The intramolecular vibrational energy redistribution threshold in S(1) deuterated p-difluorobenzene

The intramolecular vibrational energy redistribution (IVR) in S(1) deuterated p-difluorobenzene (pDFB-d(4) or -d(4)) has been studied to determine the IVR threshold. For this, the S(1) <-- S(0) fluorescence excitation (FE) spectrum of jet-cooled d(4) was investigated in the 2000-3250 cm(-1) vibronic energy range of the S(1) electronic state, and single vibronic level fluorescence (SVLF) spectra have been acquired by exciting selected levels lying between 750 and 2850 cm(-1) in vibrational energy in the S(1) excited state. Congestion of the dispersed fluorescence in this molecule first appears as the vibrational level energy climbs above 2000 cm(-1). By comparing the SVLF spectra of pDFB-d(4) with those of p-difluorobenzene (pDFB or -h(4)), it is obvious that IVR threshold in -d(4) is localized with a few hundreds cm(-1) lower than that in pDFB. This decrease is entirely due to the increase in vibrational state density due to deuteration.     

Vibrational and rotational energy transfers involving the CH B 2Sigma(-) v=1 vibrational level in collisions with Ar, CO, and N2O

With photolysis-probe technique, we have studied vibrational and rotational energy transfers of CH involving the B (2)Sigma(-) (v=1, 0F(1) transitions are larger than the reverse F(1)-->F(2) transitions in DeltaN=0 for the Ar and CO collisions. The trend of fine-structure conservation is along the order of N(2)O相似文献   

Photoabsorption spectrum of radicals produced by a pulsed discharge of trace H2O in Ar

The absorption spectrum of radicals produced by a pulsed discharge of few mTorr H₂O in 3 Torr Ar has been measured in the 1200–1370 Å region. The radicals are mainly OH in low vibrational levels of the ground state. The observed spectrum is consistent with previous report that OH has a high absorption cross section in the 1223 Å region and a small one at 1216 Å. The spectrum is tentatively interpreted with the OH potential curves preliminarily calculated by van Dishoeck. Langhoff, Wetmore, and Dalgarno.     

Motional narrowing of the rotational spectrum of trifluoropropyne at 6550 cm(-1) by intramolecular vibrational energy redistribution

We present the basic principles of dynamic rotational spectroscopy for the highly vibrationally excited symmetric top molecule trifluoropropyne (TFP,CF3CCH). Single molecular eigenstate rotational spectra of TFP were recorded in the region of the first overtone of the nu(1) acetylenic stretching mode at 6550 cm(-1) by infrared-pulsed microwave-Fourier transform microwave triple resonance spectroscopy. The average rotational constant (B) of the highly vibrationally mixed quantum states at 6550 cm(-1) is 2909.33 MHz, a value that is 40 MHz larger than the rotational constant expected for the unperturbed C-H stretch overtone (2869.39 MHz). The average rotational constant and rotational line shape of the molecular eigenstate rotational spectra are compared to the distribution of rotational constants expected for the ensemble of normal-mode vibrational states at 6550 cm(-1) that can interact by intramolecular vibrational energy redistribution (IVR). The normal-mode population distribution at 6550 cm(-1) can be described using a Boltzmann distribution with a microcanonical temperature of 1200 K. At this energy the rotational constant distribution in the normal-mode basis set is peaked at about 2910 MHz with a width of about 230 MHz. The distribution is slightly asymmetric with a tail to the high end. The experimentally measured dynamic rotational spectra are centered at the normal-mode distribution peak; however, the spectral width is significantly narrower (40 MHz) than normal-mode ensemble width (230 MHz). This reduction of the width, along with the Lorentzian shape of the eigenstate rotational spectra when compared to the Gaussian shape of the calculated ensemble distribution, illustrates the narrowing of the spectrum due to IVR exchange. The IVR exchange rate was determined to be 120 ps, about ten times faster than the rate at which energy is redistributed from the v=2 level of the acetylenic stretch.     

