Influence of short-and long-range interaction forces on the efficiency of collisional vibrational energy transfer in the vibrational quasi-continuum

Based on measurements of the time-resolved delayed fluorescence, the influence of universal interactions on the collisional vibrational energy transfer is studied in mixtures of vibrationally excited polyatomic molecules (acetophenone, benzophenone, and anthraquinone) with inert bath gases (Ar, C₂H₄, SF₆, CCl₄, and C₅H₁₂). From the dependences of the decay rates of delayed fluorescence on bath gas pressure, the efficiencies of the establishment of vibrational (V-V relaxation) and thermal (V-T relaxation) equilibrium after excitation of molecules into the vibrational quasi-continuum of a triplet state are estimated. The main emphasis is on studying the dependences of the efficiency of collisional vibrational energy transfer on temperature and the molecular characteristics of collision partners. It is found that the efficiency increases with the complication of the structure of bath gases for the V-V process and decreases upon the increasing of their mass for the V-T process. For the temperature range 273–553 K, the negative temperature dependence of the V-V transfer probability and the positive (Landau-Teller) dependence of the V-T transfer probability were obtained. It is concluded that the above regularities reflect the dominant role of long-range attractive forces in initiating the quasi-resonant V-V transfer and of short-range repulsive forces in the V-T transfer of vibrational energy.     

Relaxation Processes at High Levels of Vibrational Excitation of Polyatomic Molecules in the Ground Electronic State

By the spectral and kinetic characteristics of the luminescence of vapors of polyatomic molecules (anthracene, anthraquinone, fluorenone) initiated by selective IR multiphoton excitation (IR MPE) of molecules in the ground electronic state S ₀ the relaxation processes proceeding under vibrational excitation of molecules to energies exceeding the energies of the lower excited electronic states have been investigated. The changes in the spectral and kinetic characteristics with increasing CO₂ laser energy density and vapor P _v and foreign gas pressure P _FG are analyzed. They are similar to the characteristics obtained for normal fluorescence of these molecules with changing vibrational energy E _vib content. On the basis of experimental data and model calculations it has been concluded that at the laser radiation densities used in the case of IR MPE the molecules reach energies considerably exceeding the energies of the electronic levels. It is shown that a nonadiabatic connection between the electronic states leads to the population of mixed electronic states isoenergetic to the vibrational levels of the ground electronic state and to emission of delayed luminescence spectrally identical to the normal luminescence of these molecules. It has been found that when high vibrational levels are populated, new relaxation channels, such as reverse electron relaxation, emission from high vibrational levels of the ground electronic state, and multiquantum vibrational energy transfer at collisions leading to a rapid establishment of vibrational equilibrium become important.     

Collisional Energy Transfer from Vibrationally Excited Polyatomic Molecules

Abstract

Intensities and decay rates of delayed fluorescence initiated by CO₂ laser excitation of the triplet-state molecules are used to probe collisional relaxation of vibrationally excited polyatomic molecules. Collisional efficiencies for large polyatomic molecules are found not to exceed the value of 10^?2-10^?3 even in most favourable case of vibrational energy exchange in collisions between parent molecules. At intermediate levels of excitation (1500—12000 cm^?1) the average energies <ΔE> transferred per collision with polyatomic molecules increase as vib>^rn, where m≥2, and decrease with increasing numbers of atoms in the excited molecules.     

Photophysical Processes in the Gas Phase at High Levels of Vibrational Excitation of Triplet Molecules of Benzophenone and Fluorenone

By the delayed fluorescence activated by direct multiphoton excitation of triplet molecules by CO₂–laser radiation we have studied the prevailing deactivation pathways of triplet molecules with a high store of vibrational energy E _vib. The dependences of the kinetic characteristics of delayed fluorescence on the presence of vapors and foreign gases have been used to estimate the rates and efficiencies of intermolecular vibrational relaxation in the vibrational quasi–continuum of the triplet state T ₁. By the changes in the intensities and decay rates over a wide range of vibrational energies we have established the E _vib dependences of reversible intercombination conversion between the states T ₁ and S ₁ and interconversion from T ₁ to the ground electronic state S ₀ for both the case of isolated excited molecules and at a steady vibrational temperature. It is shown that at high vibrational temperatures the radiationless transition from the T ₁ state to S ₀ has an activation character and is accomplished through the energy barrier. The conditions for going to an exponential dependence have been determined. It has been found that the obtained dependences are in good agreement with the known experimental results. The influence of molecular and environmental characteristics on the decay rate of triplet molecules is compared.     

