Controlled subnanosecond isomerization of HCN to CNH in solution

We report a study of control of the HCN-->CNH isomerization in a liquid Ar solution. We show, using molecular dynamics simulations, nearly complete conversion from HCN to CNH can be achieved in solution on the subnanosecond time scale without requiring laser pulse shaping or molecular alignment. The mechanism of the isomerization reaction involves multiphoton rovibrational excitation on the ground electronic state potential energy surface coupled with rapid rovibrational relaxation in solution. The results demonstrate the important role of rotation-vibration coupling in multiphoton excitation of small molecules and constitute the first realistic computational demonstration of fast, robust, and high-yield laser field manipulation of solution-phase molecular processes.     

Infrared multiphoton induced isomerization and dissociation of FCN, ClCN, and BrCN in liquid Ar: a classical simulation study

We report the results of classical mechanics simulations of infrared multiphoton induced control of isomerization of FCN, ClCN, and BrCN in liquid Ar, using ab initio potential energy and dipole moment surfaces for the XCN molecules. The field induced isomerization and fragmentation dynamics of these molecules are found to be different from that of HCN in liquid Ar. In particular, the scheme that provides complete controlled conversion of HCN to CNH in liquid Ar fails to generate complete conversion of XCN to CNX in liquid Ar for X=F,Cl,Br. It is suggested that the sources of the differences in behavior arise from differences in the spectra of vibrational nonlinear resonances in HCN and XCN and to the occurrence of monodromy in the dynamics of the XCN molecules.     

Ab initio design of picosecond infrared laser pulses for controlling vibrational-rotational excitation of CO molecules

Optimal control of rovibrational excitations of the CO molecule using picosecond infrared laser pulses is described in the framework of the electric-nuclear Born-Oppenheimer approximation [G. G. Balint-Kurti et al., J. Chem. Phys. 122, 084110 (2005)]. The potential energy surface of the CO molecule in the presence of an electric field is calculated using coupled cluster theory with a large orbital basis set. The quantum dynamics of the process is treated using a full three dimensional treatment of the molecule in the laser field. The detailed mechanisms leading to efficient control of the selected excitation processes are discussed.     

Threshold ion-pair production spectroscopy of HCN

The spectroscopic technique of threshold ion-pair production spectroscopy (TIPPS) has been applied to the triatomic molecule HCN. We have recorded the total ion-pair yield and TIPP spectra for the HCN-->H(+) + CN(-) process using coherent vacuum ultraviolet excitation. From the simulation of our high-resolution TIPP spectrum we have precisely measured the HCN ion-pair threshold E(IP) (0) to be 122 244 +/- 4 cm(-1). This value could be used to determine the bond dissociation energy D(0)(H-CN) to unprecedented accuracy. Our fitting result also showed that rotationally excited instead of cold CN(-) fragment is favored as the ion-pair dissociation product in the threshold region.     

Molecular isomerization induced by ultrashort infrared pulses. II. Pump-dump isomerization using pairs of time-delayed half-cycle pulses

We investigate population transfer across the barrier in a double-well potential, induced by a pair of time-delayed single-lobe half-cycle pulses. We apply this setup both to a one-dimensional (1D) quartic model potential and to a three-dimensional potential representing HCN-->HNC isomerization. Overall the results for the two systems are similar, although in the 3D system some additional features appear not seen in the 1D case. The generic mechanism of population transfer is the preparation by the pump pulse of a wave packet involving delocalized states above the barrier, followed by the essentially 1D motion of the delocalized part of wave packet across the barrier, and the eventual de-excitation by the dump pulse to localized states in the other well. The correct timing is given by the well-to-well passage time of the wave packet and its recurrence properties, and by the signs of the field lobes which determine the direction and acceleration or deceleration of the wave packet motion. In the 3D system an additional pump-pump-dump mechanism linked to wave packet motion in the reagent well can mediate isomerization. Since the transfer time and the pulse durations are of the same order of magnitude, there is also a marked dependence of the dynamics and the transfer yield on the pulse duration. Our analysis also sheds light on the pronounced carrier envelope phase dependence previously observed for isomerization and molecular dissociation with one-cycle and sub-one-cycle pulses.     

