saito, Shuji / Endo, Yasuki / Hirota, Eizi | 1986
Quantitative photoexcitation study of SiH4 in vacuum ultraviolet
Suto, Masako / Lee, L. C. | 1986
The laser induced fluorescence spectrum of the HeCl2 van der Waals molecule
Cline, Joseph I. / Evard, Dwight D. / Thommen, Fritz / Janda, Kenneth C. | 1986
Vibrational spectroscopy of van der Waals bonds: Measurement of the perpendicular bend of ArHCl by intracavity far infrared laser spectroscopy of a supersonic jet
Ray, Douglas / Robinson, Ruth L. / Gwo, Dz‐Hung / Saykally, Richard J. | 1986
The 4f states of He2: A new spectrum of He2 in the near infrared
Herzberg, G. / Jungen, Ch. | 1986
The microwave spectrum of propyne in the 17–52 GHz region for the V10=3 vibrational state
Prakash, Vinod / Roberts, J. A. | 1986
Field‐dependent C‐13 chemical shifts in solids: A second‐order dipolar perturbation
VanderHart, D. L. | 1986
Radiationless transitions in gas phase phenol and the effects of hydrogen bonding
Sur, Abha / Johnson, Philip M. | 1986
Microwave spectrum of the boron monoxide radical, BO
Tanimoto, Mitsutoshi / Saito, Shuji / Hirota, Eizi | 1986
The photodissociation spectrum of SO+2
Thomas, Timothy F. / Dale, Fred / Paulson, John F. | 1986
Extra resonances in four‐wave mixing as a probe of exciton dynamics: The steady‐state analog of the transient grating
Loring, Roger F. / Mukamel, Shaul | 1986
EPR spectrum features of the tetrameric copper compounds of formula Cu4OX6L4
Buluggiu, E. | 1986
Theory of time and frequency resolved resonance secondary radiation from a three‐level system
Melinger, J. S. / Albrecht, A. C. | 1986
Theoretical and experimental studies of the triatomic doubly charged ions CO2+2, OCS2+, and CS2+2
Millie, P. / Nenner, I. / Archirel, P. / Lablanquie, P. / Fournier, P. / Eland, J. H. D. | 1986
The dynamic Jahn–Teller effect in sym‐triazine: Nonadiabatic wave functions and hindered fluxionality
Whetten, Robert L. / Haber, Kenneth S. / Grant, Edward R. | 1986
Picosecond laser study of the quasicontinuum of C2F5Cl
Mukherjee, P. / Kwok, H. S. | 1986
A theoretical study of the infrared transition matrix elements for the X 1Σ+ state of the CH+ and CD+ molecules
Ornellas, Fernando R. / Machado, Francisco B. C. | 1986
Exciton and vibronic effects in the spectroscopy of bianthracene in supersonic beams
Khundkar, Lutfur R. / Zewail, Ahmed H. | 1986
The calculated ν2 (inversion) spectrum of H3O+
Liu, Di‐Jia / Oka, Takeshi / Sears, Trevor J. | 1986
Microwave‐optical double resonance of HNO. II. Rotational spectrum in A˜ 1A’’(020)
Takagi, Kojiro / Saito, Shuji / Suzuki, Tetsuo / Hirota, Eizi | 1986
Photoionization and fragmentation of (N2O)n clusters
Kamke, W. / Kamke, B. / Kiefl, H. U. / Hertel, I. V. | 1986
Geminate recombination and relaxation of molecular iodine
Abul‐Haj, N. Alan / Kelley, David F. | 1986
Branching ratios for quenching and reaction in the interaction of S(1D2) with various gases
Black, Graham | 1986
Channel specific rate constants for reactions of O(1D) with HCl and HBr
Wine, P. H. / Wells, J. R / Ravishankara, A. R. | 1986
Intramolecular vibrational energy redistribution and the gas phase overtone spectra of selectively deuterated neopentanes
Tarr, Allan W. / Henry, Bryan R. | 1986
Kinematic model of oscillating thermal decomposition reactions of solids
Strobel, Hans | 1986
Average wave function method for multiple scattering
Singh, Harjinder / Dacol, Dalcio K. / Rabitz, Herschel | 1986
Resonances by the complex coordinate method with Hermitian Hamiltonian. IV. The linear correlation procedure
Engdahl, E. / Moiseyev, N. | 1986
A simple analytic model of the diffusion controlled reaction rates of asymmetric molecules
Hess, S. / Monchick, L. | 1986
The photodissociation of ClCN: A theoretical determination of the rotational state distribution of the CN fragment
Waite, Boyd A. / Dunlap, Brett I. | 1986
