Vibrational relaxation dynamics in transient grating spectroscopy studied by rate equations based on time-dependent correlation function

A modified model, a set of rate equations based on time-dependent correlation function, is used to study vibrational relaxation dynamics in transient grating spectroscopy. The dephasing, the population dynamics, and the vibrational coherence concerning two vibrational states are observed respectively in organic dye IR780 perchlorate molecules doped polyvinyl alcohol matrix. The result shows that in addition to the information concerning system-environment interac- tion and vibrational coherence, the vibrational energy transfer can be described by this modified model.     

Triplet-triplet transfer of electronic energy upon nonequilibrium vibrational excitation of triplet molecules

The specific features of the triplet-triplet (T-T) transfer of electronic excitation energy in a gas phase upon nonequilibrium vibrational excitation of the triplet molecules of a donor were studied for an anthraquinone-diacetyl donor-acceptor pair using the time-resolved slow fluoresence of anthraquinone and sensitized phosphorescence of diacetyl. It is shown that in the gas phase, which allows regular control of the number of collisions, competition between the processes of T-T transfer and intermolecular vibrational relaxation is observed for nanosecond time resolution. The T-T transfer rate for the molecular system investigated exceeded the rate of intermolecular vibrational relaxation k_V in the triplet state T₁ of the donor. The effectiveness of the T-T transfer of energy by vibrationally excited molecules turned out to be higher than the effectiveness of transfer by thermalized ones, but even the highest of them was much less than unity. An increase in the equilibrium temperature of vapors led to a decrease in the effectiveness of transfer for both vibrationally excited and thermalized triplet molecules, thus indicating the importance of the collisional complex in the intermolecular process studied. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 4, pp. 474–479, July–August, 2000.     

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.     

Investigation of intra- and intermolecular transfer processes by picosecond fluorescence gating

Fluorescence up-conversion is a promising technique for the investigation of ultrafast processes within and between poly-atomic molecules. Conditions are discussed for up converting broad-band fluorescence efficiently with a time resolution better than 1 ps. Experimental results are presented on vibrational relaxation in the first excited singlet state, internal conversion, and intermolecular energy transfer in liquid solutions.     

Theoretical insight into the excited‐state behavior of a novel Compound 1: A TDDFT investigation

In the present work, using density functional theory and time‐dependent density functional theory methods, we investigated and presented the excited‐state intramolecular proton transfer (ESIPT) mechanisms of a novel Compound 1 theoretically. Analyses of electrostatic potential surfaces and reduced density gradient (RDG) versus sign(λ₂)ρ, we confirm the existence of intramolecular hydrogen bond O1‐H2···N3 for Compound 1 in the S₀ state. Comparing the primary structural variations of Compound 1 involved in the intramolecular hydrogen bond, we find that O1‐H2···N3 should be strengthened in the S₁ state, which may facilitate the ESIPT process. Concomitantly, infrared (IR) vibrational spectra analyses further verify the stability of hydrogen bond. In addition, the role of charge transfer interaction has been addressed under the frontier molecular orbitals, which depicts the nature of electronical excited state and supports the ESIPT reaction. The theoretically scanned and optimized potential energy curves according to variational O1‐H2 coordinate demonstrate that the proton transfer process should occur spontaneously in the S₁ state. It further explains why the emission peak of Compound 1‐enol was not reported in previous experiment. This work not only presents the ESIPT mechanism of Compound 1 but also promotes the understanding of this kind of molecules for further applications in future.     