Direct Measurement of Collisional Energy Transfer Between Highly Vibrationally Excited Triplet Fluorenone and Bath Gases

Intensities and decay rates of CO₂-laser induced delayed fluorescence are used to probe collisional relaxation of vibrationally excited fluorenone diluted with bath gases: He, N₂, Kr. The average energies 〈ΔE〉 transferred per collision are found to vary with vibrational energy, the energy dependences of the collisional efficiency eventually level off.     

Effect of Supercollisions on Energy Transfer in Mixtures of Bath Gases and Laser Excited Complex Molecules

Intensities and decay rates of delayed luminescence (DL) initiated by a pulse of N₂ laser were employed to probe collisional relaxation of complex molecules (benzophenone, acetophenone) diluted with bath gases Ar, Kr, Xe, C₂H₄, SF₆, C₅H₁₂. It was shown that vibrational relaxation can be interpreted in terms of two consecutive processes: vibration-vibration (V-V) and vibration-translation (V-T). The results clearly demonstrated that fast component of DL can be used to study V-V energy transfer. It was found that at relatively small internal energy the collisional efficiences of V-V process had the values typical for molecular processes in which supercollisions contribute. The average energies transferred per collision, (ΔE), well correlated with predictions of the simple ergodic collision theory of intermolecular energy transfer.     

Intramolecular vibrational energy transfer in mixtures of anthraquinone with foreign gases

Properties of collision transfer of vibrational energy in the vibrational quasi-continuum of mixed singlet-triplet levels of anthraquinone are studied by the method of time-resolved delayed fluorescence. The two-exponential fluorescence decay is analyzed in the kinetic approximation. It is shown that dependences of the intensities and decay rates of the fast and slow components on pressure can be used for estimating the rates of the establishment of the vibrational (V-V) and thermal (V-T) equilibrium. The efficiency β and the average energy 〈ΔE〉 transferred in collisions are estimated for these processes. It is found that the V-V process is characterized by high values of β, which, however, are lower in the quasi-continuum of mixed singlet-triplet states than the gas-kinetic values (β < 0.2). The transformation of the vibrational energy to the translational energy occurs with the low efficiency (10^?2 > β > 10^?5). The average energy 〈ΔE〉 transferred during a collision in the V-V process is comparable with the energy predicted by the statistical theory of ergodic transfer. The correlation between experimental and theoretical values improves when the time resolution of the experiment is sufficient for the separation of the V-V and V-T processes.     

Photochemical reactions of triplet benzophenone and anthraquinone molecules with amines in the gas phase

The intermolecular photoinduced reactions between triplet ketone molecules and aliphatic amines and pyridine are studied by the quenching of delayed fluorescence of anthraquinone and benzophenone vapors by diethylamine, dibutylamine, cyclohexylamine, triethylamine, and pyridine. In the temperature range 423–573 K, the delayed fluorescence quenching rate constants k _q are estimated from changes in the decay rate constant and the intensity of delayed fluorescence upon increasing pressure of bath gases. It is ascertained that, in the gas phase, the mixtures under study exhibit both a negative and a positive dependence of k _q on temperature, which indicates that some photoinduced reactions do not have activation barriers. The rate constant k _q is shown to increase with decreasing ionization potential of the electron donors. This points to the importance of interactions with charge transfer in the photoreaction of triplet ketone molecules with aliphatic amines and pyridine in the gas phase. The relationship between k _q and the change in the free energy ΔG upon the photoinduced intermolecular electron transfer, which is the primary stage of the photochemical reaction, is studied. It is shown that the dependence k _q (ΔG) for the donor-acceptor pairs under study is described well by the Marcus equation, in which the average vibrational energies of the donor and acceptor are taken into account for the estimate of ΔG.     

Intermolecular Vibrational Relaxation in Mixtures of Excited Benzophenone and Anthraquinone Molecules with Water Vapor

The intermolecular vibrational energy transfer from triplet molecules of benzophenone and anthraquinone to H₂O molecules has been investigated. To determine the rates of establishment of vibrational (V-V) and thermal (V-T) equilibrium in a vibrational quasi-continuum of mixed singlet-triplet levels, the dependences of the decay rates and intensities of the fast and slow components of delayed fluorescence on the H₂O vapor pressure have been investigated. For V-V relaxation, the efficiencies ₁ and the mean energies E transferred per collision in mixtures with H₂O and other polyatomic foreign gases have been compared. It has been established that the efficiencies ₁ for quasi-resonant vibrational energy transfer (V-V) from benzophenone and anthraquinone to H₂O are an order of magnitude lower than the gas-kinetic ones and lower than those obtained under the same experimental conditions for such foreign gases as C₅H₁₂, SF₆, and CCl₄, and decrease with increasing temperature in the 433–513 K range. It has been concluded that the mechanism of V-V relaxation in mixtures with H₂O are determined by long-range attractive forces. In mixtures with H₂O, no acceleration of V-T relaxation due to the formation of hydrogen bonds has been revealed. The low-efficiency thermalization process (V-T relaxation) is controlled by short-range repulsive forces, and the differences between the intensities ₂ for mixtures of benzophenone and anthraquinone with H₂O and other polyatomic gases are determined by the change in the reduced mass of interacting molecules.     

