Dipolar collisions of ultracold 23Na87Rb molecules.

NASA Astrophysics Data System (ADS)

Guo, Mingyang; Ye, Xin; He, Junyu; Quéméner, Goulven; González-Martínez, Maykel; Dulieu, Olivier; Wang, Dajun

2017-04-01

Although ultracold polar molecules have long been proposed as a primary candidate for investigating dipolar many body physics, many of their basic properties, like their collisions in external electric fields, are still largely unknown. In fact, despite the successful production of several new ultracold molecular species in the last two years, so far the only available dipolar collision data is still from JILA's fermionic 40K87Rb experiment in 2010. In this talk, we will describe our investigation on dipolar collisions of ultracold bosonic and chemically stable 23Na87Rb molecules which possess a large permanent electric dipole moment. With a moderate electric field, an effective dipole moment large enough to strongly couple higher partial waves into the collisions can be achieved. We will report the influence of this effect on the molecular collisions observed in our experiment. Our theoretical model for understanding these observations will also be presented. This work is supported by the Hong Kong RGC CUHK404712 and the ANR/RGC Joint Research Scheme ACUHK403/13.

Molecular three-body Brauner-Briggs-Klar theory for ion-impact ionization of molecules

NASA Astrophysics Data System (ADS)

Ghanbari-Adivi, E.

2016-12-01

Molecular three-body Brauner-Briggs-Klar (M3BBK) theory is developed to study the single ionization of diatomic molecules by ion impact. The orientation-averaged molecular orbital (OAMO) approximation is used to reduce the required computer time without sacrificing the performance of the method. The post-collision interaction (PCI) between the scattered projectile and the ejected electron is included. The theory is applied to collision of protons with hydrogen molecules. Results are obtained for two different kinematical regimes: i) fast collisions and low emission energies, and ii) not so fast collisions and higher emission energies. For both considered regimes, experimental fully differential cross-sections as well as different theoretical calculations are available for comparison. These comparisons are carried out and discussed.

Collisions of ultracold 23Na87Rb molecules with controlled chemical reactivity

NASA Astrophysics Data System (ADS)

Ye, Xin; Guo, Mingyang; He, Junyu; Wang, Dajun; Quemener, Goulven; Gonzalez-Martinez, Maykel; Dulieu, Oliver

2017-04-01

The recent successful creation of several ultracold absolute ground-state polar molecules without chemical reaction channel has opened a new playground for investigating the so far poorly understood collisions between them. On one hand, these collisions are indispensable for the exploration of dipolar physics, on the other hand, they are direct manifestations of the brand-new field of ultracold chemistry. Here, we report on the study on molecular collisions with ultracold ground-state 23Na87Rb molecules prepared by transferring weakly bound Feshbach molecules with STIRAP. By tuning the Raman laser wavelength to control the internal states, samples with distinctly different chemical reactivity and inelastic channels can be prepared. Surprisingly, we found that the trap loss of the non-reactive case is nearly identical to that of the reactive case. We also developed a model based on the collision complex formation mechanism. The comparison between experiment and theory will also be presented. This work was supported by the French ANR/Hong Kong RGC COPOMOL project (Grant No. A-CUHK403/13), the RGC General Research Fund (Grant No. CUHK14301815).

Spacecraft self-contamination due to back-scattering of outgas products

NASA Technical Reports Server (NTRS)

Robertson, S. J.

1976-01-01

The back-scattering of outgas contamination near an orbiting spacecraft due to intermolecular collisions was analyzed. Analytical tools were developed for making reasonably accurate quantitative estimates of the outgas contamination return flux, given a knowledge of the pertinent spacecraft and orbit conditions. Two basic collision mechanisms were considered: (1) collisions involving only outgas molecules (self-scattering) and (2) collisions between outgas molecules and molecules in the ambient atmosphere (ambient-scattering). For simplicity, the geometry was idealized to a uniformly outgassing sphere and to a disk oriented normal to the freestream. The method of solution involved an integration of an approximation of the Boltzmann kinetic equation known as the BGK (or Krook) model equation. Results were obtained in the form of simple equations relating outgas return flux to spacecraft and orbit parameters. Results were compared with previous analyses based on more simplistic models of the collision processes.

Vibrational and Electronic Energy Transfer and Dissociation of Diatomic Molecules by Electron Collisions

NASA Technical Reports Server (NTRS)

Huo, Winifred M.; Langhoff, Stephen R. (Technical Monitor)

1995-01-01

At high altitudes and velocities equal to or greater than the geosynchronous return velocity (10 kilometers per second), the shock layer of a hypersonic flight will be in thermochemical nonequilibrium and partially ionized. The amount of ionization is determined by the velocity. For a trans atmospheric flight of 10 kilometers per second and at an altitude of 80 kilometers, a maximum of 1% ionization is expected. At a velocity of 12 - 17 kilometer per second, such as a Mars return mission, up to 30% of the atoms and molecules in the flow field will be ionized. Under those circumstances, electrons play an important role in determining the internal states of atoms and molecules in the flow field and hence the amount of radiative heat load and the distance it takes for the flow field to re-establish equilibrium. Electron collisions provide an effective means of transferring energy even when the electron number density is as low as 1%. Because the mass of an electron is 12,760 times smaller than the reduced mass of N2, its average speed, and hence its average collision frequency, is more than 100 times larger. Even in the slightly ionized regime with only 1% electrons, the frequency of electron-molecule collisions is equal to or larger than that of molecule-molecule collisions, an important consideration in the low density part of the atmosphere. Three electron-molecule collision processes relevant to hypersonic flows will be considered: (1) vibrational excitation/de-excitation of a diatomic molecule by electron impact, (2) electronic excitation/de-excitation, and (3) dissociative recombination in electron-diatomic ion collisions. A review of available data, both theory and experiment, will be given. Particular attention will be paid to tailoring the molecular physics to the condition of hypersonic flows. For example, the high rotational temperatures in a hypersonic flow field means that most experimental data carried out under room temperatures are not applicable. Also, the average electron temperature is expected to be between 10,000 and 20,000 K. Thus only data for low energy electrons are relevant to the model.