On combining molecular dynamics and stochastic dynamics simulations to compute reaction rates in liquids

An approach that combines molecular dynamics and stochastic dynamics calculations for obtaining reaction rates in liquids is investigated by studying the cis-->trans isomerization of HONO in liquid krypton. The isomerization rates are computed for several liquid densities by employing full-dimensional molecular-dynamics simulations. The rates are also computed by employing the stochastic dynamics method for a wide range of collision frequencies. Comparisons of the two sets of the computed rates show that for a wide range of liquid densities there is a simple linear relation between the liquid density rho and the collision frequency alpha, that is, alpha=crho. This suggests that once the constant c is determined from a molecular-dynamics calculation at a single density, the reaction rates can be obtained from stochastic dynamics calculations for the entire range of liquid densities where alpha=crho holds. The applicability of the combined molecular dynamics and stochastic dynamics approach provides a practical means for obtaining rate constants at considerable savings of computer time compared to that required by using full-dimensional molecular-dynamics simulations alone.     

Fourier grid Hamiltonian‐based multidimensional Floquet propagator method for continuous,pulsed, and bichromatic laser field: Application to the multiphoton dissociation dynamics of HCN molecule

We present a Fourier grid Hamiltonian‐based multidimensional propagator method for multiphoton dissociation dynamics of triatomic molecule in continuous, pulsed, and bichromatic laser field. The method has been successfully applied to the photodissociation dynamics of HCN molecule, i.e., collinear geometry. © 2006 Wiley Periodicals, Inc. Int J Quantum Chem, 2007     

Implications of the HCN → HNC process to high-temperature nitrogen-containing fuel chemistry

We have found in our recent kinetic study of the oxidation of HCN by NO₂ in the temperature range 623–773 K that HNCO and CO₂ are very important early products. The measured kinetic data cannot be accounted for by a “conventional” mechanism involving HCN reactions with NO₂, O, and OH. However, the introduction of the isomerization reaction HCN → HNC, followed by the rapid oxidation of HNC by NO₂, O, and OH, can quantitatively simulate all measured kinetic data. A similar study of the NO₂ + HCN reaction in shock waves at temperatures between 1500 and 2400 K also required the inclusion of HNC reactions in order to quantitatively account for measured product distributions. The effects of the HNC molecule on the high temperature HCN chemistry are discussed in terms of the predicted rate constants for HNC reactions with O and OH employing the BAC-MP4 method. © John Wiley & Sons, Inc.     

HNC/HCN ratio in acetonitrile, formamide, and BrCN discharge

Time-resolved Fourier transform (FT) spectrometry was used to study the dynamics of radical reactions forming the HCN and HNC isomers in pulsed glow discharges through vapors of BrCN, acetonitrile (CH(3)CN), and formamide (HCONH(2)). Stable gaseous products of discharge chemistry were analyzed by selected ion flow tube mass spectrometry (SIFT-MS). Ratios of concentrations of the HNC/HCN isomers obtained using known transition dipole moments of rovibrational cold bands v(1) were found to be in the range 2.2-3%. A kinetic model was used to assess the roles the radical chemistry and ion chemistry play in the formation of these two isomers. Exclusion of the radical reactions from the model resulted in a value of the HNC/HCN ratio 2 orders of magnitude lower than the experimental results, thus confirming their dominant role. The major process responsible for the formation of the HNC isomer is the reaction of the HCN isomer with the H atoms. The rate constant determined using the kinetic model from the present data for this reaction is 1.13 (±0.2) × 10(-13) cm(3) s(-1).     

