Vibrational Relaxation Research Articles

Nuclear Quantum Effects in Proton or Hydrogen Transfer.

Proton or hydrogen transfers, basic chemical reactions, proceed either by thermally activated barrier crossing or via tunneling. Studies of molecules undergoing single or double proton or hydrogen transfer in the ground or excited electronic state reveal that tunneling can dominate under conditions usually considered to favor the thermal process. Moreover, the tunneling probability strongly varies for excitation of certain vibrational modes, which changes the effective barrier and/or proton transfer distance. When the reaction is fast compared to vibrational relaxation, the mode selectivity can still be maintained for molecules in solutions at 293 K. These observations point to dangers of relating the calculated minimum energy paths and the associated barriers to the experimentally obtained activation energies. The multidimensional character of the reaction coordinate is obvious; it can dramatically change for slowly and rapidly relaxing environments. We postulate that the hydrogen bond definition should be extended by specifically including the role of molecular vibrations.

Mechanistic insights into the AIE properties of BF2 complexes of N-acetyl 2-aminobenzothiazoles as rotorless polyheteroaromatics

A series of four novel BF2 complexes of N-acetyl 2-aminobenzothiazoles featuring rigid rotorless polyheteroaromatic structures have been designed and synthesized. All of these compounds exhibited AIE properties with excellent solid-state fluorescence quantum yields up to 81.7%. Theoretical calculations revealed the characteristics of their ground-state structures and excitation processes. Their seemingly abnormal nonradiative decay in solutions was investigated from both direct vibrational relaxation and S0/S1 surface crossing perspectives by the two-channel model. The minimum energy conical intersection (MECI) located by SF-TDDFT method indicated that the CI is mainly induced by the deformation of the BF2 complex ring, leads to elevated energy level, and thus is not responsible for the fluorescence quenching. The potential energy curve (PEC) constructed along the distortion angle θ of BF2 complex ring showed that when θ reaches 50° (the dark-state region approaching MECI), the energy barrier is only 0.11 eV, suggesting that the deformed dark state could serve as an effective deactivation channel via ultrafast internal conversion (IC). Crystallographic analysis illustrated that the F atoms perpendicular to the polyheterocycle could effectively prohibit detrimental π-π stacking and enhance intermolecular interactions, thereby resulting in efficient solid-state emission.

Vibrational energy transfer in ammonia-helium collisions.

While the rotational energy transfer of ammonia by rare gas atoms and hydrogen molecules has been the focus of many studies, little is known about its vibrational relaxation, even though transitions involving the umbrella bending mode have been observed in many astrophysical environments. Here we explore the vibrational relaxation of the umbrella mode of ammonia induced by collisions with helium atoms by means of the close-coupling method on an ab initio potential energy surface. We compute cross sections up to kinetic energies of 1500 cm-1 and rate coefficients up to a temperature of 300 K for vibrational, rotational, and inversion transitions involving the lowest two vibrational states. We show that vibrational relaxation is much less efficient than rotation-inversion relaxation, although the rate coefficients for vibrational relaxation strongly increase with the temperature. We also observe important differences for vibrationally-elastic transitions within the lowest two vibrational states, i.e., for rotation-inversion transitions. These are a direct consequence of the difference in the tunnelling splitting of the lowest inversion levels.

Shortwave infrared polymethine dyes for bioimaging: ultrafast relaxation dynamics and excited-state decay pathways.

Excited-state relaxation in two prototypical shortwave infrared (SWIR) polymethine dyes developed for bioimaging, heptamethine chromenylium Chrom7 and flavylium Flav7, is studied by means of femtosecond transient absorption with broadband ultraviolet-to-SWIR probing complemented by steady-state and time-resolved fluorescence and phosphorescence measurements. The relaxation processes of the dyes in dichloromethane are resolved with sub-100 fs temporal resolution using SWIR, near-IR, and visible photoexcitation. Different population members of the ground-state inhomogeneous ensemble are found to equilibrate via skeletal deformation changes with time constants of 90 fs and either 230 fs (Chrom7) and 350 fs (Flav7) followed by slower evolution matching the 1-ps timescale of diffusive solvation dynamics. Molecules excited into high-lying singlet electronic states (Sn) by visible excitation repopulate with time constants of 400 fs (Chrom7) and 450 fs (Flav7) the corresponding first excited singlet S1 states, which decay within several hundreds of picoseconds in dichloromethane and chloroform solvents. Vibrational relaxation in S1 for both Chrom7 and Flav7 in dichloromethane occurs with time constants of 350 and 800 fs for excess of vibrational energy of ∼1000 and 10 000 cm-1 deposited by near-IR and visible excitation, respectively. Two competing non-radiative processes are present in S1: temperature-independent internal conversion, and thermally-activated twisting about a carbon-carbon bond of the conjugated chain, which is substantial at room temperature but essentially nonreactive, producing traces of isomer product. Intersystem crossing in S1, and thus the triplet quantum yield, is minor. The importance of absorption bands from the excited S1 state in applications requiring high-intensity excitation conditions is discussed.