Molecular dynamics simulations and instantaneous normal-mode analysis of the vibrational relaxation of the C-H stretching modes of N-methylacetamide-d in liquid deuterated water

Nonequilibrium molecular dynamics (MD) simulations and instantaneous normal mode (INMs) analyses are used to study the vibrational relaxation of the C-H stretching modes (ν(s)(CH?)) of deuterated N-methylacetamide (NMAD) in aqueous (D2O) solution. The INMs are identified unequivocally in terms of the equilibrium normal modes (ENMs), or groups of them, using a restricted version of the recently proposed Min-Cost assignment method. After excitation of the parent ν(s)(CH?) modes with one vibrational quantum, the vibrational energy is shown to dissipate through both intramolecular vibrational redistribution (IVR) and intermolecular vibrational energy transfer (VET). The decay of the vibrational energy of the ν(s)(CH?) modes is well fitted to a triple exponential function, with each characterizing a well-defined stage of the entire relaxation process. The first, and major, relaxation stage corresponds to a coherent ultrashort (τ(rel) = 0.07 ps) energy transfer from the parent ν(s)(CH?) modes to the methyl bending modes δ(CH?), so that the initially excited state rapidly evolves into a mixed stretch-bend state. In the second stage, characterized by a time of 0.92 ps, the vibrational energy flows through IVR to a number of mid-range-energy vibrations of the solute. In the third stage, the vibrational energy accumulated in the excited modes dissipates into the bath through an indirect VET process mediated by lower-energy modes, on a time scale of 10.6 ps. All the specific relaxation channels participating in the whole relaxation process are properly identified. The results from the simulations are finally compared with the recent experimental measurements of the ν(s)(CH?) vibrational energy relaxation in NMAD/D?O(l) reported by Dlott et al. (J. Phys. Chem. A 2009, 113, 75.) using ultrafast infrared-Raman spectroscopy.     

Determination of the rate constant for the OH(X2Pi) + OH(X()Pi) --> O(3P) + H2O reaction over the temperature range 293-373 K

The rate constant for the reaction OH(X2Pi) + OH(X2Pi) --> O(3P) + H2O has been measured over the temperature range 293-373 K and pressure range 2.6-7.8 Torr in both Ne and Ar bath gases. The OH radical was created by 193 nm laser photolysis of N2O to produce O(1D) atoms that reacted rapidly with H2O to produce the OH radical. The OH radical was detected by quantitative time-resolved near-infrared absorption spectroscopy using Lambda-doublet resolved rotational transitions of the first overtone of OH(2,0) near 1.47 microm. The temporal concentration profiles of OH were simulated using a kinetic model, and rate constants were determined by minimizing the sum of the squares of residuals between the experimental profiles and the model calculations. At 293 K the rate constant for the title reaction was found to be (2.7 +/- 0.9) x 10(-12) cm(3) molecule(-1) s(-1), where the uncertainty includes an estimate of both random and systematic errors at the 95% confidence level. The rate constant was measured at 347 and 373 K and found to decrease with increasing temperature.     

Picosecond IR-UV pump-probe spectroscopic study on the vibrational energy flow in isolated molecules and clusters

Intramolecular vibrational energy redistribution (IVR) and vibrational predissociation (VP) from the XH stretching vibrations, where X refers to O or C atom, of aromatic molecules and their hydrogen(H)-bonded clusters are investigated by picosecond time-resolved IR-UV pump probe spectroscopy in a supersonic beam. For bare molecules, we mainly focus on IVR of the OH stretch of phenol. We describe the IVR of the OH stretch by a two-step tier model and examine the effect of the anharmonic coupling strength and the density of states on IVR rate and mechanism by using isotope substitution. In the H-bonded clusters of phenol, we show that the relaxation of the OH stretching vibration can be described by a stepwise process and then discuss which process is sensitive to the H-bonding strength. We discuss the difference/similarity of IVR/VP between the "donor" and the "acceptor" sites in phenol-ethylene cluster by exciting the CH stretch vibrations. Finally, we study the vibrational energy transfer in the isolated molecules having the alkyl chain, namely phenylalcanol (PA). In this system, we measure the rate constant of the vibrational energy transfer between the OH stretch and the vibrations of benzene ring which are connected at the both ends of the alkyl chain. This energy transfer can be called "through-bond IVR". We investigate the three factors which are thought to control the energy transfer rate; (1) "OH <--> next CH(2)" coupling, (2) chain length and (3) conformation. We discuss the energy transfer mechanism in PAs by examining these factors.     