Constraining the sensitivity of iodide adduct chemical ionization mass spectrometry to multifunctional organic molecules using the collision limit and thermodynamic stability of iodide ion adducts

DOE PAGES

Lopez-Hilfiker, Felipe D.; Iyer, Siddarth; Mohr, Claudia; ...

2016-04-06

The sensitivity of a chemical ionization mass spectrometer (ions formed per number density of analytes) is fundamentally limited by the collision frequency between reagent ions and analytes, known as the collision limit, the ion–molecule reaction time, and the transmission efficiency of product ions to the detector. We use the response of a time-of-flight chemical ionization mass spectrometer (ToF-CIMS) to N 2O 5, known to react with iodide at the collision limit, to constrain the combined effects of ion–molecule reaction time, which is strongly influenced by mixing and ion losses in the ion–molecule reaction drift tube. A mass spectrometric voltage scanningmore » procedure elucidates the relative binding energies of the ion adducts, which influence the transmission efficiency of molecular ions through the electric fields within the vacuum chamber. Together, this information provides a critical constraint on the sensitivity of a ToF-CIMS towards a wide suite of routinely detected multifunctional organic molecules for which no calibration standards exist. Lastly, we describe the scanning procedure and collision limit determination, and we show results from the application of these constraints to the measurement of organic aerosol composition at two different field locations.« less

Modifications to Axially Symmetric Simulations Using New DSMC (2007) Algorithms

NASA Technical Reports Server (NTRS)

Liechty, Derek S.

2008-01-01

Several modifications aimed at improving physical accuracy are proposed for solving axially symmetric problems building on the DSMC (2007) algorithms introduced by Bird. Originally developed to solve nonequilibrium, rarefied flows, the DSMC method is now regularly used to solve complex problems over a wide range of Knudsen numbers. These new algorithms include features such as nearest neighbor collisions excluding the previous collision partners, separate collision and sampling cells, automatically adaptive variable time steps, a modified no-time counter procedure for collisions, and discontinuous and event-driven physical processes. Axially symmetric solutions require radial weighting for the simulated molecules since the molecules near the axis represent fewer real molecules than those farther away from the axis due to the difference in volume of the cells. In the present methodology, these radial weighting factors are continuous, linear functions that vary with the radial position of each simulated molecule. It is shown that how one defines the number of tentative collisions greatly influences the mean collision time near the axis. The method by which the grid is treated for axially symmetric problems also plays an important role near the axis, especially for scalar pressure. A new method to treat how the molecules are traced through the grid is proposed to alleviate the decrease in scalar pressure at the axis near the surface. Also, a modification to the duplication buffer is proposed to vary the duplicated molecular velocities while retaining the molecular kinetic energy and axially symmetric nature of the problem.

A cryofuge for cold-collision experiments with slow polar molecules

NASA Astrophysics Data System (ADS)

Wu, Xing; Gantner, Thomas; Koller, Manuel; Zeppenfeld, Martin; Chervenkov, Sotir; Rempe, Gerhard

2017-11-01

Ultracold molecules represent a fascinating research frontier in physics and chemistry, but it has proven challenging to prepare dense samples at low velocities. Here, we present a solution to this goal by means of a nonconventional approach dubbed cryofuge. It uses centrifugal force to bring cryogenically cooled molecules to kinetic energies below 1 K × kB in the laboratory frame, where kB is the Boltzmann constant, with corresponding fluxes exceeding 1010 per second at velocities below 20 meters per second. By attaining densities higher than 109 per cubic centimeter and interaction times longer than 25 milliseconds in samples of fluoromethane as well as deuterated ammonia, we observed cold dipolar collisions between molecules and determined their collision cross sections.

Kinematic cooling of molecules in a magneto-optical trap

NASA Astrophysics Data System (ADS)

Takase, Ken; Chandler, David W.; Strecker, Kevin E.

2008-05-01

We will present our current progress on a new experimental technique aimed at slowing and cooling hot molecules using a single collision with magneto-optically trapped atoms. Kinematic cooling, unlike buffer gas and sympathetic cooling, relies only on a single collision between the molecule and atom to stop the molecule in the laboratory frame. This technique has recently been demonstrated in a crossed atomic and molecular beam machine to produce 35mK samples of nitric oxide via a single collision with argon [1]. In this technique we replace the atomic beam with a sample magneto-optically trapped atoms. We are currently designing and building a new apparatus to attempt these experiments. [1] Kevin E. Strecker and David W. Chandler (to be published)

Infinite-order sudden approximation for collisions involving molecules in Pi electronic states: a new derivation and calculations of rotationally inelastic cross sections for NO(x superscript 2 Pi) + He and Ar

DOE Office of Scientific and Technical Information (OSTI.GOV)

Corey, G.C.; Alexander, M.H.

1986-11-15

A new derivation is presented of the infinite order sudden (IOS) approximation for rotationally inelastic collisions of a diatomic molecule in a Pi electronic state with a closed shell atom. This derivation clearly demonstrates the connection between the two sudden S functions for scattering off the adiabatic potential surface of A' and A symmetry, which would arise from an ab initio calculation on an atom + Pi-state molecule system, and the S matrix elements in diabatic basis, which are required in the quantum treatment of the collision dynamics. Coupled states and IOS calculations were carried out for collisions of NImore » X 2 Pi with helium and argon, based on a electron gas potential surface at total energies of 63, 150, and 300 meV. The IOS approximation is not reliable for collisions of NO with Ar, even at the highest collision energy considered here. However, for collisions with He at 150 and 300 meV, the IOS approximation is nearly quantitative for transitions both within and between the Omega = 1/2 and Omega = 3/2 manifolds.« less

Collinear Collision Chemistry: 1. A Simple Model for Inelastic and Reactive Collision Dynamics

ERIC Educational Resources Information Center

Mahan, Bruce H.