Local electric field in nanocavities dictates the vibrational relaxation dynamics of interfacial molecules.

Plasmonic nanocavities enable the generation of strong light-matter coupling and exhibit great potential in plasmon-mediated chemical reactions (PMCRs). Although an electric field generated by nanocavities (E n) has recently been reported, its effect on the vibrational energy relaxation (VER) of the molecules in the nanocavities has not been explored. In this study, we reveal the impact of an electric field sensed by molecules (para-substituted thiophenol derivatives) in a nanocavity (E f) on VER processes by employing advanced time-resolved femtosecond sum frequency generation vibrational spectroscopy (SFG-VS) supplemented by electrochemical measurements. The magnitude of E n is almost identical (1.0 ± 0.2 V nm-1) beyond the experimental deviation while E f varies from 0.3 V nm-1 to 1.7 V nm-1 depending on the substituent. An exponential correlation between E f and the complete recovery time of the ground vibrational C[double bond, length as m-dash]C state (T 2) of the phenyl ring is observed. Substances with a smaller T 2 are strongly correlated with the reported macroscopic chemical reactivity. This finding may aid in enriching the current understanding of PMCRs and highlights the possibility of regulating vibrational energy flow into desired reaction coordinates by using a local electric field.

Dehydrogenation of diborane on small Nbn+ clusters.

The reactivity of Nbn+ (1 ≤ n ≤ 21) clusters with B2H6 is studied by using a self-developed multiple-ion laminar flow tube reactor combined with a triple quadrupole mass spectrometer (MIFT-TQMS). The Nbn+ clusters were generated by a magnetron sputtering source and reacted with the B2H6 gas under fully thermalized conditions in the downstream flow tube where the reaction time was accurately controlled and adjustable. The complete and partial dehydrogenation products NbnB1-4+ and NbnB1-4H1,2,4+ were detected, indicative of the removal of H2 and likely BHx moieties. Interestingly, these NbnB1-4+ and NbnB1-4H1,2,4+ products are limited to 3 ≤ n ≤ 6, suggesting that the small Nbn+ clusters are relatively more reactive than the larger Nbn>6+ clusters under the same conditions. By varying the B2H6 gas concentrations and the reactant doses introduced into the flow tube, and by changing the reaction time, we performed a detailed analysis of the reaction dynamics in combination with the DFT-calculated thermodynamics. It is demonstrated that the lack of cooperative active sites on the Nb1+ cations accounts for the weakened dehydrogenation efficiency. Nb2+ forms partial dehydrogenation products at a faster rate. In contrast, the Nbn>6+ clusters are subject to more flexible vibrational relaxation which disperse the energy gain of B2H6-adsorption and thus are unable to overcome the energy barriers for subsequent hydrogen atom transfer and H2 release.

Interplay between anion-receptor and anion-solvent interactions in halide receptor complexes characterized with ultrafast infrared spectroscopies.

