Rotational State Distributions Research Articles

Direct MP2 molecular dynamics studies of H atom reaction with CD4 and CH4

The mechanism and dynamics of the H + CD(4) -> CD(3) + HD (I) and H + CH(4) -> CH(3) + H(2) (II) reactions have been investigated by electronic structure methods. The minimum-energy path and vibrational frequencies along the intrinsic reaction coordinate are calculated at MP2/cc-pVDZ level. Energy distributions of the products are also obtained by the direct classical trajectory calculations at the MP2/cc-pVDZ level. It is found that most of the available energy appears as product translational energy, and very little of the available energy is partitioned into internal excitation of the HD (H(2)) product for reaction I (II), which is in agreement with the experimental evidence. The results indicate that the experimental results could be reproduced by the direct MP2 molecular dynamics calculations. The rotational state distributions of the products show the HD (H(2)) products are formed with lower rotational quantum numbers than the CD(3) (CH(3)) products. (C) 2011 Wiley Periodicals, Inc. Int J Quantum Chem 111: 4433-4442, 2011

Non-reactive scattering of N2 from the W(110) surface studied with different exchange–correlation functionals

The non-reactive scattering of N(2) from the W(110) surface is studied with six dimensional (6D) classical dynamics and two distinct potential energy surfaces (PES). Here, we use the PESs calculated with density functional theory and two different exchange-correlation functionals, the PW91 [J. E. Perdew et al., Phys. Rev. B, 1992, 46, 6671] and the RPBE [B. Hammer et al., Phys. Rev. B, 1999, 59, 7413]. By analyzing the final rotational state and angular distributions, we extract information on the characteristics of the two PESs in the 6D configurational space. Comparison of the theoretical results with the available experimental data provides detailed information on the validity of each functional. In general, the PW91 PES is more corrugated than the RPBE one in all the configurational space, meaning that there is a stronger dependence of the potential energy on the molecular orientation and position over the surface unit cell. Furthermore, we find that the larger corrugation and the less repulsive character exhibited by the PW91 PES seems to be realistic at distances above the chemisorption well. In contrast, the less corrugated RPBE PES performs better in the region below the chemisorption well.

Coriolis coupling effects in the dynamics of deep well reactions: application to the H+ + D2 reaction

We present exact and estimated quantum differential and integral cross sections as well as product state distributions for the title reaction. We employ a time-dependent wavepacket method including all Coriolis couplings and also an adapted code where the helicity quantum number and with this the Coriolis couplings have been truncated. Results from helicity truncated as well as helicity conserving (HC) calculation are presented. The HC calculations fail to reproduce the exact results due to the influence of the centrifugal barrier. While the truncated calculation overestimate the exact integral cross sections they reproduce the features of the integral cross section very well. We also find that the product rotational state distributions are well reproduced if the maximum helicity state is chosen carefully. The helicity truncated calculations fail to give a good approximation of differential cross sections.

Coherent Correlation between Nonadiabatic Rotational Excitation and Angle-Dependent Ionization of NO in Intense Laser Fields

We investigate coherent correlation between nonadiabatic rotational excitation and angle-dependent ionization of NO in intense laser fields in the state-resolved manner. When neutral NO molecules are partly ionized in intense laser fields (I(0) > 35 TW/cm(2)), a hole in the rotational wave packet of the remaining neutral NO is created because of the ionization rate depending on the alignment angle of the molecular axis with respect to the laser polarization direction. Rotational state distributions of NO are experimentally observed, and then the characteristic feature that the population at higher J levels is increased by the ionization can be identified. Numerical calculation for solving time-dependent rotational Schrödinger equations including the effect of the ionization is carried out. The numerical results suggest that NO molecules aligned perpendicular to the laser polarization direction are dominantly ionized at the peak intensity of I(0) = 42 TW/cm(2), where the multiphoton ionization is preferred rather than the tunneling ionization.

Imaging the State-Specific Vibrational Predissociation of the Hydrogen Chloride−Water Hydrogen-Bonded Dimer

The state-to-state vibrational predissociation dynamics of the hydrogen-bonded HCl-H(2)O dimer were studied following excitation of the HCl stretch of the dimer. Velocity-map imaging and resonance-enhanced multiphoton ionization (REMPI) were used to determine pair-correlated product energy distributions. Following vibrational excitation of the HCl stretch of the dimer, HCl fragments were detected by 2 + 1 REMPI via the f (3)Delta(2) <-- X (1)Sigma(+) and V (1)Sigma(+) <-- X (1)Sigma(+) transitions. REMPI spectra clearly show HCl from dissociation produced in the ground vibrational state with J'' up to 11. The fragments' center-of-mass translational energy distributions were determined from images of selected rotational states of HCl and were converted to rotational state distributions of the water cofragment. All the distributions could be fit well when using a dimer dissociation energy of D(0) = 1334 +/- 10 cm(-1). The rotational distributions in the water cofragment pair-correlated with specific rotational states of HCl appear nonstatistical when compared to predictions of the statistical phase space theory. A detailed analysis of pair-correlated state distributions was complicated by the large number of water rotational states available, but the data show that the water rotational populations increase with decreasing translational energy.

