Energy transfer processes in monochromatically excited iodine. IX. Classical trajectory and semiclassical calculations of vibrationally and rotationally inelastic cross sections

Rubinson, Mica; Garetz, Bruce A.; Steinfeld, J. I.

doi:10.1063/1.1681494

Cited by 59 publications

(5 citation statements)

References 32 publications

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“…The dependence of the quenching cross section on the initial vibrational excitation v was found to be rather smooth, with an average quenching cross section of the order of 5Å 2 (Capelle and Broida, 1973). Vibrational energy transfer is more efficient as v increased (Steinfeld and Klemperer, 1965), and less efficient than rotational energy transfer (Rubinson et al, 1974a).…”

Section: Historical Overview 21 Collisional Ar+i Systemmentioning

confidence: 90%

“…These measurements performed under bulk conditions provided estimations for inelastic transition rate constants which do not allow straightforward inversion of the potential. Early theoretical interpretations (Kajimoto and Fueno, 1972;Rubinson et al, 1974b;Rubinson and Steinfeld, 1974) designed and used empirical potentials representing the total PES as a sum of atom-atom potentials (Hill, 1946;Kitaigorodskii, 1951). The addition of two identical potentials gives a PES with a T-shaped configuration and a saddle point in the collinear arrangement.…”

Section: Empirical Potentialsmentioning

confidence: 99%

“…A notable exception is the work of Rubinson et al (1974b), where the parameters of a model Buckingham Rg-I potential were optimized by means of three-dimensional quasiclassical trajectory calculations to reproduce observed probabilities of vibrationallyinelastic transitions in Rg + I 2 (B) collisions. Equilibrium properties of these potentials are presented in Table 1, entry 16.…”

Section: Empirical Potentialsmentioning

confidence: 99%

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Ar ··· I 2 : A model system for complex dynamics

Buchachenko

Halberstadt

Lepetit

et al. 2003

International Reviews in Physical Chemistry

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We review spectroscopic and photodissociation dynamical studies in the region of the B ← X transition of the Ar ... I 2 Van der Waals complex, both below and above the dissociation limit of the B(3 Π 0 + u) state. This very simple system constitutes a prototype for a wide range of molecular processes: vibrational predissociation involving intramolecular vibrational relaxation, electronic predissociation, cage effect... Each of these processes has been or still is the subject of differing interpretations: intramolecular vibrational relaxation involved in the vibrational predissociation of this system can be in the sparse or statistical regime, vibrational and electronic predissociation are in competition, and a direct, ballistic interpretation of the cage effect as well as a nonadiabatic one have been proposed. The study of the dependence of these dynamical processes on the relative orientation of the two partners of the complex (stereodynamics) is made possible by the coexistence of two stable Ar ... I 2 (X) isomers. Experimental as well as theoretical results are reviewed. Experiments range from frequency-resolved to time-dependent studies, including the determination of final state distributions. Theoretical studies involve potential energy surface calculations for several electronic states of the complex and their couplings, and adiabatic as well as nonadiabatic dynamical simulations.

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Section: Historical Overview 21 Collisional Ar+i Systemmentioning

confidence: 90%

Section: Empirical Potentialsmentioning

confidence: 99%

Section: Empirical Potentialsmentioning

confidence: 99%

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Ar ··· I 2 : A model system for complex dynamics

Buchachenko

Halberstadt

Lepetit

et al. 2003

International Reviews in Physical Chemistry

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“…As the molecular beam is expanded isentropically, energy of local random motion is transferred to the bulk translational motion, and the vibrational and rotational temperatures also drop considerably by V-T and R-T energy relaxations. [1][2][3][4] Then, if the collision cross sections for various kinds of activation or deactivation processes were constant parameters over the collision velocity, the total collision frequency should decrease with the decrease in the local velocity, and molecules would become isolated during the expansion of supersonic jet. If collision cross sections increase with the decrease in collision velocity, however, low energy collision plays an important role in nozzle expansion process.…”

Section: Introductionmentioning

confidence: 99%

Multiple quantum jumps in vibrational energy transfer of iodine in the B 3Πu+ state along a supersonic beam expansion

Baba

Sakurai

1985

The Journal of Chemical Physics

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An argon ion laser (514.5 nm) excites the 12 molecules to B 30 0 .+ (v' = 43) state at a certain point in the supersonic He and H2 jet, and the fluorescence spectrum is observed downstream. An extremely large vibrational energy relaxation of electronically excited iodine molecules in the expanding supersonic beam has been observed over the levels of.:1v = -10--2. The vibrational population distribution along the jet flow was analyzed with the rate equation. The.:1 v dependence of rate constant in a single collision, klJ-+v + .dv , is assumed to be a simple function asIkB Te/f), for.:1v > 0, where.:1E is the energy gain by vibrational activation, Te/f is the effective temperature and a is the fitting parameter for multiple quantum jumps, and K 1---+0' a and Te/f have been determined to be 1.70 ± 0.05 X lO-12(cm 3 /mol s), 0.0065 and 19 K, 3.2 ± 0.1 X lO-12(cm 3 /mol s), 0.009 and 30 K for He and H 2 , respectively. It was found that vibrational mUltiple quantum jumps in a single collision contributed to the relaxation process and the relaxation rate constant seemed to be almost constant along the expanding flow.

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“…For pressures as high as 13 torr, no relaxation of C2-(A3ng) was observed. A 10-15% increase in the 3/ 4 ratio could have been experimentally detected.…”

Section: Discussionmentioning

confidence: 95%

Vibrational relaxation of CO+(A2.PI.i), CS(A1.PI.), and C2(A3.PI.g) in helium

Marcoux¹,

Swaay²,

Setser³

1979

J. Phys. Chem.

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Publication costs assisted by the Department of DefenseNonequilibrium vibrational distributions of CO+(A2n,u'=0-6), CS(A1rI,u'=&5), and Cz(A3TI,u '=M) were prepared by collisional processes in a 300-I< helium flowing-afterglow apparatus. The vibrational band intensities of the electronic emission systems were used to obtain the steady-state vibrational distributions from 0.8 to 15 torr. Extensive vibrational relaxation by collisions with He was observed for CO"(A) and CS(A), but not for C,(A), over this pressure range, Electronic quenching of CS(A) probably is competitive with vibrational relaxation, even in helium. The data were fitted to relaxation models based upon Au = 1 collisional transitions by using the steady-state master equation formulation. The Au = 1 relaxation cross sections for CO+(A) and CS(A) with He are in the range of 0.01 of the gas kinetic values. The upper limit to the 4 u = -1 relaxation cross section for C,(A) is 5 X of the gas kinetic value. Studies of the relaxation of CS(A'n) in Ar were attempted, but electronic quenching appeared to dominate over vibrational relaxation. These results are compared to vibrational-translational relaxation of other electronically excited states.

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Energy transfer processes in monochromatically excited iodine. IX. Classical trajectory and semiclassical calculations of vibrationally and rotationally inelastic cross sections

Cited by 59 publications

References 32 publications

Ar ··· I 2 : A model system for complex dynamics

Ar ··· I 2 : A model system for complex dynamics

Multiple quantum jumps in vibrational energy transfer of iodine in the B 3Πu+ state along a supersonic beam expansion

Vibrational relaxation of CO+(A2.PI.i), CS(A1.PI.), and C2(A3.PI.g) in helium

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