The competition between host-guest binding and solvent interactions is a crucial factor in determining the binding affinities and selectivity of molecular receptor species. The interplay between these competing interactions, however, have been difficult to disentangle. In particular, the development of molecular-level descriptions of solute-solvent interactions remains a grand experimental challenge. Herein, we investigate the prototypical halide receptor meso-octamethylcalix[4]pyrrole (OMCP) complexed with either chloride or bromide anions in both dichloromethane (DCM) and chloroform (trichloromethane, TCM) solvent using ultrafast infrared transient absorption and 2D IR spectroscopies. OMCP·Br- complexes in both solvents display slower vibrational relaxation dynamics of the OMCP pyrrole NH stretches, consistent with weaker H-bonding interactions with OMCP compared to chloride and less efficient intermolecular relaxation to the solvent. Further, OMCP·Br- complexes show nearly static spectral diffusion dynamics compared to OMCP·Cl-, indicating larger structural fluctuations occur within chloride complexes. Importantly, distinct differences in the vibrational spectra and dynamics are observed between DCM and TCM solutions. The data are consistent with stronger and more perturbative solvent effects in TCM compared to DCM, despite DCM's larger dielectric constant and smaller reported OMCP·X- binding affinities. These differences are attributed to the presence of weak H-bond interactions between halides and TCM, in addition to competing interactions from the bulky tetrabutylammonium countercation. The data provide important experimental benchmarks for quantifying the role of solvent and countercation interactions in anion host-guest complexes.

OH-Formation following vibrationally induced reaction dynamics of H2COO.

The reaction dynamics of H2COO to form HCOOH and dioxirane as first steps for OH-elimination is quantitatively investigated. Using a machine learned potential energy surface (PES) at the CASPT2/aug-cc-pVTZ level of theory vibrational excitation along the CH-normal mode νCH with energies up to 40.0 kcal mol-1 (∼5νCH) leads almost exclusively to HCOOH which further decomposes into OH + HCO. Although the barrier to form dioxirane is only 21.4 kcal mol-1 the reaction probability to form dioxirane is two orders of magnitude lower if the CH-stretch mode is excited. Following the dioxirane-formation pathway is facile, however, if the COO-bend vibration is excited together with energies equivalent to ∼2νCH or ∼3νCOO. For OH-formation in the atmosphere the pathway through HCOOH is probably most relevant because the alternative pathways (through dioxirane or formic acid) involve several intermediates that can de-excite through collisions, relax via internal vibrational relaxation (IVR), or pass through loose and vulnerable transition states (formic acid). This work demonstrates how, by selectively exciting particular vibrational modes, it is possible to dial into desired reaction channels with a high degree of specificity.

Carbon-sulfur bond elongation as the promoting reaction coordinate in the efficient sub-nanosecond intersystem crossing in thianaphthene derivatives.

Thiophene derivatives have become integral to OLEDs, photovoltaics, and photodynamic therapy research. A deeper understanding of their excited state dynamics and electronic relaxation mechanisms is expected to provide important physical insights of direct relevance for these applications. In this study, thianaphthene (TN), 2-methylbenzothiophene (2MBT), and 3-methylbenzothiophene (3MBT) are investigated using femtosecond broadband transient absorption and steady-state spectroscopy techniques along with time-dependent density functional calculations in cyclohexane and acetonitrile. The photophysical properties and electronic relaxation mechanisms of these derivatives are elucidated. Small fluorescence quantum yields ranging from 0.4 to 1.1% are measured. It is demonstrated that excitation of TN at 290 nm leads primarily to intersystem crossing to the triplet manifold with a lifetime of 400 ± 15 ps in either solvent, whereas four- to twofold shorter intersystem crossing lifetimes are measured for 2MBT and 3MBT depending on whether cyclohexane or acetonitrile is used. Linear interpolation of internal coordinates evidence that elongation of the S-C bonds enables ultrafast intersystem crossing in these thiophene derivatives involving singlet and triplet states with ππ* and πσ* characters. Excitation at 266 nm results in an additional 5 ± 1 ps lifetime, which is assigned to intramolecular vibrational relaxation dynamics occurring in the excited singlet state.

Characterizing excited-state intramolecular proton transfer in 3-hydroxyflavone with ultrafast transient infrared spectroscopy.

Vibrational dynamics associated with excited-state intramolecular proton transfer in 3-hydroxyflavone and 3-hydroxy-2-(thiophen-2-yl)chromen-4-one are characterized with ultrafast transient infrared spectroscopy. The spectroscopic data reveal rapid (<100 fs) proton transfer dynamics in both species, followed by vibrational relaxation of the tautomer products within a few picoseconds. Coherent coupling of the shared proton to low-frequency modes along the hydrogen bond coordinate are also observed in the ground electronic states.