Rotational and Vibrational State Distributions of CsH and Relative Reactivity in Reactions of Cs(62D, 72D) with H2

By using a pump-probe technique, the nascent rotational and vibrational state distributions of CsH are obtained in the Cs(62D,72D) plus H2 reaction. The nascent CsH molecules are found to populate the lowest two vibrational (ν″ = 0 and 1) levels of the ground electronic state. By comparing the spectral intensities of the CsH action spectra with those of pertinent Cs atomic fluorescence excitation spectra, the relative reactivity with H2 is in an order of 62D3/2 > 62D5/2 > 72D3/2 > 72D5/2. The rotational temperatures are found to be slightly below the cell temperature. The relative fractions (⟨fV⟩, ⟨fR⟩, ⟨fT⟩) of average energy disposal are derived as (0.2,0.12,0.68), (0.2,0.12,0.68), (0.07,0.04,0.89) and (0.07,0.04,0.89) for the 62D3/2, 62D5/2, 72D3/2 and 72D5/2, respectively. The major available energy is released as translation. These results support that the reaction mechanism of Cs(62D,72D) plus H2 is primarily a collinear abstraction and not an insertion.

Quasi-classical trajectory study of the CD/CH product branching ratios for the C( 1D) + HD reaction

Quasi-classical trajectory (QCT) calculation of the integral cross-sections and the CD/CH product branching ratios as a function of collision energy for the C( 1D) + HD ( v, j) reaction have been performed on an ab initio potential energy surface (Bussery-Honvault et al. (2001) [8]). Our QCT calculations show that the integral cross-sections and the CD/CH product branching ratios strongly depend on the initial rotation quantum number j and the vibrational quantum number v. The integral cross-sections decrease with the increment of the collision energy. The product vibrational and rotational state distributions are also presented. The calculated results are in general good agreement with experimental data and some previous theoretical results.

Can the Fragmentation of Hydrogen-Bonded Dimers Be Predicted: Predissociation of C2H2−HX

HX rotational state distributions following vibrational predissociation (VP) of C(2)H(2)-HX (X = Cl, F, O) dimers are predicted by expressing the predissociation process as the joint probability of rovibrational excitation in the fragments following "internal collision" in the vibrationally excited dimer. Calculations of these joint probabilities for the T-shaped dimers of acetylene with HCl, DCl, HF, and OH using the angular momentum (AM) method reproduce experimental distributions with reasonable accuracy. In dimers of this complex, many different pathways for the disposal of initial energy and momentum exist in principle. The use of simple physical arguments based on (a) the direction of initial impulse upon excitation and (b) restricted relative geometries due to limited amplitude of relative motion of the dimer components allows the number of effective dissociation pathways to be much reduced. For these, the probability of rotational and rovibrational transfer into the fragments is calculated, a process that generally involves summing over a number of C(2)H(2) rovibrational states for each value of j(HX). In calculating relative rotational populations in the fragments, it was found essential to first calculate the threshold value of available energy for that transition and the threshold value of b(n), the effective impact parameter. Without these modifications, channels of lowest j(HX) and/or j(C(2)H(2)) dominate, which generally is not found experimentally. The need for these modifications is attributed to energy conservation in the dissociation and the limited range of relative orientations that the dimer pair can explore. The AM method is able to predict the very different fragment rotational excitations in this series of dimers fairly well using only readily available data. In addition, a number of new insights into the physical principles that control the dissociation of molecule-molecule dimers have emerged and are discussed. The results suggest that each fragment quantum state pair results from a very specific relative geometry of dissociation and that the balance between vibrational and rotational excitations is determined by the requirement to restrict the angular momentum "load" in the predissociation.