Threshold dependence of the vibrational excitation of molecules on laser radiation intensity

The collisionless vibrational excitation of a polyatomic molecule in an IR laser radiation field has been theoretically studied. It has been shown that (i) the degree of vibrational excitation (namely, number 0000 of vibrational quanta of a molecular mode near-resonant with the IR laser field that are absorbed by the molecule) is low if laser pulse intensity P (energy flux density in the laser beam) is lower than a certain critical value P _cr; (ii) the degree of excitation abruptly increases after crossing the boundary where P = P _cr; (iii) this effect is attributed to two properties inherent in polyatomic molecules, namely, the anharmonicity of the vibrational mode interacting with the laser field and the energy exchange with other modes; and (iv) at P > P _cr, number 00000 is determined only by energy density Φ = Pτ_P, where τ_P is the laser pulse duration, 00000 monotonically increases with increasing Φ. The model is in good agreement with the experimental data.     

Studies of vibrational relaxation in CDF3 following intense laser excitation

The V-T/R relaxation time of CDF₃ was measured studying the laser-induced infrared fluorescence emitted by vibrationally excited CDF₃. Following excitation by the 10R(12) line of a TEA CO₂ laser infrared fluorescence has been detected without spectral resolution in the 1100–700 cm^–1 range. A decay rate of 28.8 ms^–1 Torr^–1 was obtained for pure CDF₃ when it is excited with a fluence of 390 mJ/cm². Measurements have also been made in the presence of different bath gases (He, Ne, Ar, Xe, and CHF₃).     

Temperature Dependence of the Efficiency of Collisional Transfer of Vibrational Energy in Mixtures of Vibrationally Excited Triplet Molecules with Foreign Gases

By the pressure dependences of the decay rates of delayed fluorescence activated by vibrational excitation of triplet molecules of benzophenone and anthraquinone, the efficiencies of collisional transfer of vibrational energy (V–V-transfer) in the vibrational quasi-continuum of the triplet state have been estimated. It is shown that the efficiencies of the process in mixtures with foreign gases increase with increasing dipole moment and polarizability of colliding molecules. In the temperature range 433–513 K, we obtained an inverse temperature dependence of the V–V-transfer efficiency, which is satisfactorily described by empirical relations taking into account long-range attractive forces. The results obtained point to the determining role of long-range attractive forces in quasi-resonance V–V-transfer of vibrational energy by molecules excited in vibrational quasi-continuum.     

Strong selective excitation of Raman-active vibrations and energy transfer between low-lying vibrational states of a CO2 molecule studied by PARS and CARS

We experimentally demonstrate the novel technique of inducing the highly nonequilibrium distribution of molecules over vibrational states by two-frequency coherent Raman excitation. The technique can be used for selective excitation of totally symmetric and other Raman-active molecular transitions. Two counter propagating focused laser beams (second harmonic of Nd: YAG and dye laser) were used to induce population difference changes at the 00⁰0–10⁰0 transition in CO₂ molecules. The excitation and relaxation kinetics of this and neighbours vibrational modes of CO₂ were studied both by CARS and PARS. Vibrational excitation of up to 20% of the total number of irradiated molecules is measured; previously unknown desactivation constant of CO₂ (10⁰0) and CO₂ (02⁰0) states via CO₂ (01¹0) state is estimated to be K = (3±1) × 1 ⁵s^-1torr^-1.     

Vibrational excitation of a molecule by a resonance current

Correct expressions are obtained for calculating a tunnel-resonance current through molecules. The participation of molecular vibrations in the resonance charge transfer through a molecule and vibrational excitation of the molecule are determined by the reorganization energy E _r of the vibrational system depending on the displacement of the equilibrium position of vibrational modes in passing from the neutral molecule to the resonance state of a molecular ion. The mean excitation energy of the molecule during the propagation of an elementary charge changes from E _r at the voltage across electrodes close to the threshold up to 2E _r at voltages considerably exceeding the threshold voltage. An expression is obtained for the stationary vibrational temperature of the molecule, which is proportional to the resonance current.     