Nonlinear Scattering of 248 nm Wavelength Light in High-Pressure SF6 and CH4 Gases for the Temporal Compression of a 20 ns KrF Laser Pulse

The nonlinear compression of narrowband (Δν ≈ 0.2 cm−1) 20 ns KrF laser pulses in SF6 at 10 atm and in CH4 at 50 atm pressure was studied. Both SBS and SRS optically phase-conjugated backward-reflected radiation was registered with an energy reflectivity of 10–14% in SF6 and CH4. In SF6, the SBS pulses gradually shortened from 10 ns to 2–3 ns with a decrease in pumping to the SBS threshold of ~10 mJ, while the SRS pulse had the shortest length of 30–60 ps for the maximal pumping of 120 mJ and broadened near the SRS threshold of ~30 mJ. For the SRS pulse energy, the ~2 mJ peak power 5 × 107 W was tenfold higher than the pump power. The theoretical model predicted a soliton-like SRS pulse compression to a temporal length of the order of the vibrational relaxation time. There was no pulse compression of backward SBS and SRS radiation in CH4, while, in the forward direction, SRS pulses shortened to 3–4 ns at reduced pumping.

Supersonically expanded sodium metal-dilute halogen gas interactions. The importance of reaction populated and energy storing reservoir states and population inversion created amplification in Na2.

The reactions of Cl, Br, and I with Nan=2,3 produced in a supersonic expansion form Na2* and Na* excited states extending across the visible and ultraviolet regions. Emission in the region extending from 410 to 600nm indicates selectively formed excited state Na2 emission features. Experimental evidence suggests that this emission is associated with Na3 + X reactions. Broadband (0.5cm-1) laser measurements demonstrate gain (population inversion) for select features at∼524-528(1%), ∼492(0.3%), and ∼458.7-461(0.8%) nm. Single mode (0.007cm-1) measurements extending from 528.03 to 527.63nm demonstrate amplification involving five to six individual rovibronic levels with a maximum gain close to 3% recorded at 527.9nm. The observed gain is associated with select transitions from levels of the Na2 11Πu state populated, via identified curve crossings, through collision induced transfer from long-lived Na2 21Σg+ and 11Πg reservoir states. Collision induced population buildup in the lowest vibrational levels of these reservoir states and collision induced transfer to the Na2 11Πu state create a population inversion in transitions to the X 1Σg+ state of Na2. The observed amplification is aided by rapid vibrational and rotational relaxation in both the Na2 ground and excited reservoir states producing amplifiers in the visible region like the HF amplifier in the infrared. This study suggests the importance of reaction populated and energy storing long-lived reservoir states in small sodium molecule combustion processes and indicates the potential for providing new short wavelength visible and ultraviolet amplifiers for future laser-based chemical propulsion concepts.

Photo-physical characteristics of color N3-center in diamond studied via UV femtosecond-laser pumped luminescence.

Micro-joule UV-range (350-415 nm) femtosecond-laser pulses generated via frequency-doubled parametric conversion of 525-nm 150-fs pulses of Yb-glass laser were used for "hot" photoluminescence excitation in a diamond plate enriched by blue-emitting N3-centers (zero-phonon line, ZPL, at 415 nm). Photoluminescence spectra acquired in the range of 400-500 nm exhibited wavelength-independent well-resolved ZPL and phonon progression bands, where the involved phonons possessed the only energies of 0.09 eV (LA-phonons) and 0.15 eV (softened LO/TO-phonons), potentially, as a result of a Clemens decay mechanism. Photoluminescence yield in the ZPL and other phonon bands exhibited the power slope of 1.8 at lower energies and ≈1 at higher energies. The transition zone at fluence ∼1014-15 photons/cm2 was related to the saturation of the pumped resonance transition and the slower non-radiative vibrational relaxation to the ZPL-related excited electronic state and the nanosecond spontaneous photoluminescence transition to the ground state. As a result, the absorption cross section σ(370-390 nm) ≈1·10-15 cm2 and concentration [N3] ≈6·1014 cm-3 were determined along with the ZPL absorption cross section σ(415 nm) ≈2.5·10-15 cm2, and the non-radiative vibrational relaxation rate was estimated, providing altogether the crucial information on lasing possibilities in N3-doped diamonds.

