Classical Trajectory Study of Energy Transfer in Pyrazine−CO Collisions

Higgins, Cortney J.; Quan, Ju; Seiser, and Natalie; Flynn, George W.; Chapman, Sally

doi:10.1021/jp003980i

Cited by 21 publications

(27 citation statements)

References 53 publications

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“…75 Chapman and co-workers found a biexponential rotational distribution for CO following single collisions with pyrazine(E). 76,77 When they doubled the length of the CO molecule to mimic CO 2 , while preserving other potential parameters, they found reasonable agreement with the high-energy tail from pyrazine(E)/CO 2 collisions.…”

Section: Discussionmentioning

confidence: 83%

Full State-Resolved Energy Gain Profiles of CO₂ (J = 2−80) from Collisions of Highly Vibrationally Excited Molecules. 1. Relaxation of Pyrazine (E = 37900 cm⁻¹)

Havey

Liu

et al. 2009

J. Phys. Chem. A

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State-resolved energy gain profiles for "strong" and "weak" collisions of pyrazine (E = 37900 cm(-1)) and CO(2) are reported. Nascent energy profiles for scattered CO(2) (00(0)0, J = 2-64) were measured using high-resolution transient IR absorption spectroscopy at lambda = 2.7 microm. The data are combined with earlier data for CO(2) (J = 58-80) to yield the full state-resolved distribution of scattered CO(2) (00(0)0). The scattered CO(2) (00(0)0, J = 2-80) molecules have a biexponential rotational distribution with T(lowJ) = 437 +/- 50 K for J < 50 and T(highJ) = 1145 +/- 110 K for J > 50. Fitting the data with a two-component exponential model yields CO(2) product distributions with T(rot) = 329 and 1241 K. The cooler distribution accounts for 78% of the scattered population and results from elastic or weakly inelastic collisions that induce very little rotational excitation in CO(2). The hotter distribution involves large changes in CO(2) rotational energy and accounts for 22% of collisions. The relative translational energy of the scattered molecules increases as a function of final CO(2) rotational state with T(rel) = 860 K for J = 2, 1650 K for J = 60, and 5500 K for J = 80. The total rate constant for appearance of scattered CO(2) (00(0)0) is k(app) = (4.8 +/- 1.4) x 10(-10) cm(3) molecule(-1) s(-1), which is approximately 85% of the Lennard-Jones collision rate. Population depletion measurements yield a collision rate of k(dep) = (5.7 +/- 1.8) x 10(-10) cm(3) molecule(-1) s(-1), which is in very good agreement with the Lennard-Jones collision rate. The full energy transfer probability distribution function P(DeltaE) for pyrazine(E)-CO(2) collisions is presented and compared to results from other studies.

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Section: Discussionmentioning

confidence: 83%

Full State-Resolved Energy Gain Profiles of CO₂ (J = 2−80) from Collisions of Highly Vibrationally Excited Molecules. 1. Relaxation of Pyrazine (E = 37900 cm⁻¹)

Havey

Liu

et al. 2009

J. Phys. Chem. A

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“…Much work has also gone into developing the theory to explain energy transfer processes. This effort includes classical trajectory studies, [17][18][19][20][21][22] and quantum-scattering studies. 21 Of particular importance to the work reported here are trajectory studies of Lendvay and co-worker 17,20 and the work of Clary et al 21 They conclude that low-frequency donor vibrational modes, with out-of-plane-type motions, are more efficient at transferring large amounts of energy in collisions.…”