Fluorescence anisotropy of indole molecules under two-photon excitation in the spectral range of 485–510 nm

Decay of polarized fluorescence in indole dissolved in propylene glycol under two-photon excitation by femtosecond laser pulses in the wavelength range of 485–510 nm has been studied. It is shown that under the experimental conditions used the fluorescence decay signal can be well described by a single excited state lifetime τ_f and a single rotation diffusion time τ_rot. By processing the data obtained, the times τ_f and τ_rot as well as anisotropy parameter r ₀ characterizing the symmetry of two-photon excitation of indole molecules have been determined. Decreasing of the anisotropy parameter r₀ down to zero under two-photon excitation energy higher than 5.1 eV has been observed. Interpretation of the obtained results have been done on the basis of ab initio quantum-mechanical computations. A model of energy relaxation under the condition of twophoton excitation of indole in a polar solvent has been discussed.     

Influence of the polarity of a medium on the photonics of a merocyanine dye with a high quadratic polarizability

The influence of the polarity of a medium on the spectral and luminescent properties of 2-[(2E,4E)-6-(1,3,3-trimethyl-2,3-dihydro-1H-2-indolyliden)-2,4-hexadienyliden]malononitrile (THDM) in solutions and polymer matrices is studied at room temperature under conditions of steady-state and pulsed laser excitation. A large bathochromic shift of the absorption spectra observed upon an increase in the polarity of a solvent is caused by a strong increase in the molecular dipole moment μ due to a transition of molecules from the ground state (μ_g = 7.6 D) to an excited Franck-Condon state (μ^FC = 33.5 D). Based on the solvatochromic data, the quadratic polarizability was calculated to be β = (3.2 ± 0.6) × 10^?28 esu, which is close to the experimentally determined value β_ex = (3.9 ± 0.2) × 10^?28 esu. A strong narrowing of the fluorescence spectra in comparison with the absorption spectra is observed upon an increase in the solvent polarity. This narrowing is explained by a decrease in the bond length alternation parameter and by weakening of vibronic interactions in the singlet excited state. The dynamic solvatofluorochromism of THDM in the picosecond range is caused by reorientations of molecules of the polar environment occurring during a time period consistent with the dielectric relaxation time of these molecules.     

Study of the dissipation of vibrational energy excess using pulse fluorometry

The dependence of the emission anisotropy decay of dye fluorescence versus excitation wavelength was measured in order to study the relaxation of the vibrational energy excess. The results of these measurements allow the conclusion (in accordance with earlier findings) that the heat transfer in the solvent is a fast enough process not to influence Brownian rotations of dye molecules.     

Spectral and luminescent properties of jet-cooled dinaphthofuran

The fluorescence and fluorescence excitation spectra of jet-cooled dinaphtho[2,1-b:1′,2′-d]furan (dinaphthofuran) molecules, as well as their complexation with inert gases Ar, Kr, and Xe, are studied. The indicatrices of the degree of polarization of fluorescence of dinaphthofuran molecules upon excitation of the electronic transitions S ₀?S ₁ and S ₀?S ₂ are calculated as functions of the intramolecular orientation of the transition dipole moments. The fluorescence polarization spectrum is measured under excitation within the rotational contour of the line of the purely electronic transition v ₀ ⁰ = 29 294 cm^?1. In contrast to complex planar molecules, the S ₀?S ₂ fluorescence excitation spectrum of dinaphthofuran is found to be continuous, with the Q branch of the rotational contour being absent. The fluorescence excitation spectra of van der Waals complexes of dinaphthofuran with inert gases exhibit multiplet lines, which is associated with the helical structure of the molecules studied.     

Direct measurement of multiphoton molecular absorption of IR laser radiation by pyroelectric detector

The applicability of a pyroelectric detector (PED) to multiphoton absorption measurements (MPA) under ir laser excitation of molecules was examined. The possibility of MPA measurement of SF₆ molecules in the pressure range of 10⁻³÷10⁻¹ Torr with a time resolution of ∼ 7 μs has been shown. It has been demonstrated that the degree of vibrational relaxation of highly vibrationally excited molecules at PED surface does not depend on excitation level under the studied conditions.     

Slow intermolecular redistribution of vibrational energy in SF6 gas excited by a tea CO2 laser

Infra-red fluorescence (IRF) spectra of SF₆ excited by the 944.2 cm^-1 line of a pulsed CO₂ laser were observed at various times after the time of the laser excitation. Each spectrum showed a strong IRF peak of the v₃ mode which was red shifted relative to the room temperature fundamental (948 cm^-1) by an amount which depended, apart from the level of excitation, on the different times employed. For a strong excitation with 〈n〉 ≈ 11 photons absorbed per molecule, a significant decrease of red shift versus time was observed, indicating mainly excitation losses by IRF emission. For weak excitation with 〈n〉 ≈ 1.4, almost an constant red shift versus time is observed. This result, and the previous finding that at weak excitation a nonthermal energy distribution in the ensemble of molecules exists, leads to the conclusion that intermolecular redistribution of vibrational energy in SF₆ is slow, and does not exceed the observed fluorescence duration (～1 ms).