Fragmentation of singly charged adenine induced by neutral fluorine beam impact at 3 keV

The fragmentation scheme of singly charged adenine molecule (H(5)C(5)N(5)(+)) has been studied via neutral fluorine impact at 3 keV. By analyzing in correlation the kinetic energy loss of the scattered projectile F(-) produced in single charge transfer process and the mass of the charged fragments, the excitation energy distribution of the parent adenine molecular ions has been determined for each of the main dissociation channels. Several fragmentation pathways unrevealed in standard mass spectra or in appearance energy measurements are investigated. Regarding the well-known hydrogen cyanide (HCN) loss sequence, we demonstrate that although the loss of a HCN is the dominant decay channel for the parent H(5)C(5)N(5)(+) (m = 135), the decay of the first daughter ion H(4)C(4)N(4)(+) (m = 108) involves not only the HNC (m = 27) loss but also the symmetric breakdown into two dimers of HCN.     

Competition between photochemistry and energy transfer in UV-excited diazabenzenes. 4. UV photodissociation of 2,3-, 2,5-, and 2,6-dimethylpyrazine

The quantum yield for HCN formation via 248 nm photodissociation of 2,3-, 2,5-, and 2,6-dimethylpyrazine (DMP, C6N2H8) was measured using diode laser probing of the HCN photoproduct. The total quantum yield is phi = 0.039 +/- 0.07, 0.14 +/- 0.02, and 0.30 +/- 0.06 for 248 nm excitation of 2,3-, 2,5- and 2,6-DMP, respectively. Analysis of the quenching data within the context of a gas kinetic, strong collision model allows an estimate of the rate constant for HCN production via DMP photodissociation, ks = 4.1 x 10(3), 1.0 x 10(3), and 1.3 x 10(4) s(-1) for 2,3-, 2,5- and 2,6-DMP, respectively. Unlike HCN produced from the photodissociation of pyrazine and methylpyrazine, the amount of HCN produced via a prompt, unquenched dissociation channel was essentially zero, suggesting little multiphoton UV absorption. The rate constants for HCN formation together with previously measured rate constants for HCN production from photodissociation of pyrazine and methylpyrazine have been used to investigate possible reaction mechanisms. The position of the methyl group affects the HCN rate constant, suggesting that the mechanism for pyrazine dissociation involves an initial step that is hindered by the addition of the methyl groups. The proposed initial molecular motion of the mechanism, an out-of-plane H atom migration across a N atom, is consistent with (1) the position of the methyl groups, (2) the dissociation lifetime of the various pyrazine molecules studied, and (3) the observed large energy transfer magnitudes from pyrazine near dissociation. These so-called "supercollisions" have been linked to low-frequency, out-of-plane motion, suggesting that the molecular motions leading to efficient energy transfer are the same motions involved in dissociation. In addition, the pyrazine (C4N2H4) 248 nm photoproduct (C3H3N) was identified as acrylonitrile using IR spectroscopy, an observation that aids in understanding the dissociation mechanism.     

Gas-phase photodissociation of CH3COCN at 308 nm by time-resolved Fourier-transform infrared emission spectroscopy

By using time-resolved Fourier-transform infrared emission spectroscopy, the fragments of HCN(v = 1, 2) and CO(v = 1-3) are detected in one-photon dissociation of acetyl cyanide (CH(3)COCN) at 308 nm. The S(1)(A(")), (1)(n(O), π(?) (CO)) state at 308 nm has a radiative lifetime of 0.46 ± 0.01 μs, long enough to allow for Ar collisions that induce internal conversion and enhance the fragment yields. The rate constant of Ar collision-induced internal conversion is estimated to be (1-7) × 10(-12) cm(3) molecule(-1) s(-1). The measurements of O(2) dependence exclude the production possibility of these fragments via intersystem crossing. The high-resolution spectra of HCN and CO are analyzed to determine the ro-vibrational energy deposition of 81 ± 7 and 32 ± 3 kJ∕mol, respectively. With the aid of ab initio calculations, a two-body dissociation on the energetic ground state is favored leading to HCN + CH(2)CO, in which the CH(2)CO moiety may further undergo secondary dissociation to release CO. The production of CO(2) in the reaction with O(2) confirms existence of CH(2) and a secondary reaction product of CO. The HNC fragment is identified but cannot be assigned, as restricted to a poor signal-to-noise ratio. Because of insufficient excitation energy at 308 nm, the CN and CH(3) fragments that dominate the dissociation products at 193 nm are not detected.     