1974-01-01

Discusses a model for the collinear collision of an atom with a diatomic molecule on a simple potential surface. Indicates that the model can provide a framework for thinking about molecular collisions and reveal many factors which affect the dynamics of reactive and inelastic collisions. (CC)

Interpretation of ES, CS, and IOS approximations within a translational--internal coupling scheme. IV. ES and IOS molecule--molecule cross sections

DOE Office of Scientific and Technical Information (OSTI.GOV)

Snider, R.F.; Parvatiyar, M.G.

1981-05-15

Properties of energy sudden and infinite order sudden translational--internal reduced S matrices are given for general molecule--molecule collisions. Formal similarities with the distorted wave Born approximation are discussed. Structural simplifications of energy dependent and kinetic cross sections associated with making the ES approximation are described. Conceptual difficulties associated with applying the ES and IOS approximations to kinetic processes dominated by energetically inelastic collisions are pointed out.

Cryogenic buffer-gas loading and magnetic trapping of CrH and MnH molecules

NASA Astrophysics Data System (ADS)

Stoll, Michael; Bakker, Joost M.; Steimle, Timothy C.; Meijer, Gerard; Peters, Achim

2008-09-01

We report on the buffer-gas cooling and trapping of CrH and MnH molecules in a magnetic quadrupole trap with densities on the order of 106cm-3 at a temperature of 650mK . Storage times of up to 180ms have been observed, corresponding to a 20-fold lifetime enhancement with respect to the field-free diffusion through the He3 buffer-gas. Using Monte Carlo trajectory simulations, inelastic molecule- He3 collision cross sections of 1.6×10-18 and 3.1×10-17cm2 are extracted for CrH and MnH, respectively. Furthermore, elastic molecule- He3 collision cross sections of 1.4(±0.5)×10-14cm2 are determined for both species. We conclude that the confinement time of these molecules in a magnetic trapping field is limited by inelastic collisions with the helium atoms leading to Zeeman relaxation.

The Schwinger Variational Method

NASA Technical Reports Server (NTRS)

Huo, Winifred M.

1995-01-01

Variational methods have proven invaluable in theoretical physics and chemistry, both for bound state problems and for the study of collision phenomena. The application of the Schwinger variational (SV) method to e-molecule collisions and molecular photoionization has been reviewed previously. The present chapter discusses the implementation of the SV method as applied to e-molecule collisions. Since this is not a review of cross section data, cross sections are presented only to server as illustrative examples. In the SV method, the correct boundary condition is automatically incorporated through the use of Green's function. Thus SV calculations can employ basis functions with arbitrary boundary conditions. The iterative Schwinger method has been used extensively to study molecular photoionization. For e-molecule collisions, it is used at the static exchange level to study elastic scattering and coupled with the distorted wave approximation to study electronically inelastic scattering.

The Schwinger Variational Method

NASA Technical Reports Server (NTRS)

Huo, Winifred M.

1995-01-01

Variational methods have proven invaluable in theoretical physics and chemistry, both for bound state problems and for the study of collision phenomena. For collisional problems they can be grouped into two types: those based on the Schroedinger equation and those based on the Lippmann-Schwinger equation. The application of the Schwinger variational (SV) method to e-molecule collisions and photoionization has been reviewed previously. The present chapter discusses the implementation of the SV method as applied to e-molecule collisions.

Progress in Computational Electron-Molecule Collisions

NASA Astrophysics Data System (ADS)

Rescigno, Tn

1997-10-01

The past few years have witnessed tremendous progress in the development of sophisticated ab initio methods for treating collisions of slow electrons with isolated small molecules. Researchers in this area have benefited greatly from advances in computer technology; indeed, the advent of parallel computers has made it possible to carry out calculations at a level of sophistication inconceivable a decade ago. But bigger and faster computers are only part of the picture. Even with today's computers, the practical need to study electron collisions with the kinds of complex molecules and fragments encountered in real-world plasma processing environments is taxing present methods beyond their current capabilities. Since extrapolation of existing methods to handle increasingly larger targets will ultimately fail as it would require computational resources beyond any imagined, continued progress must also be linked to new theoretical developments. Some of the techniques recently introduced to address these problems will be discussed and illustrated with examples of electron-molecule collision calculations we have carried out on some fairly complex target gases encountered in processing plasmas. Electron-molecule scattering continues to pose many formidable theoretical and computational challenges. I will touch on some of the outstanding open questions.

Two-dimensional model of resonant electron collisions with diatomic molecules and molecular cations

NASA Astrophysics Data System (ADS)

Vana, Martin; Hvizdos, David; Houfek, Karel; Curik, Roman; Greene, Chris H.; Rescigno, Thomas N.; McCurdy, C. William

2016-05-01

A simple model for resonant collisions of electrons with diatomic molecules with one electronic and one nuclear degree of freedom (2D model) which was solved numerically exactly within the time-independent approach was used to probe the local complex potential approximation and nonlocal approximation to nuclear dynamics of these collisions. This model was reformulated in the time-dependent picture and extended to model also electron collisions with molecular cations, especially with H2+.This model enables an assessment of approximate methods, such as the boomerang model or the frame transformation theory. We will present both time-dependent and time-independent results and show how we can use the model to extract deeper insight into the dynamics of the resonant collisions.

Resonant inelastic collisions of electrons with diatomic molecules

NASA Astrophysics Data System (ADS)

Houfek, Karel

2012-05-01

In this contribution we give a review of applications of the nonlocal resonance theory which has been successfully used for treating the nuclear dynamics of low-energy electron collisions with diatomic molecules over several decades. We give examples and brief explanations of various structures observed in the cross sections of vibrational excitation and dissociative electron attachment to diatomic molecules such as threshold peaks, boomerang oscillations below the dissociative attachment threshold, or outer-well resonances.

