Chen-Lin Liu

Supercollisions and energy transfer of highly vibrationally excited molecules

Collisional energy-transfer probability distribution functions of highly vibrationally excited molecules and the existence of supercollisions remain as the outstanding questions in the field of intermolecular energy transfer. In this investigation, collisional interactions between ground state Kr atoms and highly vibrationally excited azulene molecules (4.66 eV internal energy) were examined at a collision energy of 410 cm-1 using a crossed molecular beam apparatus and time-sliced ion imaging techniques. A large amount of energy transfer (1000-5000 cm-1) in the backward direction was observed. We report the experimental measurement for the shape of the energy-transfer probability distribution function along with a direct observation of supercollisions.

Energy transfer of highly vibrationally excited azulene. III. Collisions between azulene and argon.

The energy transfer dynamics between highly vibrationally excited azulene molecules (37 582 cm(-1) internal energy) and Ar atoms in a series of collision energies (200, 492, 747, and 983 cm(-1)) was studied using a crossed-beam apparatus along with time-sliced velocity map ion imaging techniques. The angular resolved collisional energy-transfer probability distribution functions were measured directly from the scattering results of highly vibrationally excited azulene. Direct T-VR energy transfer was found to be quite efficient. In some instances, nearly all of the translational energy is transferred to vibrational/rotational energy. On the other hand, only a small fraction of vibrational energy is converted to translational energy (V-T). Significant amount of energy transfer from vibration to translation was observed at large collision energies in backward and sideway directions. The ratios of total cross sections between T-VR and V-T increases as collision energy increases. Formation of azulene-argon complexes during the collision was observed at low enough collision energies. The complexes make only minor contributions to the measured translational to vibrational/rotational (T-VR) energy transfer.

Energy transfer of highly vibrationally excited naphthalene. I. Translational collision energy dependence.

Energy transfer between highly vibrationally excited naphthalene and Kr atom in a series of translational collision energies (108-847 cm(-1)) was studied separately using a crossed-beam apparatus along with time-sliced velocity map ion imaging techniques. Highly vibrationally excited naphthalene in the triplet state (vibrational energy: 16,194 cm(-1); electronic energy: 21,400 cm(-1)) was formed via the rapid intersystem crossing of naphthalene initially excited to the S(2) state by 266 nm photons. The collisional energy transfer probability density functions were measured directly from the scattering results of highly vibrationally excited naphthalene. At low collision energies a short-lived naphthalene-Kr complex was observed, resulting in small amounts of translational to vibrational-rotational (T-->VR) energy transfer. The complex formation probability decreases as the collision energy increases. T-->VR energy transfer was found to be quite efficient at all collision energies. In some instances, nearly all of the translational energy is transferred to vibrational-rotational energy. On the other hand, only a small fraction of vibrational energy is converted to translational energy. The translational energy gained from vibrational energy extend to large energy transfer (up to 3000 cm(-1)) as the collision energy increases to 847 cm(-1). Substantial amounts of large V-->T energy transfer were observed in the forward and backward directions at large collision energies.

Energy transfer of highly vibrationally excited naphthalene. II. Vibrational energy dependence and isotope and mass effects

The vibrational energy dependence, H and D atom isotope effects, and the mass effects in the energy transfer between rare gas atoms and highly vibrationally excited naphthalene in the triplet state were investigated using crossed-beam/time-sliced velocity-map ion imaging at various translational collision energies. Increase of vibrational energy from 16 194 to 18 922 cm(-1) does not make a significant difference in energy transfer. The energy transfer properties also remain the same when H atoms in naphthalene are replaced by D atoms, indicating that the high vibrational frequency modes do not play important roles in energy transfer. They are not important in supercollisions either. However, as the Kr atoms are replaced by Xe atoms, the shapes of energy transfer probability density functions change. The probabilities for large translation to vibration/rotation energy transfer (T-->VR) and large vibration to translation energy transfer (V-->T) decrease. High energy tails in the backward scatterings disappear, and the probability for very large vibration to translation energy transfer such as supercollisions also decreases.

Energy transfer of highly vibrationally excited azulene. II. Photodissociation of azulene-Kr van der Waals clusters at 248 and 266 nm

Photodissociation of azulene-Kr van der Waals clusters at 266 and 248 nm was studied using velocity map ion imaging techniques with the time-sliced modification. Scattered azulene molecules produced from the dissociation of clusters were detected by one-photon vacuum ultraviolet ionization. Energy transfer distribution functions were obtained from the measurement of recoil energy distributions. The distribution functions can be described approximately by multiexponential functions. Fragment angular distributions were found to be isotropic. The energy transfer properties show significantly different behavior from those of bimolecular collisions. No supercollisions were observed under the signal-to-noise ratios S/N=400 and 100 at 266 and 248 nm, respectively. Comparisons with the energy transfer of bimolecular collisions in thermal systems and the crossed-beam experiment within detection limit are made.