Experimental and numerical studies on the thermal nonequilibrium behaviors of CO with Ar, He, and H2

The time-dependent rotational and vibrational temperatures were measured to study the shock-heated thermal nonequilibrium behaviors of CO with Ar, He, and H2 as collision partners. Three interference-free transition lines in the fundamental vibrational band of CO were applied to the fast, in situ, and state-specific measurements. Vibrational relaxation times of CO were summarized over a temperature range of 1110–2820 K behind reflected shocks. The measured rotational temperature instantaneously reached an equilibrium state behind shock waves. The measured vibrational temperature experienced a relaxation process before reaching the equilibrium state. The measured vibrational temperature time histories were compared with predictions based on the Landau–Teller model and the state-to-state approach. The state-to-state approach treats the vibrational energy levels of CO as pseudo-species and accurately describes the detailed thermal nonequilibrium processes behind shock waves. The datasets of state-specific inelastic rate coefficients of CO–Ar, CO–He, CO–CO, and CO–H2 collisions were calculated in this study using the mixed quantum-classical method and the semiclassical forced harmonic oscillator model. The predictions based on the state-to-state approach agreed well with the measured data and nonequilibrium (non-Boltzmann) vibrational distributions were found in the post-shock regions, while the Landau–Teller model predicted slower vibrational temperature time histories than the measured data. Modifications were applied to the Millikan–White vibrational relaxation data of the CO–Ar and CO–H2 systems to improve the performance of the Landau–Teller model. In addition, the thermal nonequilibrium processes behind incident shocks, the acceleration effects of H2O on the relaxation process of CO, and the characterization of vibrational temperature were highlighted.

Bending Relaxation of H2 O by Collision with Para- and Ortho-H2.

We extend our recent theoretical work on the bending relaxation of H2 O in collisions with H2 by including the three water modes of vibration coupled with rotation, as well as the rotation of H2 . Our full quantum close-coupling method (excluding the H2 vibration) is combined with a high-accuracy nine-dimensional potential energy surface. The collisions of para-H2 O and ortho-H2 O with the two spin modifications of H2 are considered and compared for several initial states of H2 O. The convergence of the results as a function of the size of the rotational basis set of the two colliders is discussed. In particular, near-resonant energy transfer between H2 O and H2 is found to control the vibrational relaxation process, with a dominant contribution of transitions with = , and being respectively the H2 initial and final rotational quantum numbers. Finally, the calculated value of the H2 O bending relaxation rate coefficient at 295 K is found to be in excellent agreement with its experimental estimate.

A priori tests of turbulence models for compressible flows

PurposeThe purpose of the paper is to analyse the performances of closures and compressibility corrections classically used in turbulence models when applied to highly-compressible turbulent boundary layers (TBLs) over flat plates.Design/methodology/approachA direct numerical simulation (DNS) database of TBLs, covering a wide range of thermodynamic conditions, is presented and exploited to perform a priori analyses of classical and recent closures for turbulent models. The results are systematically compared to the “exact” terms computed from DNS.FindingsThe few compressibility corrections available in the literature are not found to capture DNS data much better than the uncorrected original models, especially at the highest Mach numbers. Turbulent mass and heat fluxes are shown not to follow the classical gradient diffusion model, which was shown instead to provide acceptable results for modelling the vibrational turbulent heat flux.Originality/valueThe main originality of the present paper resides in the DNS database on which the a priori tests are conducted. The database contains some high-enthalpy simulations at large Mach numbers, allowing to test the performances of the turbulence models in the presence of both chemical dissociation and vibrational relaxation processes.

Mechanism of Ultraviolet-Induced CO Desorption from CO Ice: Role of Vibrational Relaxation Highlighted.

Although UV photon-induced CO ice desorption is clearly observed in many cold regions of the Universe as well as in the laboratory, the fundamental question of the mechanisms involved at the molecular scale remains debated. In particular, the exact nature of the involved energy transfers in the indirect desorption pathway highlighted in previous experiments is not explained. Using abinitio molecular dynamics simulations, we explore a new indirect desorption mechanism in which a highly vibrationally excited CO (v=40) within an aggregate of 50 CO molecules triggers the desorption of molecules at the surface. The desorption originates first from a mutual attraction between the excited molecule and the surrounding molecule(s), followed by a cascade of energy transfers, ultimately resulting in the desorption of vibrationally cold CO (∼95% in v=0). The theoretical vibrational distribution, along with the kinetic energy one, which peaks around 25meV for CO with low rotational levels (v=0, J<7), is in excellent agreement with the results obtained from VUV laser induced desorption (157nm) of CO (v=0, 1) probed using REMPI.