Vibrational relaxation of CN stretch of pseudo-halide anions (OCN-, SCN-, and SeCN-) in polar solvents

The vibrational relaxation dynamics of pseudo-halide anions XCN- (X = O, S, Se) in polar solvents were studied to understand the effect of charge on solute-to-solvent intermolecular energy transfer (IET) and solvent assisted intramolecular vibrational relaxation (IVR) pathways. The T1 relaxation times of the CN stretch in these anions were measured by IR pump/IR probe spectroscopy, in which the 0-1 transition was excited, and the 0-1 and 1-2 transitions were monitored to follow the recovery of the ground state and decay of the excited state. For these anions in five solvents, H2O, D2O, CH3OH, CH3CN, and (CH3)2SO, relaxation rates followed the trend of OCN- > SCN- > SeCN-. For these anions and isotopes of SCN-, the relaxation rate was a factor of a few (2.5-10) higher in H2O than in D2O. To further probe the solvent isotope effect, the relaxation rates of S12C14N-, S13C14N-, and S12C15N- in deuterated methanols (CH3OH, CH3OD, CH3OH, CD3OD) were compared. Relaxation rate was found to be affected by the change of solvent vibrational band at the CN- stretching mode (CD3 symmetric stretch) and lower frequency regions, suggesting the presence of both direct IET and solvent assisted IVR relaxation pathways. The possible relaxation pathways and mechanisms for the observed trends in solute and solvent dependence were discussed.     

Absolute rate coefficient of the OH + CH(3)C(O)OH reaction at T = 287-802 K. The two faces of pre-reactive H-bonding

The rate constants for the reaction OH + CH3C(O)OH --> products (1) were determined over the temperature range 287-802 K at 50 and 100 Torr of Ar or N2 bath gas using pulsed laser photolysis generation of OH by CH3C(O)OH photolysis at 193 nm coupled with OH detection by pulsed laser-induced fluorescence. The rate coefficient displays a complex temperature dependence with a sharp minimum at 530 K, indicating the competition between a reaction proceeding through a pre-reactive H-bonded complex to form CH3C(O)O + H2O, expected to prevail at low temperatures, and a direct methyl-H abstraction channel leading to CH2C(O)OH + H2O, which should dominate at high temperatures. The temperature dependence of the rate constant can be described adequately by k1(287-802 K) = 2.9 x 10(-9) exp{-6030 K/T} + 1.50 x 10(-13) exp{515 K/T} cm3 molecule(-1)(s-1), with a value of (8.5 +/- 0.9) x 10-13 cm3 molecule(-1)(s-1) at 298 K. The steep increase in rate constant in the range 550-800 K, which is reported for the first time, implies that direct abstraction of a methyl-H becomes the dominant pathway at temperatures greater than 550 K. However, the data indicates that up to about 800 K direct methyl-H abstraction remains adversely affected by the long-range H-bonding attraction between the approaching OH radical and the carboxyl -C(O)OH functionality.     

Thermal decomposition of ethanol. 4. Ab initio chemical kinetics for reactions of H atoms with CH3CH2O and CH3CHOH radicals

The potential energy surfaces of H-atom reactions with CH(3)CH(2)O and CH(3)CHOH, two major radicals in the decomposition and oxidation of ethanol, have been studied at the CCSD(T)/6-311+G(3df,2p) level of theory with geometric optimization carried out at the BH&HLYP/6-311+G(3df,2p) level. The direct hydrogen abstraction channels and the indirect association/decomposition channels from the chemically activated ethanol molecule have been considered for both reactions. The rate constants for both reactions have been calculated at 100-3000 K and 10(-4) Torr to 10(3) atm Ar pressure by microcanonical VTST/RRKM theory with master equation solution for all accessible product channels. The results show that the major product channel of the CH(3)CH(2)O + H reaction is CH(3) + CH(2)OH under atmospheric pressure conditions. Only at high pressure and low temperature, the rate constant for CH(3)CH(2)OH formation by collisonal deactivation becomes dominant. For CH(3)CHOH + H, there are three major product channels; at high temperatures, CH(3)+CH(2)OH production predominates at low pressures (P < 100 Torr), while the formation of CH(3)CH(2)OH by collisional deactivation becomes competitive at high pressures and low temperatures (T < 500 K). At high temperatures, the direct hydrogen abstraction reaction producing CH(2)CHOH + H(2) becomes dominant. Rate constants for all accessible product channels in both systems have been predicted and tabulated for modeling applications. The predicted value for CH(3)CHOH + H at 295 K and 1 Torr pressure agrees closely with available experimental data. For practical modeling applications, the rate constants for the thermal unimolecular decomposition of ethanol giving key accessible products have been predicted; those for the two major product channels taking place by dehydration and C-C breaking agree closely with available literature data.     