NIR‐FT Raman and FT‐IR spectral investigations of the nonlinear optical chromophore p‐bromoacetanilide

Vibrational spectral analysis of the hydrogen‐bonded nonlinear optical (NLO) material p‐bromo acetanilide (PBA) was carried out using NIR‐FT‐Raman and FT‐IR spectroscopy. Ab initio molecular orbital computations were performed at HF/6‐31G (d) level to derive equilibrium geometry, vibrational wavenumbers, intensities and first hyperpolarizability. The lowering of the imino stretching wavenumbers suggests the existence of strong intermolecular N H···O hydrogen bonding, which was substantiated by the natural bond orbital (NBO) analysis. The vibrational spectra confirm that the charge‐transfer interaction between the  NHCOCH₃ group and—Br through phenyl ring is responsible for simultaneous strong IR and Raman activation of the ring mode 8a. Vibrational analysis indicates that the lowering of stretching wavenumbers of methyl group due to electronic effects simultaneously caused by induction and hyperconjugation is due to the presence of the oxygen atom. The presence of blue‐shifting H‐bonds of CH stretching wavenumbers, simultaneous activation of carbonyl stretching mode, the strong activity of low‐wavenumber H‐bond stretching vibrations and the role of intramolecular charge transfer in making the molecule NLO active have been analyzed on the basis of the vibrational spectral features. Copyright © 2007 John Wiley & Sons, Ltd.     

Heterodyne interferometric polarization coherent anti‐Stokes Raman scattering (HIP‐CARS) spectroscopy

We demonstrate a new technique that combines polarization sensitivity of the coherent anti‐Stokes Raman scattering (CARS) response with heterodyne amplification for background‐free detection of CARS signals. In this heterodyne interferometric polarization CARS (HIP‐CARS), the major drawbacks of polarization and heterodyne CARS are rectified. Using a home‐built picosecond optical parametric oscillator, we are able to address vibrational stretches between 600 and 1650 cm⁻¹ and record continuous high‐resolution Raman equivalent HIP‐CARS spectra. Copyright © 2010 John Wiley & Sons, Ltd.     

Vibrational energy redistribution and vibrational dynamics of methanol mixed with Rhodamine 101 dye

Vibrational energy transfer that occurs after photoexcitation can be tracked in the first several femtoseconds by ultrafast time- and frequency-resolved CARS (coherent anti-Stokes Raman scattering) spectroscopy. Vibrational energy transfer from high-frequency modes to lower ones through chemical bond of pure methanol and methanol/Rhodamine 101 (Rh101) solution is detected. Through comparison and analysis of the experimental results, it is found that surrounding molecules have a significant influence on vibrational energy transfer and vibrational couplings among relevant modes.     

Intermolecular Processes in Excited Electronic States in the Gas Phase (Review)

A brief review of works on the temperature dependences of the rate constants k_q of the intermolecular processes proceeding in the excited electronic states in the gas phase is given. The dependences k_q(T) for such biomolecular processes as intermolecular vibrational energy transfer in the triplet state vibrational quasi-continuum, triplet-triplet electron excitation energy transfer, and intermolecular photoinduced electron transfer have been compared. The experimental data have shown that in the gas phase for all analyzed intermolecular processes both an increase and a decrease in k_q with increasing temperature (T) is observed, which is not associated with the specific intermolecular interactions leading to the formation of long-lived components. The change in the type of temperature dependence is due to the change in the mechanisms of the radiationless transitions with increasing density of vibrational levels in the final electronic state. The applicability of the known models based on the theory of radiationless transitions for predicting the temperature dependences k_q(T) is discussed. __________ Translated from Zhurnal Prikladnoi Spektros-kopii, Vol. 72, No. 4, pp. 429–439, July–August, 2005.     

Time‐resolved coherent anti‐Stokes Raman spectroscopy impulsively excited by supercontinuum

Time‐resolved coherent anti‐Stokes Raman scattering (CARS) impulsively excited by a supercontinuum (SC) is investigated. We show that it is critical to optimize the temporal overlapping of the constituent solitons of a SC in order to impulsively excite vibrational modes over a broad frequency range. The cross‐correlation frequency‐resolved optical gating technique is utilized to retrieve the optical response function of molecules under SC impulsive excitation, and background‐free CARS with spectral resolution significantly better than the bandwidth of the probe pulses is achieved. Copyright © 2011 John Wiley & Sons, Ltd.     