Fe(+) chemical ionization of peptides.

PubMed

Speir, J P; Gorman, G S; Amster, I J

1993-02-01

Laser-desorbed peptide neutral molecules were allowed to react with Fe(+) in a Fourier transform mass spectrometer, using the technique of laser desorption/chemical ionization. The Fe(+) ions are formed by laser ablation of a steel target, as well as by dissociative charge-exchange ionization of ferrocene with Ne(+). Prior to reaction with laser-desorbed peptide molecules, Fe(+) ions undergo 20-100 thermalizin collisions with xenon to reduce the population of excited-state metal ion species. The Fe(+) ions that have not experienced thermalizing collisions undergo charge exchange with peptide molecules. Iron ions that undergo thermalizing collisions before they are allowed to react with peptides are found to undergo charge exchange and to form adduct species [M + Fe(+)] and fragment ions that result from the loss of small, stable molecules, such as H2O, CO, and CO2, from the metal ion-peptide complex.

Particle behavior simulation in thermophoresis phenomena by direct simulation Monte Carlo method

NASA Astrophysics Data System (ADS)

Wada, Takao

2014-07-01

A particle motion considering thermophoretic force is simulated by using direct simulation Monte Carlo (DSMC) method. Thermophoresis phenomena, which occur for a particle size of 1 μm, are treated in this paper. The problem of thermophoresis simulation is computation time which is proportional to the collision frequency. Note that the time step interval becomes much small for the simulation considering the motion of large size particle. Thermophoretic forces calculated by DSMC method were reported, but the particle motion was not computed because of the small time step interval. In this paper, the molecule-particle collision model, which computes the collision between a particle and multi molecules in a collision event, is considered. The momentum transfer to the particle is computed with a collision weight factor, where the collision weight factor means the number of molecules colliding with a particle in a collision event. The large time step interval is adopted by considering the collision weight factor. Furthermore, the large time step interval is about million times longer than the conventional time step interval of the DSMC method when a particle size is 1 μm. Therefore, the computation time becomes about one-millionth. We simulate the graphite particle motion considering thermophoretic force by DSMC-Neutrals (Particle-PLUS neutral module) with above the collision weight factor, where DSMC-Neutrals is commercial software adopting DSMC method. The size and the shape of the particle are 1 μm and a sphere, respectively. The particle-particle collision is ignored. We compute the thermophoretic forces in Ar and H2 gases of a pressure range from 0.1 to 100 mTorr. The results agree well with Gallis' analytical results. Note that Gallis' analytical result for continuum limit is the same as Waldmann's result.

State-to-state time-of-flight measurements of NO scattering from Au(111): direct observation of translation-to-vibration coupling in electronically nonadiabatic energy transfer.

PubMed

Golibrzuch, Kai; Shirhatti, Pranav R; Altschäffel, Jan; Rahinov, Igor; Auerbach, Daniel J; Wodtke, Alec M; Bartels, Christof

2013-09-12

Translational motion is believed to be a spectator degree of freedom in electronically nonadiabatic vibrational energy transfer between molecules and metal surfaces, but the experimental evidence available to support this view is limited. In this work, we have experimentally determined the translational inelasticity in collisions of NO molecules with a single-crystal Au(111) surface-a system with strong electronic nonadiabaticity. State-to-state molecular beam surface scattering was combined with an IR-UV double resonance scheme to obtain high-resolution time-of-flight data. The measurements include vibrationally elastic collisions (v = 3→3, 2→2) as well as collisions where one or two quanta of molecular vibration are excited (2→3, 2→4) or de-excited (2→1, 3→2, 3→1). In addition, we have carried out comprehensive measurements of the effects of rotational excitation on the translational energy of the scattered molecules. We find that under all conditions of this work, the NO molecules lose a large fraction (∼0.45) of their incidence translational energy to the surface. Those molecules that undergo vibrational excitation (relaxation) during the collision recoil slightly slower (faster) than vibrationally elastically scattered molecules. The amount of translational energy change depends on the surface temperature. The translation-to-rotation coupling, which is well-known for v = 0→0 collisions, is found to be significantly weaker for vibrationally inelastic than elastic channels. Our results clearly show that the spectator view of the translational motion in electronically nonadiabatic vibrational energy transfer between NO and Au(111) is only approximately correct.

Adiabatic Variational Theory for Cold Atom-Molecule Collisions: Application to a Metastable Helium Atom Colliding with ortho- and para-Hydrogen Molecules.

PubMed

Pawlak, Mariusz; Shagam, Yuval; Klein, Ayelet; Narevicius, Edvardas; Moiseyev, Nimrod

2017-03-16

We recently developed an adiabatic theory for cold molecular collision experiments. In our previous application of this theory ( Pawlak, M.; et al. J. Chem. Phys. 2015 , 143 , 074114 ), we assumed that during the experiment the collision of an atom with a diatom takes place when the diatom is in the ground rotational state and is located in a plane. In this paper, we present how the variational approach of the adiabatic theory for low-temperature collision experiments can be used for the study a 5D collision between the atom and the diatomic molecule with no limitations on its rotational quantum states and no plane restrictions. Moreover, we show here the dramatic differences in the measured reaction rates of He(2 3 S 1 ) + ortho/para-H 2 → He(1s 2 ) + ortho/para-H 2 + + e - resulting from the anisotropic long-range interactions in the reaction. In collisions of metastable helium with molecular hydrogen in the ground rotational state, the isotropic potential term dominates the dynamics. When the collision is with molecular hydrogen in the first excited rotational state, the nonisotropic interactions play an important role in the dynamics. The agreement of our results with the latest experimental findings ( Klein , A. ; et al. Nat. Phys. 2017 , 13 , 35 - 38 ) is very good.