Influence of restricted geometries on the direct energy transfer
Blumen, A. / Klafter, J. / Zumofen, G. | 1986
State‐to‐state vibrational excitation of I2 in collisions with H2 and D2
Hall, Gregory / Liu, Kopin / McAuliffe, Michael J. / Giese, Clayton F. / Gentry, W. R. | 1986
Energy transfer collisions between vibrationally excited molecular nitrogen and atoms
Schearer, Laird D. | 1986
An amplified Oregonator model simulating alternative excitabilities, transitions in types of oscillations, and temporary bistability in a closed system
Ruoff, Peter / Noyes, Richard M. | 1986
Photodissociation of the energy selected nitrobenzene ion
Bunn, Thomas L. / Richard, Ann M. / Baer, Tomas | 1986
Trajectory calculations of ion‐quadrupolar molecule collision rate constants
Bhowmik, Pradip K. / Su, Timothy | 1986
Delayed ionization following resonant photon absorption and intracluster electron transfer
Dao, P. D. / Castleman, A. W. | 1986
Orbitally selective chemical reaction in Hg–H2 van der Waals complexes
Breckenridge, W. H. / Jouvet, Christophe / Soep, Benoit | 1986
Near‐resonant electronic‐to‐rotational energy transfer in Rb(7S→5D)–H2, D2 collisions at thermal energy
Cuvellier, J. / Petitjean, L. / Mestdagh, J. M. / Paillard, D. / de Pujo, P. / Berlande, J. | 1986
Temperature and pressure dependence of the reaction of He+ ions with H2
Bo¨hringer, H. / Arnold, F. | 1986
Collinear quasiclassical trajectory study of collision‐induced dissociation on a model potential energy surface
Kaye, Jack A. / Kuppermann, Aron | 1986
Propensities for rotational energy transfer in the B 3Πg (v=3) state of nitrogen
Katayama, D. H. | 1986
Processes involved in the Cs(7P)+H2→CsH reaction and nascent rotational distribution
Visticot, J. P. / Ferray, M. / D’Oliveira, P. / Sayer, B. | 1986
Rotational state distributions of H2 and CO following the photofragmentation of formaldehyde
Schinke, Reinhard | 1986
Propagation of a chemical pulse in an illuminated thermochemical bistable system
Kramer, Jesse / Reiter, Johannes / Ross, John | 1986
Rotational and vibrational state dependence on intramolecular coupling and dynamics in the S1 state of pyrazine
Amirav, Aviv / Jortner, Joshua | 1986
Unimolecular reactions near threshold: The overtone vibration initiated decomposition of HOOH (5νOH)
Ticich, T. M. / Rizzo, T. R. / Du¨bal, H.‐R. / Crim, F. F. | 1986
Kinetic energy dependence of Al++O2→AlO++O
Weber, M. E. / Elkind, J. L. / Armentrout, P. B. | 1986
The applicability of a percolation model to photoconductivity in guest–host thermotropic nematic liquid crystal systems
Chapoy, L. Lawrence | 1986
On the use of adiabatic switching to locate quantized, periodic orbits: Application to bound and reactive multidimensional problems
Skodje, Rex T. / Borondo, F. | 1986
Rotationally inelastic collisions between a molecule in a 2S+1Σ electronic state and an open‐shell target: General quantum analysis and experimental measurement of state‐resolved cross sections for CaCl(X 2Σ+)+NO(X 2Σ)
Corey, Gregory C. / Alexander, Millard H. / Dagdigian, Paul J. | 1986
Probability oscillations in single pass curve crossings: Semiclassical predictions of nonmonotonic dependence on crossing velocity
Nesbitt, David J. / Hynes, James T. | 1986
Large amplitude bending vibrations of the triatomic molecule: Low angular momentum states
Sage, Martin L. | 1986
On the dynamics of polaron formation in a deformable medium
Brown, David W. / Lindenberg, Katja / West, Bruce J. | 1986
Graph theoretical approach to the evaluation of matrix elements of one‐body operators in SU(n)
Kent, R. D. / Schlesinger, M. | 1986
Semiempirical treatment of the benzophenone molecule as a function of twist angle
Weitzel, K.‐M. / Ba¨ssler, H. | 1986
Molecular overlap integrals with exponential‐type orbitals
Bhattacharya, A. K. / Dhabal, S. C. | 1986