Section: Introductionmentioning

confidence: 99%

Quenching of highly vibrationally excited pyrimidine by collisions with CO2

Johnson

Duffin

Hom

et al. 2008

The Journal of Chemical Physics

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Relaxation of highly vibrationally excited pyrimidine (C(4)N(2)H(4)) by collisions with carbon dioxide has been investigated using diode laser transient absorption spectroscopy. Vibrationally hot pyrimidine (E(')=40 635 cm(-1)) was prepared by 248-nm excimer laser excitation, followed by rapid radiationless relaxation to the ground electronic state. The nascent rotational population distribution (J=58-80) of the 00(0)0 ground state of CO(2) resulting from collisions with hot pyrimidine was probed at short times following the excimer laser pulse. Doppler spectroscopy was used to measure the CO(2) recoil velocity distribution for J=58-80 of the 00(0)0 state. Rate constants and probabilities for collisions populating these CO(2) rotational states were determined. The measured energy transfer probabilities, indexed by final bath state, were resorted as a function of DeltaE to create the energy transfer distribution function, P(E,E(')), from E(')-E approximately 1300-7000 cm(-1). P(E,E(')) is fitted to a single exponential and a biexponential function to determine the average energy transferred in a single collision between pyrimidine and CO(2) and parameters that can be compared to previously studied systems using this technique, pyrazineCO(2), C(6)F(6)CO(2), and methylpyrazineCO(2). P(E,E(')) parameters for these four systems are also compared to various molecular properties of the donor molecules. Finally, P(E,E(')) is analyzed in the context of two models, one which suggests that the shape of P(E,E(')) is primarily determined by the low-frequency out-of-plane donor vibrational modes and one which suggests that the shape of P(E,E(')) can be determined by how the donor molecule final density of states changes with DeltaE.

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“…In the study of pyrazine-CO energy transfer [117], Chapman and co-workers showed that the initial rotation of energy acceptor CO molecules has effect on the relaxation of pyrazine vibrational energy. The increase of initial CO rotation results in an increasing fraction of energy-up collisions and an increasing average energy in the energy-up collisions.…”

Section: Effects Of Initial Rotational Temperaturementioning

confidence: 99%

Energy transfer of highly vibrationally excited molecules studied by crossed molecular beam/time-sliced velocity map ion imaging

Hsu

Tsai

Dyakov

et al. 2012

International Reviews in Physical Chemistry

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Energy transfer of highly vibrationally excited molecules has been studied extensively under bulk conditions in the past 40 years. On the other hand, in 1973 Fisk and co-workers reported the first experimental results of collisional energy transfer of highly vibrationally excited KBr using cross-molecular beams. Surprisingly, it is the only crossed molecular beam experiment about the energy transfer of highly vibrationally excited molecules. No other similar crossed molecular beam experiments have been reported in the following four decades. Recently we have studied the energy transfer of highly vibrationally excited molecules using crossed molecular beams/time-of-flight mass spectrometer in combination with time-sliced velocity map ion imaging techniques. Energy transfer probability density functions were accurately obtained and details of energy transfer mechanisms were evidenced from the cross-molecular beam scatterings. This paper reviews our recent work of energy transfer of highly vibrationally excited molecules. The effects of long-lived complex, initial translational energy, initial rotational temperature, vibrational motions, alkylation, attractive potential and electronic state on the energy transfer and supercollisions were discussed, and comparisons to theoretical calculations and experiments conducted under bulk conditions were made.

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Classical Trajectory Study of Energy Transfer in Pyrazine−CO Collisions

Cited by 21 publications

References 53 publications

Full State-Resolved Energy Gain Profiles of CO₂ (J = 2−80) from Collisions of Highly Vibrationally Excited Molecules. 1. Relaxation of Pyrazine (E = 37900 cm⁻¹)

Full State-Resolved Energy Gain Profiles of CO₂ (J = 2−80) from Collisions of Highly Vibrationally Excited Molecules. 1. Relaxation of Pyrazine (E = 37900 cm⁻¹)

Quenching of highly vibrationally excited pyrimidine by collisions with CO2

Energy transfer of highly vibrationally excited molecules studied by crossed molecular beam/time-sliced velocity map ion imaging

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Classical Trajectory Study of Energy Transfer in Pyrazine−CO Collisions

Cited by 21 publications

References 53 publications

Full State-Resolved Energy Gain Profiles of CO2 (J = 2−80) from Collisions of Highly Vibrationally Excited Molecules. 1. Relaxation of Pyrazine (E = 37900 cm−1)

Full State-Resolved Energy Gain Profiles of CO2 (J = 2−80) from Collisions of Highly Vibrationally Excited Molecules. 1. Relaxation of Pyrazine (E = 37900 cm−1)

Quenching of highly vibrationally excited pyrimidine by collisions with CO2

Energy transfer of highly vibrationally excited molecules studied by crossed molecular beam/time-sliced velocity map ion imaging

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Full State-Resolved Energy Gain Profiles of CO₂ (J = 2−80) from Collisions of Highly Vibrationally Excited Molecules. 1. Relaxation of Pyrazine (E = 37900 cm⁻¹)

Full State-Resolved Energy Gain Profiles of CO₂ (J = 2−80) from Collisions of Highly Vibrationally Excited Molecules. 1. Relaxation of Pyrazine (E = 37900 cm⁻¹)