Kinematic Slowing and Electrostatic Guiding of KBr Molecules Formed by the Reactive Collision Process: K + HBr → KBr + H

We have generated a beam of translationally cold KBr molecules formed by exoergic reactive collisions in counterpropagating beams of K atoms and HBr molecules. The method relies on the extreme mass ratio of the products and the proper choice of the beam velocities (Liu, N.-N.; Loesch, H. J. Phys. Rev. Lett. 2007, 98, 10300). Here, we report the results of experiments on guiding the slow molecules from the site of their creation to the detector by a linear electrostatic quadrupole field. The device enhances the total intensity by a factor of 2.3 and the intensity at 14.2 m/s (1.4K) by an order of magnitude. The density velocity distributions, deduced directly from the observed time-of-flight profiles, peak at 20 m/s (2.9K). A numerical simulation of the guiding efficiency indicates that the polarization of the nascent molecules is first altered by a sudden change of the quantization axis from parallel to the initial relative velocity to parallel to the fringing field and thereafter follows adiabatically the local field as quantization axis. Drastic differences between the velocity and rotational state distributions of the molecules entering and leaving the energized quadrupole field are predicted. The counterpropagating beams can be used to continuously load an electrostatic trap. The equilibrium density of confined molecules is estimated to 1 x 10(7) cm(-3).

Detection of OH Radical in the Photodissociation ofp-Aminobenzoic Acid at 266 nm

Photodissociation of p-aminobenzoic acid at 266 nm was investigated by probing the nascent OH photoproduct employing the laser-induced fluorescence technique. It was found that the nascent OH radical was vibrationally cold and its rotational state distribution conformed to be a Boltzmann behavior, characterized by a rotational temperature of 1040 110 K. The rotational energy of OH was determined to be 8.78 0.84 kJ/mol. Between the two spin-orbit states of OH, 23/2 and 21/2, the former was found to be preferentially populated. The distribution of the (A) state for the -doublet was dominant. Finally, a probable mechanism for the formation of OH produced from the photodissociation of p-aminobenzoic acid is discussed.

Ultraviolet photodissociation of H3+

As a step towards in situ probing of the rotational-state distribution of H3+ ions in a stored beam, we have realized their photodissociation in a storage ring by a parallel ultraviolet laser beam. The decay of the photodissociation signal of H3+ for 4.9 eV photons into the channel H+2 + H was identified and showed a time constant of about 2 ms, typical for vibrational levels of H3+ over a wide range of binding energies. The photodissociation products of H3+ at this photon energy were further investigated for a single pass ion beam by kinetic energy release and charge-exchange measurements.

Imaging the State-Specific Vibrational Predissociation of the Ammonia−Water Hydrogen-Bonded Dimer

The state-to-state vibrational predissociation (VP) dynamics of the hydrogen-bonded ammonia-water dimer were studied following excitation of the bound OH stretch. Velocity-map imaging (VMI) and resonance-enhanced multiphoton ionization (REMPI) were used to determine pair-correlated product energy distributions. Following vibrational excitation of the bound OH stretch fundamental, ammonia fragments were detected by 2 + 1 REMPI via the B1E" <-- X1A1' transition. The REMPI spectra show that NH3 is produced with one and two quanta of the symmetric bend (nu2 umbrella mode) excitation, as well as in the ground vibrational state. Each band is quite congested, indicating population in a large number of rotational states. The fragments' center-of-mass (c.m.) translational energy distributions were determined from images of selected rotational levels of ammonia with zero, one, or two quanta in nu2 and were converted to rotational state distributions of the water cofragment. All the distributions could be fit well by using a dimer dissociation energy of D0 = 1538 +/- 10 cm(-1). The rotational state distributions in the water cofragment pair-correlated with specific rovibrational states of ammonia are broad and include all the J(KaKc) states allowed by energy conservation. The rotational populations increase with decreasing c.m. translational energy. There is no evidence for ammonia products with significant excitation of the asymmetric bend (nu4) or water products with bend (nu2) excitation. The results show that only restricted pathways lead to predissociation, and these do not always give rise to the smallest possible translational energy release, as favored by momentum gap models.