Relativistic and correlation effects in pseudopotential calculations for Br, I, HBr, HI, Br2, and I2
Schwerdtfeger, P. / Szentpa´ly, L. v. / Vogel, K. / Silberbach, H. / Stoll, H. / Preuss, H. | 1986
Hartree–Fock–Slater‐LCAO implementation of the moderately large‐embedded‐cluster approach to chemisorption. Calculations for hydrogen on lithium (100)
Ravenek, Walter / Geurts, Ferdie M. M. | 1986
Study of eigenvalue singularities from perturbation series: Application to two‐electron atoms
Arteca, Gustavo A. / Ferna´ndez, Francisco M. / Castro, Eduardo A. | 1986
An improved intermolecular potential for nitrogen
van der Avoird, A. / Wormer, P. E. S. / Jansen, A. P. J. | 1986
Accurate coefficient of the Axilrod–Teller triple‐dipole term for three hydrogen atoms
Koga, Toshikatsu | 1986
Nature and location of excited charge‐transfer states in porphyrin dimers: Development of preliminary design characteristics for biomimetic solar energy conversion systems
Petke, J. D. / Maggiora, G. M. | 1986
Calculations on species relevant to the photoionization of the van der Waals molecule (H2S)2
Ferna´ndez, Pelayo F. / Ortiz, J. V. / Walters, Edward A. | 1986
Density functional theory of bound states of positrons in negative ions
Harrison, Joseph G. | 1986
The silicon analog of benzene–hexasilabenzene (Si6H6)
Clabo, D. Allen / Schaefer, Henry F. | 1986
Energetic consideration of the vibrational potential function in the effective nuclear charge model. V
Ohwada, Ken | 1986
Electron affinity of hydroxyl radical
Chipman, Daniel M. | 1986
An ab initio calculation of the near‐equilibrium potential energy surface and vibrational frequencies of H2Br+ and its isotopomers
Botschwina, P. / Zilch, A. / Rosmus, P. / Werner, H.‐J. / Reinsch, E.‐A. | 1986
Theoretical dissociation energies for the alkali and alkaline‐earth monofluorides and monochlorides
Langhoff, Stephen R. / Bauschlicher, Charles W. / Partridge, Harry | 1986
The atom in a molecule: A wave function approach
Rychlewski, Jacek / Parr, Robert G. | 1986
The atom in a molecule: A density matrix approach
Li, Lemin / Parr, Robert G. | 1986
Molecular conformational equilibria in liquids
Zichi, Dominic A. / Rossky, Peter J. | 1986
Non‐Gaussian influence functional for quantum systems
Allinger, Kurt / Carmeli, Benny / Chandler, David | 1986
Optical birefringence and temperature range of the biaxial nematic phase in a lyotropic liquid crystal
Galerne, Y. / Neto, A. M. Figueiredo / Liebert, L. | 1986
Shear viscosity measurements near a critical endpoint
Rzoska, S. J. / Chrapec´, J. / Ziol&slash;o, J. | 1986
On the critical behavior of optical activity of a nonpolar binary liquid mixture
Lee, Dong J. / Kim, Shoon K. | 1986
Changes of thermodynamic quantities at the glass transition
Bengtzelius, U. / Sjo¨gren, L. | 1986
Generalized Langevin theory for many‐body problems in chemical dynamics: The equivalent chain equations for solute motion in molecular solvents
Adelman, Steven A. / Balk, Michael W. | 1986
Classical response theory propagators: An illustrative example
Holian, B. L. | 1986
Transition flow ion transport: Experimental
French, J. B. / Darcie, T. E. | 1986
A molecular theory for freezing: Comparison of theories, and results for hard spheres
Haymet, A. D. J. / Oxtoby, David W. | 1986
On the relationship between principal fluctuations and stability coefficients in multicomponent systems
Debenedetti, Pablo G. | 1986
Non‐Markovian activated rate processes: Comparison of current theories with numerical simulation data
Straub, John E. / Borkovec, Michal / Berne, Bruce J. | 1986
Free energy difference calculations comparing fcc and hcp structures using molecular dynamics computer simulations
Moody, Michael C. / Ray, John R. / Rahman, Aneesur | 1986
Isothermal–isobaric computer simulations of melting and crystallization of a Lennard‐Jones system
Nose´, Shuichi / Yonezawa, Fumiko | 1986