Selective preparation of the zeroth-order vibrational states in the HOD molecule by ultrashort infrared laser pulses

An approach for controlling the molecular dynamics competing aginst intramolecular vibrational-energy redistribution and selective preparation of the zeroth-order vibrational states on a picosecond time scale is developed and demonstrated for the HOD molecule. The zeroth-order states of the local OH bond are prepared selectively and demonstrate the coherent oscillatory behaviour after the end of the laser escitation. Coherent in-phase and out-of-phase oscillations are demonstrated by two single zeroth-order states efficiently coupled to each other. Quasi-periodic in-phase and out-of-phase oscillations occur if a single zeroth-order state is coupled to several other zeroth-order states. The frequence of these oscillations depends on the laser field which appears the state. The laser control scheme includes superposition of properly optimized infrared laser pulses of a subpicosecond duration.     

New double many-body expansion potential energy surface for ground-state HCN from a multiproperty fit to accurate ab initio energies and rovibrational calculations

An accurate single-sheeted double many-body expansion potential energy surface has been obtained for the ground electronic state of the hydrogen cyanide molecule via a multiproperty fit to ab initio energies and rovibrational data. This includes 106 rovibrational levels and 2313 discrete points, which are fit with a rmsd of 4 cm(-1) and 2.42 kcal mol(-1), respectively, and seven zero first-derivatives that are reproduced at three stationary points. Since the potential also describes accurately the appropriate asymptotic limits at the various dissociation channels, it is commended both for the simulation of rovibrational spectra and reaction dynamics.     

Dipole-resonance assisted isomerization in the electronic ground state using few-cycle infrared pulses

A computational investigation of HCN → HNC isomerization in the electronic ground state by one- and few-cycle infrared pulses is presented. Starting from a vibrationally pre-excited reagent state, isomerization yields of more than 50% are obtained using single one- to five-cycle pulses. The principal mechanism includes two steps of population transfer by dipole-resonance (DR), and hence, the success of the method is closely linked to the polarity of the system and, in particular, the stepwise change of the dipole moment from reactant to transition state and on to products. The yield drops massively if the diagonal dipole matrix elements are artificially set to zero. In detail, the mechanism includes DR-induced preparation of a delocalized vibrational wavepacket, which traverses the barrier region and is finally trapped in the product well by DR-dominated de-excitation. The excitation and de-excitation steps are triggered by pulse lobes of opposite field direction. As the number of optical cycles is increased, the leading field lobes prepare a vibrational superposition state by off-resonant ladder climbing, which is then subjected to the three steps of the principal isomerization mechanism. DR excitation is more efficient from a preformed vibrational wavepacket than from a molecular eigenstate. The entire process can be loosely described as Tannor-Kosloff-Rice type transfer mechanism on a single potential surface effected by a single pulse, individual field lobes assuming the roles of pump- and dump-pulses. Pre-excitation to a transient wavepacket can be enhanced by applying a separate, comparatively weak few-cycle prepulse, in which the prepulse prepares a vibrational wavepacket. The two-pulse setup corresponds to a double Tannor-Kosloff-Rice control scheme on a single potential surface.     