Generation and characterization of highly vibrationally excited molecular beam

A simple method to generate and characterize a pure highly vibrationally excited azulene molecular beam is demonstrated. Azulene molecules initially excited to the S4 state by 266-nm UV photons reach high vibrationally excited levels of the ground electronic state upon rapid internal conversion from the S4 electronically excited state. VUV laser beams at 157 and 118 nm, respectively, are used to characterize the relative concentrations of the highly vibrationally excited azulene and the rotationally and vibrationally cooled azulene in the molecular beam. With a laser intensity of 34 mJ/cm2, 75% of azulene molecules absorb a single 266-nm photon and become highly vibrationally excited molecules. The remaining ground-state azulene molecules absorb two or more UV photons, ending up either as molecular cations, which are repelled out of the beam by an electric field, or as dissociation fragments, which veer off the molecular-beam axis. No azulene without absorption of UV photons is left in the molecular beam. The molecular beam that contains only highly vibrationally excited molecules and carrier gas is useful in various experiments related to the studies of highly vibrationally excited molecules.

Rotationally resolved laser-induced fluorescence of biacetyl in A 1Au–X 1Ag

Laser-induced fluorescence of jet-cooled biacetyl was recorded in the region of 22 177–22 277 cm−1 with a resolution of 0.012 cm−1. Three bands, 000, 1501, and 2101 with transitions J″⩽3 were observed and analyzed. For the 000 band, E2–E1 and G–G subbands were observed. However, only c-type transitions, ΔKa=odd, ΔKc=even, were observed. Another kind of transition, d-type (ΔKa=even, ΔKc=even), which is allowed by selection rules, was not observed. For the 1501 band, two subbands E3–E3 and G–G were observed. The E3–E3 subband can be described by the rigid rotor model, and it contains only ΔKa=odd, ΔKc=even transitions. On the other hand, the G–G subband cannot be even approximately described by the rigid rotor model. It is dominated by c-type transitions. In addition, a/b-type and d-type transitions were all observed, though the intensities are small. For the 2101 band, E2–E1, G–G, and A3–A1 subbands were observed. The E2–E1, G–G subbands contain all the possible types of transitions, i.e., a/b-and c/d-type...

Energy transfer of highly vibrationally excited naphthalene. III. Rotational effects.

The rotational effects in the energy transfer between Kr atoms and highly vibrationally excited naphthalene in the triplet state were investigated using crossed-beam/time-sliced velocity map ion imaging at various translational collision energies. As the initial rotational temperature changes from less than 10 to approximately 350 K, the ratio of vibrational to translational (V-->T) energy transfer cross section to translational to vibrational/rotational (T-->VR) energy transfer cross section increases, but the probability of forming a complex during the collisions decreases. Significant increases in the large V-->T energy transfer probabilities, termed supercollisions, at high initial rotational temperature were observed.

Energy transfer of highly vibrationally excited 2-methylnaphthalene : Methylation effects

The methylation effects in the energy transfer between Kr atoms and highly vibrationally excited 2-methylnaphthalene in the triplet state were investigated using crossed-beam/time-sliced velocity-map ion imaging at a translational collision energy of approximately 520 cm(-1). Comparison of the energy transfer between naphthalene and 2-methylnaphthalene shows that the difference in total collisional cross section and the difference in energy transfer probability density functions are small. The ratio of the total cross sections is sigma(naphthalene): sigma(methylnaphthalene)=1.08+/-0.05:1. The energy transfer probability density function shows that naphthalene has a little larger probability at small T-->VR energy transfer, DeltaE(u)<300 cm(-1), and 2-methylnaphthalene has a little larger probability at large V-->T energy transfer, -800 cm(-1)<DeltaE(d)<-100 cm(-1). However, these differences are close to our experimental uncertainty. No significant difference in the probability of very large energy transfer, such as supercollisions defined arbitrarily as DeltaE(d)<-1500 cm(-1), was observed. The possible methylation effects due to the subsequent successive collisions were discussed.

Time-sliced ion imaging study of I2 and I2+ photolysis at 532 nm

Photodissociation of I2 and I2+ at 532.10 nm was studied using VUV photoionization/time-sliced velocity map imaging. The dissociation energies D0 of I2(X 1sigma g+) and I2(X 2pi 1/2g) were found to be 12,416 +/- 48 and 16,439 +/- 48 cm(-1), respectively. Absorption of 532.10 nm mainly corresponds to the excitation of I2(X 1sigma g+) to the 1pi(1u) and/or A3pi(1u) states, and the excitation of I2+(X 2pi 1/2g) to the A2pi 1/2u state, with a small fraction to the A2pi 3/2u and 4sigma u+ states. A method for accurate calibration of magnification factor of ion imaging system was presented. The improvement of energy resolution for large ionization volume experiments, like the crossed molecular beam and one-photon VUV photoionization experiments, was discussed.