Anisotropic kinetic energy release and gyroscopic behavior of CO2 super rotors from an optical centrifuge.

PubMed

Murray, Matthew J; Ogden, Hannah M; Mullin, Amy S

2017-10-21

An optical centrifuge is used to generate an ensemble of CO 2 super rotors with oriented angular momentum. The collision dynamics and energy transfer behavior of the super rotor molecules are investigated using high-resolution transient IR absorption spectroscopy. New multipass IR detection provides improved sensitivity to perform polarization-dependent transient studies for rotational states with 76 ≤ J ≤ 100. Polarization-dependent measurements show that the collision-induced kinetic energy release is spatially anisotropic and results from both near-resonant energy transfer between super rotor molecules and non-resonant energy transfer between super rotors and thermal molecules. J-dependent studies show that the extent and duration of the orientational anisotropy increase with rotational angular momentum. The super rotors exhibit behavior akin to molecular gyroscopes, wherein molecules with larger amounts of angular momentum are less likely to change their angular momentum orientation through collisions.

Anisotropic kinetic energy release and gyroscopic behavior of CO2 super rotors from an optical centrifuge

NASA Astrophysics Data System (ADS)

Murray, Matthew J.; Ogden, Hannah M.; Mullin, Amy S.

2017-10-01

An optical centrifuge is used to generate an ensemble of CO2 super rotors with oriented angular momentum. The collision dynamics and energy transfer behavior of the super rotor molecules are investigated using high-resolution transient IR absorption spectroscopy. New multipass IR detection provides improved sensitivity to perform polarization-dependent transient studies for rotational states with 76 ≤ J ≤ 100. Polarization-dependent measurements show that the collision-induced kinetic energy release is spatially anisotropic and results from both near-resonant energy transfer between super rotor molecules and non-resonant energy transfer between super rotors and thermal molecules. J-dependent studies show that the extent and duration of the orientational anisotropy increase with rotational angular momentum. The super rotors exhibit behavior akin to molecular gyroscopes, wherein molecules with larger amounts of angular momentum are less likely to change their angular momentum orientation through collisions.

IMS - MS Data Extractor

DOE Office of Scientific and Technical Information (OSTI.GOV)

2015-10-20

An automated drift time extraction and computed associated collision cross section software tool for small molecule analysis with ion mobility spectrometry-mass spectrometry (IMS-MS). The software automatically extracts drift times and computes associated collision cross sections for small molecules analyzed using ion mobility spectrometry-mass spectrometry (IMS-MS) based on a target list of expected ions provided by the user.

Ab initio R-matrix calculations of e+-molecule scattering

NASA Technical Reports Server (NTRS)

Danby, Grahame; Tennyson, Jonathan

1990-01-01

The adaptation of the molecular R-matrix method, originally developed for electron-molecule collision studies, to positron scattering is discussed. Ab initio R-matrix calculations are presented for collisions of low energy positrons with a number of diatomic systems including H2, HF and N2. Differential elastic cross sections for positron-H2 show a minimum at about 45 deg for collision energies between 0.3 and 0.5 Ryd. The calculations predict a bound state of positronHF. Calculations on inelastic processes in N2 and O2 are also discussed.

Computation of Hypersonic Shock Wave Flows of Multi-Component Reactive Gas Mixtures Using the Generalized Boltzmann Equation

DTIC Science & Technology

2009-03-27

ones like the Lennard - Jones potential with established parameters for each gas (e.g. N2 and 02), and for inelastic collisions DSMC method employs...solution of the collision integral. Lennard - Jones potential with two free parameters is used to obtain the elastic cross-section of the gas molecules...and the so called "combinatory relations" are used to obtain parameters of Lennard - Jones potential for an interaction of molecule A with molecule B

Calculation of ground state rotational populations for kinetic gas homonuclear diatomic molecules including electron-impact excitation and wall collisions.

PubMed

Farley, David R

2010-09-07

A model has been developed to calculate the ground state rotational populations of homonuclear diatomic molecules in kinetic gases, including the effects of electron-impact excitation, wall collisions, and gas feed rate. The equations are exact within the accuracy of the cross sections used and of the assumed equilibrating effect of wall collisions. It is found that the inflow of feed gas and equilibrating wall collisions can significantly affect the rotational distribution in competition with nonequilibrating electron-impact effects. The resulting steady-state rotational distributions are generally Boltzmann for N≥3, with a rotational temperature between the wall and feed gas temperatures. The N=0,1,2 rotational level populations depend sensitively on the relative rates of electron-impact excitation versus wall collision and gas feed rates.

Time-Dependent Wave Packet Dynamics Calculations of Cross Sections for Ultracold Scattering of Molecules

NASA Astrophysics Data System (ADS)

Huang, Jiayu; Liu, Shu; Zhang, Dong H.; Krems, Roman V.

2018-04-01

Because the de Broglie wavelength of ultracold molecules is very large, the cross sections for collisions of molecules at ultracold temperatures are always computed by the time-independent quantum scattering approach. Here, we report the first accurate time-dependent wave packet dynamics calculation for reactive scattering of ultracold molecules. Wave packet dynamics calculations can be applied to molecular systems with more dimensions and provide real-time information on the process of bond rearrangement and/or energy exchange in molecular collisions. Our work thus makes possible the extension of rigorous quantum calculations of ultracold reaction properties to polyatomic molecules and adds a new powerful tool for the study of ultracold chemistry.

Time-Dependent Wave Packet Dynamics Calculations of Cross Sections for Ultracold Scattering of Molecules.