Determination of the Thickness of Interfacial Water by Time-Resolved Sum-Frequency Generation Vibrational Spectroscopy.

The physics and chemistry of a charged interface are governed by the structure of the electrical double layer (EDL). Determination of the interfacial water thickness (diw) of the charged interface is crucial to quantitatively describe the EDL structure, but it can be utilized with very scarce experimental methods. Here, we propose and verify that the vibrational relaxation time (T1) of the OH stretching mode at 3200 cm-1, obtained by time-resolved sum frequency generation vibrational spectroscopy with ssp polarizations, provides an effective tool to determine diw. By investigating the T1 values at the SiO2/NaCl solution interface, we established a time-space (T1-diw) relationship. We find that water has a T1 lifetime of ≥0.5 ps for diw ≤ 3 Å, while it displays bulk-like dynamics with T1 ≤ 0.2 ps for diw ≥ 9 Å. T1 decreases as diw increases from ∼3 Å to 9 Å. The hydration water at the DPPG lipid bilayer and LK15β protein interfaces has a thickness of ≥9 Å and shows a bulk-like feature. The time-space relationship will provide a novel tool to pattern the interfacial topography and heterogeneity in Ångstrom-depth resolution by imaging the T1 values.

Availability and reactivity of N2(v) for NH3 synthesis by plasma catalysis

Production of vibrationally excited N2 (N2(v)) in atmospheric pressure nonthermal plasma and loss of N2(v) by gas-phase reactions and reactions on catalytic surfaces are analyzed to examine the role of N2(v) in NH3 formation by plasma catalysis. Vibrational state-to-state kinetic models complemented with molecular beam mass spectrometry (MBMS) measurements demonstrate that N2(v> 0) is produced with densities 100× greater than the density of N radicals by a radiofrequency atmospheric pressure plasma jet. The experimentally measured loss of N2(v) corresponds with a state-to-state kinetic model that describes loss of N2(v) by surface-mediated vibrational relaxation without consideration of reactions that convert N2(v) to NH3 over the catalyst surface. Rate constants for vibrational relaxation of N2(v) on catalyst surfaces exceed upper bounds on proposed rate constants for NH3 formation reactions from N2(v) over Fe when v < 9, Ni when v < 18, and Ag when v < 39, which indicates that only higher vibrational levels can possibly contribute to catalytic NH3 formation faster than they undergo vibrational relaxation on the surface. Densities of N2(v> 8), vibrational levels that can possibly react over Fe to form NH3 faster than they undergo vibrational relaxation, are less than or similar to N densities at the inlet of the catalyst bed and measured NH3 formation for the investigated conditions in this work, while densities of N2(v> 17) and N2(v> 38) are orders of magnitude below the N density at the inlet of the catalyst bed and the measured NH3 formation. The loss of N2(v) by vibrational relaxation on the surface limits the ability of N2(v) to contribute to catalytic NH3 formation and explains why N2(v) does not produce NH3 in quantities that are comparable to NH3 formation from N even though N2(v > 0) is more abundantly produced by the plasma.

Vibrational Anharmonicity and Energy Relaxation in Nanoscale Acoustic Resonators.

The fundamental and n = 3 overtones of Au nanoplate thickness vibrations have been studied by transient absorption microscopy. The frequencies of the n = 3 overtone are less than 3× the frequency of the fundamental. This anharmonicity is explained through a continuum mechanics model that includes organic layers on top of the nanoplate and between the nanoplate and the glass substrate. In this model, anharmonicity arises from coupling between the vibrations of the nanoplate and the organic layers, which creates avoided crossings that reduce the overtone frequencies compared to the fundamental. Comparison of the experimental and calculated quality factors shows that coupling occurs to the top organic layer. Good agreement between the measured and calculated quality factors is obtained by introducing internal damping for the nanoplate. These results show that engineering layers of soft material around metal nanostructures can be used to control the vibrational lifetimes.