Time‐resolved investigation of the ν1 ro‐vibrational Raman band of H2CO with fs‐CARS

The technique of femtosecond time‐resolved coherent anti‐Stokes scattering (fs‐CARS) is used to investigate the strongly perturbed ν₁ ro‐vibrational Raman band of formaldehyde (H₂CO). The time‐dependent signal is simulated using a ‘Watson‐’Hamiltonian in A‐type reduction and Raman theory for asymmetric rotors. The results are compared with the experimental data. The fs‐CARS method measures the evolution of the polarization in a molecular ensemble via superposition of many states and is sensitive to spectral irregularities or line shifts of the involved transitions. ‘Coriolis’ interactions play a major role in the analysis of the ν₁ band of formaldehyde. We successfully simulate the fs‐CARS transient signal from the ν₁ band of formaldehyde including a model for multiple ‘Coriolis’ interactions, without the necessity of describing the complete interaction between all the vibrational levels. ‘Coriolis’ coupling coefficients and energy shifts are derived from the experiment by a least‐square fit. The results are discussed and compared to literature values. Copyright © 2006 John Wiley & Sons, Ltd.     

UV resonance Raman study of cation–π interactions in an indole crown ether

UV resonance Raman (UVRR) spectroscopy is used to probe changes in vibrational structure associated with cation–π interactions for the most prevalent amino acid π–donor, tryptophan. The model compound studied here is a diaza crown ether with two indole substituents. In the presence of sodium or potassium sequestered in the crown ether, or a protonated diaza group on the compound, the indole moieties participate in a cation–π interaction in which the pyrrolo group acts as the primary π‐donor. Systematic shifts in relative intensity in the 760–780 cm⁻¹ region are observed upon formation of this cation–π interaction; we propose that these modifications reflect shifts of the delocalized, ring‐breathing W18 and hydrogen‐out‐of‐plane (HOOP) vibrational modes in this spectral region. The observed changes are attributed to perturbations of the π‐electron density as well as of normal modes that involve large displacement of the hydrogen atom on the C2 position of the pyrrole ring. Modest variations in the UVRR spectra for the three complexes studied here are correlated to differences in cation–π strength. Specifically, the UVRR spectrum of the sodium‐bound complex differs from those of the potassium‐bound or protonated‐diaza complexes, and may reflect the observation that the C2 hydrogen atom in the sodium‐bound complex exhibits the greatest perturbation relative to the other species. Normal modes sensitive to hydrogen‐bonding, such as the tryptophan W10, W9, and W8 modes, also undergo shifts in the presence of the salts. These shifts reflect the strength of interaction of the indole N H group with the iodide or hexafluorophosphate counteranion. The current observation that the W18 and HOOP normal mode regions of the indole crown ether compound are sensitive to cation–pyrrolo π interactions suggests that this region may provide reliable spectroscopic evidence of these important interactions in proteins. Copyright © 2010 John Wiley & Sons, Ltd.     

Experimental vibrational spectra (Raman,infrared) and DFT calculations on monomeric and dimeric structures of 2‐ and 6‐bromonicotinic acid

In this work, the Fourier transform infrared and Raman spectra of 2‐bromonicotinic acid and 6‐bromonicotinic acid (abbreviated as 2‐BrNA and 6‐BrNA, C₆H₄BrNO₂) have been recorded in the region 4000–400 and 3500–50 cm⁻¹. The optimum molecular geometry, normal mode wavenumbers, infrared intensities and Raman scattering activities, corresponding vibrational assignments and intermolecular hydrogen bonds were investigated with the help of B3LYP density functional theory (DFT) method using 6‐311++G(d,p) basis set. Reliable vibrational assignments were made on the basis of total energy distribution (TED) calculated with scaled quantum mechanical (SQM) method. From the calculations, the molecules are predicted to exist predominantly as the C1 conformer. Copyright © 2009 John Wiley & Sons, Ltd.     