Quantum-mechanical calculations on pressure and temperature dependence of three-body recombination reactions: application to ozone formation rates

A quantum-mechanical model is designed for the calculation of termolecular association reaction rate coefficients in the low-pressure fall-off regime. The dynamics is set up within the energy transfer mechanism and the kinetic scheme is the steady-state approximation. We applied this model to the formation of ozone O + O2 + M --> O3 + M for M = Ar, making use of semiquantitative potential energy surfaces. The stabilization process is treated by means of the vibrational close-coupling infinite order sudden scattering theory. Major approximations include the neglect of the O3 vibrational bending mode and rovibrational couplings. We calculated individual isotope-specific rate constants and rate constant ratios over the temperature range 10-1000 K and the pressure fall-off region 10(-7)-10(2) bar. The present results show a qualitative and semiquantitative agreement with available experiments, particularly in the temperature region of atmospheric interest.     

Vibronic structure in the S1-S0 transition of jet-cooled dibenzofuran

Fluorescence excitation spectra of dibenzofuran in a supersonic jet are observed and the vibronic structure is analyzed for the S(1) (1)A(1) (pipi) and S(0) states. An observation of the rotational envelopes reveals that the band is a B-type band. However, it is shown that most of the strong vibronic bands are A-type bands. The intensity arises from vibronic coupling with the S(2) (1)B(2) state. We find a broad emission in the dispersed fluorescence spectrum for the excitation of the high vibrational levels in the S(1) state. This indicates that intramolecular vibrational redistribution (IVR) occurs efficiently in the isolated dibenzofuran molecule.     

Intramolecular vibrational redistribution in the vibrational predissociation dynamics of He-I2

The intramolecular vibrational redistribution (IVR) process is investigated in wave packet simulations of the vibrational predissociation dynamics of He-I(2)(B,upsilon') in the region of high upsilon' levels, upsilon' = 35-65. The simulations indicate that for upsilon' < or = 45 the dynamics is dominated by direct predissociation, whereas for higher upsilon' levels the onset of IVR appears and becomes increasingly important. The IVR process occurs via coupling of the initial state in the upsilon' manifold to intermediate long-lived resonances belonging to the lower upsilon < upsilon' vibrational manifolds. The IVR dynamics manifests itself in multiexponential behavior and oscillations in the time-dependent population curves associated with the He-I(2)(B,upsilon') initial state, the He-I(2)(B,upsilon < upsilon') intermediate complexes, and the final product states. The population curves corresponding to the upsilon'- 1 intermediate resonances located below the He + I(2)(B,upsilon'-1,j=0) dissociation limit are analyzed. It is found that initial population is transferred to all the intermediate resonance states considered, including those more separated in energy from the initial one. The results obtained for population transfer between the initial and the intermediate states can be explained by the intensity of the matrix elements coupling the initial and the intermediate resonances, in combination with the Rabi's formula for population exchange between two coupled states.     

An application of error reduction and harmonic inversion schemes to the semiclassical calculation of molecular vibrational energy levels

A singular value decomposition based harmonic inversion signal processing scheme is applied to the semiclassical initial value representation (IVR) calculation of molecular vibrational states. Relative to usual IVR procedure of Fourier analysis of a signal made from the Monte Carlo evaluation of the phase space integral in which many trajectories are needed, the new procedure obtains acceptable results with many fewer trajectories. Calculations are carried out for vibrational energy levels of H2O to illustrate the overall procedure.     