PubMed

Huang, Jiayu; Liu, Shu; Zhang, Dong H; Krems, Roman V

2018-04-06

Because the de Broglie wavelength of ultracold molecules is very large, the cross sections for collisions of molecules at ultracold temperatures are always computed by the time-independent quantum scattering approach. Here, we report the first accurate time-dependent wave packet dynamics calculation for reactive scattering of ultracold molecules. Wave packet dynamics calculations can be applied to molecular systems with more dimensions and provide real-time information on the process of bond rearrangement and/or energy exchange in molecular collisions. Our work thus makes possible the extension of rigorous quantum calculations of ultracold reaction properties to polyatomic molecules and adds a new powerful tool for the study of ultracold chemistry.

Collision-induced absorption with exchange effects and anisotropic interactions: theory and application to H2 - H2.

PubMed

Karman, Tijs; van der Avoird, Ad; Groenenboom, Gerrit C

2015-02-28

We discuss three quantum mechanical formalisms for calculating collision-induced absorption spectra. First, we revisit the established theory of collision-induced absorption, assuming distinguishable molecules which interact isotropically. Then, the theory is rederived incorporating exchange effects between indistinguishable molecules. It is shown that the spectrum can no longer be written as an incoherent sum of the contributions of the different spherical components of the dipole moment. Finally, we derive an efficient method to include the effects of anisotropic interactions in the computation of the absorption spectrum. This method calculates the dipole coupling on-the-fly, which allows for the uncoupled treatment of the initial and final states without the explicit reconstruction of the many-component wave functions. The three formalisms are applied to the collision-induced rotation-translation spectra of hydrogen molecules in the far-infrared. Good agreement with experimental data is obtained. Significant effects of anisotropic interactions are observed in the far wing.

Making More-Complex Molecules Using Superthermal Atom/Molecule Collisions

NASA Technical Reports Server (NTRS)

Shortt, Brian; Chutjian, Ara; Orient, Otto

2008-01-01

A method of making more-complex molecules from simpler ones has emerged as a by-product of an experimental study in outer-space atom/surface collision physics. The subject of the study was the formation of CO2 molecules as a result of impingement of O atoms at controlled kinetic energies upon cold surfaces onto which CO molecules had been adsorbed. In this study, the O/CO system served as a laboratory model, not only for the formation of CO2 but also for the formation of other compounds through impingement of rapidly moving atoms upon molecules adsorbed on such cold interstellar surfaces as those of dust grains or comets. By contributing to the formation of increasingly complex molecules, including organic ones, this study and related other studies may eventually contribute to understanding of the origins of life.

Collisional transfer of population and orientation in NaK

NASA Astrophysics Data System (ADS)

Wolfe, C. M.; Ashman, S.; Bai, J.; Beser, B.; Ahmed, E. H.; Lyyra, A. M.; Huennekens, J.

2011-05-01

Collisional satellite lines with |ΔJ| ≤ 58 have been identified in recent polarization spectroscopy V-type optical-optical double resonance (OODR) excitation spectra of the Rb2 molecule [H. Salami et al., Phys. Rev. A 80, 022515 (2009)]. Observation of these satellite lines clearly requires a transfer of population from the rotational level directly excited by the pump laser to a neighboring level in a collision of the molecule with an atomic perturber. However to be observed in polarization spectroscopy, the collision must also partially preserve the angular momentum orientation, which is at least somewhat surprising given the extremely large values of ΔJ that were observed. In the present work, we used the two-step OODR fluorescence and polarization spectroscopy techniques to obtain quantitative information on the transfer of population and orientation in rotationally inelastic collisions of the NaK molecules prepared in the 2(A)1Σ+(v' = 16, J' = 30) rovibrational level with argon and potassium perturbers. A rate equation model was used to study the intensities of these satellite lines as a function of argon pressure and heat pipe oven temperature, in order to separate the collisional effects of argon and potassium atoms. Using a fit of this rate equation model to the data, we found that collisions of NaK molecules with potassium atoms are more likely to transfer population and destroy orientation than collisions with argon atoms. Collisions with argon atoms show a strong propensity for population transfer with ΔJ = even. Conversely, collisions with potassium atoms do not show this ΔJ = even propensity, but do show a propensity for ΔJ = positive compared to ΔJ = negative, for this particular initial state. The density matrix equations of motion have also been solved numerically in order to test the approximations used in the rate equation model and to calculate fluorescence and polarization spectroscopy line shapes. In addition, we have measured rate coefficients for broadening of NaK 31Π ← 2(A)1Σ+spectral lines due to collisions with argon and potassium atoms. Additional broadening, due to velocity changes occurring in rotationally inelastic collisions, has also been observed.

Collisional transfer of population and orientation in NaK.

PubMed

Wolfe, C M; Ashman, S; Bai, J; Beser, B; Ahmed, E H; Lyyra, A M; Huennekens, J

2011-05-07

Collisional satellite lines with |ΔJ| ≤ 58 have been identified in recent polarization spectroscopy V-type optical-optical double resonance (OODR) excitation spectra of the Rb(2) molecule [H. Salami et al., Phys. Rev. A 80, 022515 (2009)]. Observation of these satellite lines clearly requires a transfer of population from the rotational level directly excited by the pump laser to a neighboring level in a collision of the molecule with an atomic perturber. However to be observed in polarization spectroscopy, the collision must also partially preserve the angular momentum orientation, which is at least somewhat surprising given the extremely large values of ΔJ that were observed. In the present work, we used the two-step OODR fluorescence and polarization spectroscopy techniques to obtain quantitative information on the transfer of population and orientation in rotationally inelastic collisions of the NaK molecules prepared in the 2(A)(1)Σ(+)(v' = 16, J' = 30) rovibrational level with argon and potassium perturbers. A rate equation model was used to study the intensities of these satellite lines as a function of argon pressure and heat pipe oven temperature, in order to separate the collisional effects of argon and potassium atoms. Using a fit of this rate equation model to the data, we found that collisions of NaK molecules with potassium atoms are more likely to transfer population and destroy orientation than collisions with argon atoms. Collisions with argon atoms show a strong propensity for population transfer with ΔJ = even. Conversely, collisions with potassium atoms do not show this ΔJ = even propensity, but do show a propensity for ΔJ = positive compared to ΔJ = negative, for this particular initial state. The density matrix equations of motion have also been solved numerically in order to test the approximations used in the rate equation model and to calculate fluorescence and polarization spectroscopy line shapes. In addition, we have measured rate coefficients for broadening of NaK 3(1)Π ← 2(A)(1)Σ(+)spectral lines due to collisions with argon and potassium atoms. Additional broadening, due to velocity changes occurring in rotationally inelastic collisions, has also been observed.