CARS investigation of collisional shift of the hydrogen Q‐branch transitions by water at high temperatures

A high‐resolution (∼0.1 cm⁻¹) spectroscopic method based on the application of a Fabry–Pérot interferometer to the spectral analysis of the coherent anti‐Stokes Raman scattering (CARS) signal from an individual Raman transition was used to obtain single‐shot spectra of hydrogen Q‐branch transitions directly in the flame of a pulsed, high‐pressure H₂/O₂ combustion chamber. Simultaneously with the Fabry–Pérot pattern, a broadband CARS spectrum of the complete H₂Q ‐branch structure was recorded in order to measure the temperature of the probe volume. During every cycle of the combustion chamber, a pressure pulse together with single‐shot CARS spectra, providing information on individual line shapes and medium temperature, was recorded. On the basis of the experimental data, the temperature dependences of lineshift coefficients for several Q‐branch lines of hydrogen molecules under collisions with water molecules were determined in the temperature range 2100 < T < 3500 K, and an empirical ‘fitting law’ for H₂ H₂O lineshift coefficients is proposed. Copyright © 2010 John Wiley & Sons, Ltd.     

Broadening of vibrational spectra of carbon dioxide upon absorption and condensation in nanopores

Coherent anti-Stokes Raman Spectroscopy (CARS) has been used to study the vibrational Q-branch with the frequency of 1388 cm^?1 of the ν₁ mode of carbon dioxide molecules filling a sample made of nanopore glass at room temperature (20.5°C). The measurements were carried out in a gas cell at pressures approaching saturation P _sat. When pressure was increased above 0.8 P _sat, in addition to the spectral component due to the gaseous phase molecules, the CARS spectra featured a component due to the molecules adsorbed on the pore walls. Simulation of spectra taking the interference of these two contributions into account enabled the estimation of the broadening of the vibrational molecular spectra in the adsorbed layer. The spectral width of the component due to the adsorbed molecules was nearly a factor of two times larger than that of molecules in the bulk liquid phase. At pressures above 0.94 P _sat, the spectral width of the component due to the adsorbed molecules decreased to values close to those measured in the bulk liquid phase, which corresponds to the condensation of molecules in nanopores.     

Ultrasonic dispersion due to vibrational relaxation in dichloromethane-m-xylene mixtures

Velocity dispersion due to vibrational relaxation in liquid dichloromethane-m-xylene mixtures is observed from ultrasonic and hypersonic measurements. The results indicate that the vibrational modes of both molecules are coupled with each other by near-resonant intermolecular V-V transfer.     

The effect of benzo‐annelation on intermolecular hydrogen bond and proton transfer of 2‐methyl‐3‐hydroxy‐4(1H)‐quinolone in methanol: A TD‐DFT study

Excited‐state intermolecular or intramolecular proton transfer (ESIPT) reaction has important potential applications in biological probes. In this paper, the effect of benzo‐annelation on intermolecular hydrogen bond and proton transfer reaction of the 2‐methyl‐3‐hydroxy‐4(1H)‐quinolone (MQ) dye in methanol solvent is investigated by the density functional theory and time‐dependent density functional theory approaches. Both the primary structure parameters and infrared vibrational spectra analysis of MQ and its benzo‐analogue 2‐methyl‐3‐hydroxy‐4(1H)‐benzo‐quinolone (MBQ) show that the intermolecular hydrogen bond O₁―H₂?O₃ significantly strengthens in the excited state, whereas another intermolecular hydrogen bond O₃―H₄?O₅ weakens slightly. Simulated electron absorption and fluorescence spectra are agreement with the experimental data. The noncovalent interaction analysis displays that the intermolecular hydrogen bonds of MQ are obviously stronger than that of MBQ. Additionally, the energy profile analysis via the proton transfer reaction pathway illustrates that the ESIPT reaction of MBQ is relatively harder than that of MQ. Therefore, the effect of benzo‐annelation of the MQ dye weakens the intermolecular hydrogen bond and relatively inhibits the proton transfer reaction.     