Vibrationally state-selective photoassociation by infrared sub-picosecond laserr pulses: model simulations for O + H → OH(ν)

The quantum dynamics of a photoassociation reaction in the electronic ground state controlled by an infrared picosecond laser pulse is investigated. The association reaction O + H → OH(ν) is simulated by representative wavepackets. The OH molecule to be formed is modeled as a non-rotating Morse oscillator. It is shown that the initial free continuum state of O + H can be transferred selectively into a specified vibrational bound state by interaction with an infrared laser pulse. Optimal design of the laser control field leads to high association probability with very high vibrational state selectivity.     

Quantum-state-resolved CO2 scattering dynamics at the gas-liquid interface: incident collision energy and liquid dependence

Quantum-state-resolved dynamics at the gas-liquid interface are probed by colliding supersonically cooled molecular beams of CO(2) with freshly formed liquid surfaces in a vacuum. Translational, rotational, and vibrational state distributions of both incident and scattered fluxes are measured by high-resolution direct infrared absorption spectroscopy and laser dopplerimetry in the 00(0)0 and 01(1)0 rovibrational manifolds of CO(2) in the asymmetric stretch manifold. The present studies investigate the role of incident molecular beam energy (E(inc) = 1.6(1), 4.7(2), 7.7(2), and 10.6(8) kcal/mol) on these distributions for a series of perfluorinated, hydrocarbon, and hydrogen-bonded liquids. Boltzmann analysis of the internal quantum-state populations provide evidence for nonthermal scattering dynamics, as confirmed by Dopplerimetry on the absorption profiles. The data provide quantum-state-resolved support for a dual channel picture of the scattering process, consisting of either prompt impulsive scattering (IS) or longer duration trapping-desorption (TD) events, with the fraction observed in each channel dependent on incident kinetic energy and the physical properties of the liquid surface. The clear evidence that internal CO(2) rotational populations arising from the IS channel can be adequately described by a Boltzmann temperature (albeit with E(IS) > RT(S)) is consistent with previous gas-solid scattering studies and suggests that even nominally "prompt" IS events reflect both single (i.e. direct) and multiple impulsive interactions with the liquid interface.     

Collision induced dissociation of doubly-charged ions: Coulomb explosion vs. neutral loss in [Ca(urea)](2+) gas phase unimolecular reactivity via chemical dynamics simulations

In this paper we report different theoretical approaches to study the gas-phase unimolecular dissociation of the doubly-charged cation [Ca(urea)](2+), in order to rationalize recent experimental findings. Quantum mechanical plus molecular mechanical (QM/MM) direct chemical dynamics simulations were used to investigate collision induced dissociation (CID) and rotational-vibrational energy transfer for Ar + [Ca(urea)](2+) collisions. For the picosecond time-domain of the simulations, both neutral loss and Coulomb explosion reactions were found and the differences in their mechanisms elucidated. The loss of neutral urea subsequent to collision with Ar occurs via a shattering mechanism, while the formation of two singly-charged cations follows statistical (or almost statistical) dynamics. Vibrational-rotational energy transfer efficiencies obtained for trajectories that do not dissociate during the trajectory integration were used in conjunction with RRKM rate constants to approximate dissociation pathways assuming complete intramolecular vibrational energy redistribution (IVR) and statistical dynamics. This statistical limit predicts, as expected, that at long time the most stable species on the potential energy surface (PES) dominate. These results, coupled with experimental CID from which both neutral loss and Coulomb explosion products were obtained, show that the gas phase dissociation of this ion occurs by multiple mechanisms leading to different products and that reactivity on the complicated PES is dynamically complex.     

Rovibrational excitation of a diatomic molecule due to ion impact in the presence of IR laser beam

A theoretical study is made of rovibrational excitation of a CO molecule due to proton impact in the presence of an infrared laser beam taken in the electric dipole approximation. Non-perturbative quasi-energy method has been applied to describe laser-molecule interaction. Effect of laser and collision parameters on cross-section is investigated. To show the effect of laser on collision process we have compared our results with field free results.