Electron collisions with atoms, ions, molecules, and surfaces: Fundamental science empowering advances in technology

PubMed Central

Bartschat, Klaus; Kushner, Mark J.

2016-01-01

Electron collisions with atoms, ions, molecules, and surfaces are critically important to the understanding and modeling of low-temperature plasmas (LTPs), and so in the development of technologies based on LTPs. Recent progress in obtaining experimental benchmark data and the development of highly sophisticated computational methods is highlighted. With the cesium-based diode-pumped alkali laser and remote plasma etching of Si3N4 as examples, we demonstrate how accurate and comprehensive datasets for electron collisions enable complex modeling of plasma-using technologies that empower our high-technology–based society. PMID:27317740

Energy Deposition and Escape Fluxes Induced by Energetic Solar Wind Ions and ENAs Precipitating into Mars Atmosphere: Accurate Consideration of Energy Transfer Collisions

NASA Astrophysics Data System (ADS)

Kharchenko, V. A.; Lewkow, N.; Gacesa, M.

2014-12-01

Formation and evolution of neutral fluxes of atoms and molecules escaping from the Mars atmosphere have been investigated for the sputtering and photo-chemical mechanisms. Energy and momentum transfer in collisions between the atmospheric gas and fast atoms and molecules have been considered using our recently obtained angular and energy dependent cross sections[1]. We have showed that accurate angular dependent collision cross sections are critical for the description of the energy relaxation of precipitating keV energetic ions/ENAs and for computations of altitude profiles of the fast atom and molecule production rates in recoil collisions. Upward and escape fluxes of the secondary energetic He and O atoms and H2, N2, CO and CO2 molecules, induced by precipitating ENAs, have been determined and their non-thermal energy distribution functions have been computed at different altitudes for different solar conditions. Precipitation and energy deposition of the energetic H2O molecules and products of their dissociations into the Mars atmosphere in the Comet C/2013 A1 (Siding Spring) - Mars interaction have been modeled using accurate cross sections. Reflection of precipitating ENAs by the Mars atmosphere has been analyzed in detail. [1] N. Lewkow and V. Kharchenko, "Precipitation of Energetic Neutral Atoms and Escape Fluxes induced from the Mars Atmosphere, ApJ, v.790, p.98 (2014).

Space Dust Collisions as a Planetary Escape Mechanism.

PubMed

Berera, Arjun

2017-12-01

It is observed that hypervelocity space dust, which is continuously bombarding Earth, creates immense momentum flows in the atmosphere. Some of this fast space dust inevitably will interact with the atmospheric system, transferring energy and moving particles around, with various possible consequences. This paper examines, with supporting estimates, the possibility that by way of collisions the Earth-grazing component of space dust can facilitate planetary escape of atmospheric particles, whether they are atoms and molecules that form the atmosphere or larger-sized particles. An interesting outcome of this collision scenario is that a variety of particles that contain telltale signs of Earth's organic story, including microbial life and life-essential molecules, may be "afloat" in Earth's atmosphere. The present study assesses the capability of this space dust collision mechanism to propel some of these biological constituents into space. Key Words: Hypervelocity space dust-Collision-Planetary escape-Atmospheric constituents-Microbial life. Astrobiology 17, 1274-1282.

Electrondriven processes in polyatomic molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

McKoy, Vincent

2017-03-20

This project developed and applied scalable computational methods to obtain information about low-energy electron collisions with larger polyatomic molecules. Such collisions are important in modeling radiation damage to living systems, in spark ignition and combustion, and in plasma processing of materials. The focus of the project was to develop efficient methods that could be used to obtain both fundamental scientific insights and data of practical value to applications.

Cold chemistry with cold molecules

NASA Astrophysics Data System (ADS)

Shagam, Yuval

Low temperature chemistry has been predicted to be dominated by quantum effects, such as shape resonances, where colliding particles exhibit wave-like behavior and tunnel through potential barriers. Observation of these quantum effects provides valuable insight into the microscopic mechanism that governs scattering processes. Our recent advances in the control of neutral supersonic molecular beams, namely merged beam experiments, have enabled continuous tuning of collision energies from the classical regime at room temperature down to 0.01 kelvin, where a quantum description of the dynamics is necessary. I will discuss our use of this technique to study how the dynamics change when molecules participate in collisions, demonstrating the crucial role the molecular quantum rotor plays. We have found that at low temperatures rotational state of the molecule can strongly affect collision dynamics considerably changing reaction rates, due to the different symmetries of the molecular wavefunction.

Quantum effects in the capture of charged particles by dipolar polarizable symmetric top molecules. I. General axially nonadiabatic channel treatment.

PubMed

Auzinsh, M; Dashevskaya, E I; Litvin, I; Nikitin, E E; Troe, J

2013-08-28

The rate coefficients for capture of charged particles by dipolar polarizable symmetric top molecules in the quantum collision regime are calculated within an axially nonadiabatic channel approach. It uses the adiabatic approximation with respect to rotational transitions of the target within first-order charge-dipole interaction and takes into account the gyroscopic effect that decouples the intrinsic angular momentum from the collision axis. The results are valid for a wide range of collision energies (from single-wave capture to the classical limit) and dipole moments (from the Vogt-Wannier and fly-wheel to the adiabatic channel limit).