Chirped pulse multiphoton ionization of nitrogen: Control of selective rotational excitation in N2+(B Σ2u+)

We report on fluorescence spectra of N(2)(+)(B (2)Sigma(u)(+)) --> N(2)(+)(X (2)Sigma(g)(+)) obtained from multiphoton ionization of molecular nitrogen by 804 nm femtosecond laser pulses. The analysis of the fluorescence spectra reveals that the vibrational levels v = 0 and v = 4 in the B (2)Sigma(u)(+)-state of N(2)(+) are primarily populated. The rotational state distribution of N(2)(+)(B (2)Sigma(u)(+), v = 0) is determined from the rotationally resolved fluorescence spectra. It is demonstrated that the linear chirp of the 804 nm femtosecond laser pulse has a strong influence on the rotational state distribution of the vibrational ground state of the molecular cation N(2)(+)(B (2)Sigma(u)(+), v = 0). Possible mechanisms leading to the experimental results are discussed. The particular population of the vibrational levels as well as the linear chirp dependence of the fluorescence signal gives evidence for the importance of a resonant intermediate state. The N(2) a (1)Pi-state is likely involved in a resonant multiphoton excitation process. This permits to selectively control the rotational population of the cation that is formed via chirped pulse multiphoton ionization.

OH produced from o-nitrophenol photolysis: A combined experimental and theoretical investigation

Photodissociation dynamics of o-nitrophenol in the gas phase at different photolysis wavelengths (361-390 nm) is investigated, and the nascent OH radical is observed by the single-photon laser-induced fluorescence technique. At all the photolysis wavelengths, the OH radicals are formed in vibrationally cold state (upsilon(")=0) and have similar rotational state distributions. The average rotational temperature for all the photolysis wavelengths is approximately 970+/-120 K, corresponding to a rotational energy of 1.9+/-0.2 kcal mol(-1). The spin orbit and Lambda-doublet states of the OH fragments formed in the dissociation are measured to have nonstatistical distributions. To get an insight into the dissociative mechanism leading to OH formation in the photolysis of o-nitrophenol, the potential energy surfaces of the OH-forming channels are mapped by ab initio theoretical calculations. According to both experimental and theoretical results, a possible mechanism for OH formation is proposed.

Information-theoretic analysis of rotational distributions from quantal and quasiclassical computations of reactive and nonreactive scattering

An information-theoretic approach to the analysis of rotational excitation cross sections was developed by Levine, Bernstein, Johnson, Procaccia, and coworkers and applied to state-to-state cross sections available from numerical computations of reactive and nonreactive scattering (for example, by Wyatt and Kuppermann and their coworkers and by Pack and Pattengill and others). The rotational surprisals are approximately linear in the energy transferred, thereby accounting for the so-called “exponential gap law” for rotational relaxation discovered experimentally by Polanyi, Woodall, and Ding. For the “linear surprisal” case the unique relation between the surprisal parameter θR and the first moment of the rotational energy distribution provides a link between the pattern of the rotational state distribution and those features of the potential surface which govern the average energy transfer.

Photolysis of o‐Nitrobenzaldehyde in the Gas Phase: A New OH. Formation Channel

Photolysis of gaseous o-nitrobenzaldehyde (o-NBA) with selected different excitation wavelengths (355-400 nm) is investigated, and the nascent OH radical is detected by the single-photon laser-induced fluorescence (LIF) technique. The relative quantum yield and rotational excitation of OH formation are found to be dependent on the excitation energy. The distributions of rotational, spin-orbit, and Lambda-doublet states are obtained at 355-400 nm by analyzing the experimental data. The OH radicals are found to be vibrationally cold at all photolysis wavelengths. The spin-orbit and Lambda-doublet states have nonstatistical distributions. To understand the dissociative process involved in the OH-generating channel, DFT calculations are performed. Based on both experimental and theoretical results, possible photolysis channels of o-NBA leading to the OH fragment are proposed and discussed.

Dynamics of OH Formation in the Photodissociation of o-Nitrobenzoic Acid at 295 and 355 nm

Photodissociation dynamics of o-nitrobenzoic acid at 295 and 355 nm is studied by probing the nascent OH photoproduct employing the single-photon laser-induced fluorescence technique. At both of the photolysis wavelengths, the OH fragments are found to be vibrationally cold but have different rotational state distributions. Upon photolysis at 295 nm, the relative population of OH in different rotational states does not follow the Boltzmann equilibrium distribution, whereas upon photolysis at 355 nm, a Boltzmann distribution is observed with a rotational temperature of 1010 +/- 100 K. Between the two spin-orbit states, (2)Pi(3/2) and (2)Pi(1/2), the former is found to be preferentially populated, and the distribution of the Pi(A') state for the Lambda-doublet is dominant at both of the wavelengths studied. Several possible dissociation pathways of o-nitrobenzoic acid leading to formation of the OH fragment are investigated computationally. On the basis of the theoretical and experimental studies, a possible mechanism of OH formation from the photodissociation of o-nitrobenzoic acid at 295 and 355 nm is proposed.