Quasi-classical trajectory simulations of intramolecular vibrational energy redistribution in HONO2 and DONO2

By use of an analytic potential energy surface developed in this work for nitric acid, the quasi-classical trajectory method was used to simulate intramolecular vibrational energy redistribution (IVR). A method was developed for monitoring the average vibrational energy in the OH (or OD) mode that uses the mean-square displacement of the bond length calculated during the trajectories. This method is effective for both rotating and nonrotating molecules. The calculated IVR time constant for HONO(2) decreases exponentially with increasing excitation energy, is almost independent of rotational temperature, and is in excellent agreement with the experimental determination (Bingemann, D.; Gorman, M. P.; King, A. M.; Crim, F. F. J. Chem.Phys. 1997, 107, 661). In DONO(2), the IVR time constants show more complicated behavior with increasing excitation energy, apparently due to 2:1 Fermi-resonance coupling with lower frequency modes. This effect should be measurable in experiments.     

Intramolecular vibrational energy redistribution in bridged azulene-anthracene compounds: ballistic energy transport through molecular chains

Intramolecular vibrational energy flow in excited bridged azulene-anthracene compounds is investigated by time-resolved pump-probe laser spectroscopy. The bridges consist of molecular chains and are of the type (CH(2))(m) with m up to 6 as well as (CH(2)OCH(2))(n) (n=1,2) and CH(2)SCH(2). After light absorption into the azulene S(1) band and subsequent fast internal conversion, excited molecules are formed where the vibrational energy is localized at the azulene side. The vibrational energy transfer through the molecular bridge to the anthracene side and, finally, to the surrounding medium is followed by probing the red edge of the azulene S(3) absorption band at 300 nm and/or the anthracene S(1) absorption band at 400 nm. In order to separate the time scales for intramolecular and intermolecular energy transfer, most of the experiments were performed in supercritical xenon where vibrational energy transfer to the bath is comparably slow. The intramolecular equilibration proceeds in two steps. About 15%-20% of the excitation energy leaves the azulene side within a short period of 300 fs. This component accompanies the intramolecular vibrational energy redistribution (IVR) within the azulene chromophore and it is caused by dephasing of normal modes contributing to the initial local excitation of the azulene side and extending over large parts of the molecule. Later, IVR in the whole molecule takes place transferring vibrational energy from the azulene through the bridge to the anthracene side and thereby leading to microcanonical equilibrium. The corresponding time constants tau(IVR) for short bridges increase with the chain length. For longer bridges consisting of more than three elements, however, tau(IVR) is constant at around 4-5 ps. Comparison with molecular dynamics simulations suggests that the coupling of these chains to the two chromophores limits the rate of intramolecular vibrational energy transfer. Inside the bridges the energy transport is essentially ballistic and, therefore, tau(IVR) is independent on the length.     

Argon cluster-mediated isolation and vibrational spectra of peroxy and nominally D(3h) isomers of CO3(-) and NO3(-)

Vibrational predissociation spectra are reported for two isomeric forms of the gas-phase ions, CO(3)(-) and NO(3)(-). The peroxy forms, (OOCO(-) and OONO(-)) were isolated using an Ar-mediated synthetic scheme involving exchange of CO and NO for the more weakly bound Ar ligands in O(2)(-)Ar(m) clusters, while the forms based on a central heteroatom (CO(3)(-) and NO(3)(-)) were generated by electron impact on CO(2) and HNO(3) vapor. The simple two-band spectrum of OOCO(-) indicates that it is best described as the O(2)(-) x CO ion-molecule complex, whereas the covalently bound CO(3)(-) form yields a much more complicated vibrational spectrum with bands extending out to 4000 cm(-1). In contrast, the NO(3)(-) ion yields a simple spectrum with only one transition as expected for the antisymmetric NO stretching fundamental of a species with D(3h) structure. The spectrum of the peroxynitrite isomer, OONO(-), displays intermediate complexity that can be largely understood in the context of fundamentals associated with its cis and trans structures previously characterized in an Ar matrix.     