Influence of Vibrational Excitation of Triplet Molecules of Anthraquinone on the Photochemical Processes in Gas Mixtures with Amines

By the quenching of the delayed fluorescence (DF) of anthraquinone vapors by aliphatic amines (diethylamine, dibutylamine, cyclohexylamine) and pyridine the photoinduced processes proceeding with the participation of vibrationally excited triplet molecules of anthraquinone have been investigated. The DF quenchingrate constants K _q varying from 1·10⁶ sec^–1·torr^–1 in mixtures with diethylamine to 7·10³ sec^–1·torr^–1 in mixtures with pyridine have been estimated. A correlation between the values of K _q and the ionization potentials of foreign gases confirming the important role of interactions with charge transfer in the quenching of triplet molecules in the gas phase has been established. The influence of other relaxation processes on the DF quenching is considered. It is shown that the intermolecular vibrational relaxation in the T ₁ triplet state leading to the establishment of relaxation equilibrium at a vibrational temperature T _vib considerably increasing the medium temperature is the fastest process among the biomolecular processes (rate constants K _col ^V > 10⁶ sec^–1·torr^–1 > K _q). The values of T _vib and the vibrational energies E _vib of the triplet molecules after the energy exchange in the collisional complex have been estimated. It has been concluded that the photochemical reaction yield is determined by the intermolecular processes proceeding in the T ₁ state at a vibrational equilibrium characterized by high values of T _vib. The influence of E _vib of triplet molecules on the DF quenching rates at a photoinduced electron transfer is considered.     

Collisional Energy Transfer of Highly Vibrationally Excited Polyatomic Molecules. The Effect of Excited Molecule Complexity

Collisional relaxation was probed by CO₂ laser activated delayed fluorescence. The experimental information was adopted to determine the average energies transferred per collision (ΔE) from highly vibrationally excited polyatomic molecules to parent collider. The values of (ΔE) decreased with increasing the number of atoms in the excited molecules in line: biacetyl, acetophenone, benzophenone, antraquinone. The dependences of (ΔE) on the number of factors such as: 1) the average vibrational energy residing in the vibrational modes of excited molecules; 2) the potential of intermolecular interaction; 3) the reduced mass, and others were analyzed in details. The general interplay was noticed between (ΔE) and the molecular parameters which determined the increasing interaction strength and the decreasing energy transfer efficiency due to the adiabatic constraints on the energy transfer.     

Herman-Wallis factor to improve thermometric accuracy of vibrational coherent anti-Stokes Raman spectra of H2

The Herman-Wallis factor is a molecular parameter that measures the influence of centrifugal force on the intensity of spectral lines. Understandably, the effect is significant for very light molecules that necessarily have large couplings between vibrational and rotational degrees of freedom. Although known, the conceptual basis of the Herman-Wallis factor are nevertheless not clearly established in the literature. Over the years, different approaches have been proposed to explain the corrections to spectral line-strengths and, recently, an experimental study has demonstrated that Q-branch Raman transitions of H₂ are highly sensitive to the theoretical model employed to determine the Herman-Wallis factor. In this paper, this fact is used to analyze the consequences on thermometry based on coherent anti-Stokes Raman scattering (CARS) designed to probe H₂ molecules in combustion studies. It is found that the different Herman-Wallis factors lead to relative thermometric disagreements from several tens up to hundreds of degrees. This analysis could explain why H₂ CARS thermometry has been considered less reliable than thermometric predictions based on CARS of more common molecules such as N₂, O₂ and others. In particular, it is remarked that unreliable expressions of Herman-Wallis factors have been used so far to interpret Q-branch H₂ CARS experiments.