Nonequilibrium statistical mechanics of concentrated colloidal dispersions: Hard spheres in weak flows
Russel, W. B. / Gast, A. P. | 1986
Ionic pairing in binary liquids of charged hard spheres with nonadditive diameters
Pastore, G. / Giaquinta, P. V. / Thakur, J. S. / Tosi, M. P. | 1986
Analytic solution of the molecular Ornstein–Zernike equation for nonspherical molecules. Spheres with anisotropic surface adhesion
Cummings, Peter T. / Blum, Lesser | 1986
Embedded‐cluster model for the effect of phonons on hydrogen surface diffusion on copper
Lauderdale, Jack G. / Truhlar, Donald G. | 1986
On the distribution of included angles for the Rouse chain in strong steady shear flow
O¨ttinger, Hans Christian | 1986
Average wave function method for gas–surface scattering
Singh, Harjinder / Dacol, Dalcio K. / Rabitz, Herschel | 1986
On the manifestation of electronic structure effects in metal clusters
Kappes, Manfred M. / Scha¨r, Martin / Radi, Peter / Schumacher, Ernst | 1986
Bridge/atop site conversion of CO on Ni(111): Determination of the binding energy difference
Tang, S. L. / Lee, M. B. / Yang, Q. Y. / Beckerle, J. D. / Ceyer, S. T. | 1986
An exact correspondence between Eigen’s evolution model and a two‐dimensional Ising system
Leutha¨usser, Ira | 1986
Surface‐suppressed electron resonance spectroscopies
Barkley, P. Glenn / Hornak, Joseph P. / Freed, Jack H. | 1986
A model for photoinjection into polar fluids
Bennett, G. T. / Thompson, J. C. | 1986
Phase transitions of semiflexible lattice polymers
Baumga¨rtner, Artur | 1986
Computer simulation of adsorption equilibrium for a gas on a solid surface using the potential distribution theory
Knight, J. F. / Monson, P. A. | 1986
Circular intensity differential scattering of light by hierarchical molecular structures
Patterson, Chris W. / Singham, Shermila B. / Salzman, Gary C. / Bustamante, Carlos | 1986
On the short time dynamics of dense polymeric systems and the origin of the glass transition: A model system
Kolinski, Andrzej / Skolnick, Jeffrey / Yaris, Robert | 1986
Direct picosecond time resolution of unimolecular reactions initiated by local mode excitation
Scherer, N. F. / Doany, F. E. / Zewail, A. H. / Perry, J. W. | 1986
Total reactive cross sections for the reaction H+D2=HD+D
Tsukiyama, K. / Katz, B. / Bersohn, R. | 1986
The far infrared spectrum of magnesium hydride
Leopold, K. R. / Zink, L. R. / Evenson, K. M. / Jennings, D. A. / Mizushima, M. | 1986
Spectroscopic and dynamical differences between exciplex and electronically excited EDA complex
Lim, B. T. / Okajima, S. / Lim, E. C. | 1986
Single quantum state molecular beam scattering of vibrationally excited NO from Ag(111) and Ag(110)
Misewich, J. / Loy, M. M. T. | 1986
Extended model potential calculations on I2 and HI molecules
Barandiara´n, Zoila / Seijo, Luis | 1986
Intramolecular hydrogen transfer in the o‐tolyl radical studied by time resolved absorption measurements
Ichimura, Teijiro / Mori, Yuji / Sumitani, Minoru / Yoshihara, Keitaro | 1986
Electron paramagnetic resonance of VO2+in K2M’’ (SeO4)2 ⋅ 6H2O (M’’=Mg, Co)
Jain, V. K. | 1986
A new threshold energy for NO+O3→NO*2 +O2
Kahler, Carol C. / Kowalczyk, Marta | 1986
Fine structure effect on the charge transfer reaction of Ar+(2P3/2,1/2)+N2 (X˜ 1Σ+g, v=0)
Liao, C. L. / Xu, R. / Ng, C. Y. | 1986
Ab initio calculation of the dynamic polarizability of N2
Stroyer‐Hansen, T. / Svendsen, E. No&slash;rby | 1986
Heuristic model for hydrogen chemisorption on transition metal clusters
Phillips, J. C. | 1986
Erratum: A simple new way to help speed up Monte Carlo convergence rates: Energy‐scaled displacement Monte Carlo [J. Chem. Phys. 79, 3938 (1983)]
Goldman, S. | 1986
Erratum: Energy transfer in condensed media. I. Two‐level systems [J. Chem. Phys. 83, 4118 (1985)]
West, Bruce J. / Lindenberg, Katja | 1986