A gas-phase kinetic study of the reaction between bromine monoxide and methylperoxy radicals at atmospheric temperatures

The rate constant of the reaction of BrO with CH(3)O(2) was determined to be k1 = (6.2 +/- 2.5) x 10(-12) cm3 molecule(-1) s(-1) at 298 K and 100-200 Torr of O2 diluent. Quoted uncertainty was two standard deviations. No significant pressure dependence of the rate constants was observed at 100-200 Torr total pressure of N2 or O2 diluents. Temperature dependence of the rate constants was further investigated over the range 233-333 K, and an Arrhenius type expression was obtained for k1 = 4.6 x 10(-13) exp[(798 +/- 76)/T] cm3 molecule(-1) s(-1). The product branching ratios were evaluated and the atmospheric implications were discussed.     

Quasiclassical trajectory simulations of OH(v) + NO2 --> HONO2* --> OH(v') + NO2: capture and vibrational deactivation rate constants

Quasiclassical trajectory calculations are used to investigate the dynamics of the OH(v) + NO(2) --> HONO(2) --> OH(v') + NO(2) recombination/dissociation reaction on an analytic potential energy surface (PES) that gives good agreement with the known structure and vibrational frequencies of nitric acid. The calculated recombination rate constants depend only weakly on temperature and on the initial vibrational energy level of OH(v). The magnitude of the recombination rate constant is sensitive to the potential function describing the newly formed bond and to the switching functions in the PES that attenuate inter-mode interactions at long range. The lifetime of the nascent excited HONO(2) depends strongly not only on its internal energy but also on the identity of the initial state, in disagreement with statistical theory. This disagreement is probably due to the effects of slow intramolecular vibrational energy redistribution (IVR) from the initially excited OH stretching mode. The vibrational energy distribution of product OH(v') radicals is different from statistical distributions, a result consistent with the effects of slow IVR. Nonetheless, the trajectory results predict that vibrational deactivation of OH(v) via the HONO(2) transient complex is approximately 90% efficient, almost independent of initial OH(v) vibrational level, in qualitative agreement with recent experiments. Tests are also carried out using the HONO(2) PES, but assuming the weaker O-O bond strength found in HOONO (peroxynitrous acid). In this case, the predicted vibrational deactivation efficiencies are significantly lower and depend strongly on the initial vibrational state of OH(v), in disagreement with experiments. This disagreement suggests that the actual HOONO PES may contain more inter-mode coupling than found in the present model PES, which is based on HONO(2). For nitric acid, the measured vibrational deactivation rate constant is a useful proxy for the recombination rate, but IVR randomization of energy is not complete, suggesting that the efficacy of the proxy method must be evaluated on a case-by-case basis.     

Relaxation of H2O from its /04>- vibrational state in collisions with H2O, Ar, H2, N2, and O2

We report rate coefficients at 293 K for the collisional relaxation of H2O molecules from the highly excited /04>(+/-) vibrational states in collisions with H2O, Ar, H2, N2, and O2. In our experiments, the mid R:04(-) state is populated by direct absorption of radiation from a pulsed dye laser tuned to approximately 719 nm. Evolution of the population in the (/04>(+/-)) levels is observed using the combination of a frequency-quadrupled Nd:YAG laser, which selectively photolyses H2O(/04>(+/-)), and a frequency-doubled dye laser, which observes the OH(v=0) produced by photodissociation via laser-induced fluorescence. The delay between the pulse from the pump laser and those from the photolysis and probe lasers was systematically varied to generate kinetic decays. The rate coefficients for relaxation of H2O(/04>(+/-)) obtained from these experiments, in units of cm3 molecule(-1) s(-1), are: k(H2O)=(4.1+/-1.2) x 10(-10), k(Ar)=(4.9+/-1.1) x 10(-12), k(H2)=(6.8+/-1.1) x 10(-12), k(N2)=(7.7+/-1.5) x 10(-12), k(O2)=(6.7+/-1.4) x 10(-12). The implications of these results for our previous reports of rate constants for the removal of H2O molecules in selected vibrational states by collisions with H atoms (P. W. Barnes et al., Faraday Discuss. Chem. Soc. 113, 167 (1999) and P. W. Barnes et al., J. Chem. Phys. 115, 4586 (2001).) are fully discussed.