Dynamics of the Reaction of O(3P) Atoms with Alkylthiol Self-assembled Monolayers

We have studied the dynamics of the reactions of O((3)P) atoms with alkylthiol self-assembled monolayers (SAMs). Superthermal O((3)P) atoms, with a fairly broad distribution of laboratory-frame kinetic energies (mean = 16 kJ mol(-1), fwhm = 26 kJ mol(-1)), were generated by 355 nm photolysis of NO(2) introduced at a low pressure above the SAM surface. Nascent OH v' = 0 products were detected by laser-induced fluorescence. SAMs of two different alkyl chain lengths, C(6) and C(18), were studied. The existence of SAM layers, and their robustness under our experimental conditions during the relevant measurement period, were confirmed by scanning-tunneling microscopy (STM). Reaction at the SAM surface was verified as the authentic source of the hydroxyl radicals using a perdeuterated C(6)D(13)-SAM sample. The OH appearance profiles as a function of photolysis-probe delay, and the rotational-state distributions at their peaks, were compared with those of liquid squalane (C(30)H(62), 2,6,10,15,19,23-hexamethyltetracosane). The reactivity of the SAMs and of squalane was found to be comparable. We conclude that the O((3)P) atoms must be able to access the more reactive secondary hydrogen atoms along the alkyl chains of the SAMs. We find no perceptible differences in reactivity or product energy disposal between the two SAM chain lengths. Both produce a substantial fraction of the OH with relatively high velocities, which must result from direct, impulsive reaction. There is also a slower component, with velocities consistent with a thermal, trapping-desorption mechanism. The proportion of this component appears to be lower for SAMs than for squalane. This would be compatible with the expected greater smoothness of the SAM surface at the molecular scale. We find little evidence for significant rotational excitation of the OH products, although the details of any correlation between translational and rotational energy release require further investigation. We compare our results with the limited available prior theoretical modeling of O((3)P) + SAM systems.

Photodissociation Dynamics of Alkyl Nitrites at 266 and 355 nm: The OH Product Channel

Photodissociation of methyl nitrite and n-butyl nitrite at 266 and 355 nm has been investigated in the gas phase at room temperature. OH photoproducts were observed, and their internal state distributions were measured by the one-photon laser-induced fluorescence (LIF) technique. It was found that the nascent OH from the 266 nm photolysis of methyl nitrite was vibrationally cold, and its rotational state distribution conformed to a Boltzmann behavior with a rotational temperature of T(rot) = 2200 +/- 150 K. In contrast, the nascent OH from the 266 nm photolysis of n-butyl nitrite was found to be vibrationally excited, and the measured relative population of v'' = 0:1 was 0.78:0.22. The rotational state distribution of the OH v'' = 1 state conformed to Boltzmann behavior, with a rotational temperature of T(rot) = 1462 +/- 120 K. However, a simple Boltzmann distribution was not found for the OH v'' = 0 state. In the photolysis of n-butyl nitrite at 355 nm, the OH fragment was found to be vibrationally cold and its rotational state distribution showed non-Boltzmann behavior. A photodissociation mechanism involving an intramolecular hydrogen atom transfer process is proposed for the OH product pathway for methyl nitrite, which has been compared with the potential energy surfaces obtained from density functional theory (DFT) calculations. A photodissociation mechanism of n-butyl nitrite is also proposed for the OH product pathway, which differs from that of methyl nitrite due to the effects of the different alkoxy substituents.

Transition State Theory: A Reaction Dynamics Tool Applied to Gas-Surface Reactions

Recombinative desorption of molecules from a metal surface is a fundamental step in heterogeneous catalytic reactions. Understanding this elementary mechanism can bring precious information on both the dynamics and the kinetics of gas-surface reactions.The aim of this work was to combine classical trajectory calculations and transition state theory (TST) based approaches to study the dynamics of molecular associative desorption. We were particularly interested in the description of state distributions in the products of associative molecular desorption. For late barrier processes such as H2/Pt(111), energy transfers between vibrational, rotational and translational motions of the departing molecule are too weak to alter its state distributions estimated at the transition state (TS). Accordingly, TST gives a straightforward description of final state distributions. On the opposite, for early barrier processes, such as H2/Cu(111), strong energy transfers occur along the exit channel. Therefore, we must apply the so-called Statistico-Dynamical Approach (SDA). This method is partly based upon TST and takes into account energy transfers which occur between rotational and translational motions en route to the gas phase. Therefore, SDA gives a description of rotational state distributions of desorbed molecules. For both processes under investigation, statistical methods were found to be in good agreement with both classical trajectory calculations and experimental results.