Analysis of a semiclassical model for rotational transition probabilities. [in highly nonequilibrium flow of diatomic molecules

NASA Technical Reports Server (NTRS)

Deiwert, G. S.; Yoshikawa, K. K.

1975-01-01

A semiclassical model proposed by Pearson and Hansen (1974) for computing collision-induced transition probabilities in diatomic molecules is tested by the direct-simulation Monte Carlo method. Specifically, this model is described by point centers of repulsion for collision dynamics, and the resulting classical trajectories are used in conjunction with the Schroedinger equation for a rigid-rotator harmonic oscillator to compute the rotational energy transition probabilities necessary to evaluate the rotation-translation exchange phenomena. It is assumed that a single, average energy spacing exists between the initial state and possible final states for a given collision.

Rotational relaxation of CS by collision with ortho- and para-H{sub 2} molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Denis-Alpizar, Otoniel; Departamento de Física, Universidad de Matanzas, Matanzas 40100; Stoecklin, Thierry, E-mail: t.stoecklin@ism.u-bordeaux1.fr

Quantum mechanical investigation of the rotationally inelastic collisions of CS with ortho- and para-H{sub 2} molecules is reported. The new global four-dimensional potential energy surface presented in our recent work is used. Close coupling scattering calculations are performed in the rigid rotor approximation for ortho- and para-H{sub 2} colliding with CS in the j = 0–15 rotational levels and for collision energies ranging from 10{sup −2} to 10{sup 3} cm{sup −1}. The cross sections and rate coefficients for selected rotational transitions of CS are compared with the ones previously reported for the collision of CS with He. The largest discrepanciesmore » are observed at low collision energy, below 1 cm{sup −1}. Above 10 cm{sup −1}, the approximation using the square root of the relative mass of the colliders to calculate the cross sections between a molecule and H{sub 2} from the data available with {sup 4}He is found to be a good qualitative approximation. The rate coefficients calculated with the electron gas model for the He-CS system show more discrepancy with our accurate results. However, scaling up these rates by a factor of 2 gives a qualitative agreement.« less

A quasi-classical study of energy transfer in collisions of hyperthermal H atoms with SO2 molecules.

PubMed

da Silva, Ramon S; Garrido, Juan D; Ballester, Maikel Y

2017-08-28

A deep understanding of energy transfer processes in molecular collisions is at central attention in physical chemistry. Particularly vibrational excitation of small molecules colliding with hot light atoms, via a metastable complex formation, has shown to be an efficient manner of enhancing reactivity. A quasi-classical trajectory study of translation-to-vibration energy transfer (T-V ET) in collisions of hyperthermal H( 2 S) atoms with SO 2 (X̃ 1 A ' ) molecules is presented here. For such a study, a double many-body expansion potential energy surface previously reported for HSO 2 ( 2 A) is used. This work was motivated by recent experiments by Ma et al. studying collisions of H + SO 2 at the translational energy of 59 kcal/mol [J. Ma et al., Phys. Rev. A 93, 040702 (2016)]. Calculations reproduce the experimental evidence that during majority of inelastic non-reactive collision processes, there is a metastable intermediate formation (HOSO or HSO 2 ). Nevertheless, the analysis of the trajectories shows that there are two distinct mechanisms in the T-V ET process: direct and indirect. Direct T-V processes are responsible for the high population of SO 2 with relatively low vibrational excitation energy, while indirect ones dominate the conversion from translational energy to high values of the vibrational counterpart.

Calculation of total cross sections for charge exchange in molecular collisions

NASA Technical Reports Server (NTRS)

Ioup, J.

1979-01-01

Areas of investigation summarized include nitrogen ion-nitrogen molecule collisions; molecular collisions with surfaces; molecular identification from analysis of cracking patterns of selected gases; computer modelling of a quadrupole mass spectrometer; study of space charge in a quadrupole; transmission of the 127 deg cylindrical electrostatic analyzer; and mass spectrometer data deconvolution.

Rotational excitation of hydrogen molecules by collisions with hydrogen atoms. [interstellar gas energetics

NASA Technical Reports Server (NTRS)

Green, S.; Truhlar, D. G.

1979-01-01

Rate constants for rotational excitation of hydrogen molecules by collisions with hydrogen atoms have been obtained from quantum-mechanical calculations for kinetic temperatures between 100 and 5000 K. These calculations involve the rigid-rotator approximation, but other possible sources of error should be small. The calculations indicate that the early values of Nishimura are larger than accurate rigid-rotator values by about a factor of 20 or more.

Efficient quantum-classical method for computing thermal rate constant of recombination: application to ozone formation.

PubMed

Ivanov, Mikhail V; Babikov, Dmitri

2012-05-14

Efficient method is proposed for computing thermal rate constant of recombination reaction that proceeds according to the energy transfer mechanism, when an energized molecule is formed from reactants first, and is stabilized later by collision with quencher. The mixed quantum-classical theory for the collisional energy transfer and the ro-vibrational energy flow [M. Ivanov and D. Babikov, J. Chem. Phys. 134, 144107 (2011)] is employed to treat the dynamics of molecule + quencher collision. Efficiency is achieved by sampling simultaneously (i) the thermal collision energy, (ii) the impact parameter, and (iii) the incident direction of quencher, as well as (iv) the rotational state of energized molecule. This approach is applied to calculate third-order rate constant of the recombination reaction that forms the (16)O(18)O(16)O isotopomer of ozone. Comparison of the predicted rate vs. experimental result is presented.

Absolute fragmentation cross sections in atom-molecule collisions: Scaling laws for non-statistical fragmentation of polycyclic aromatic hydrocarbon molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, T.; Gatchell, M.; Stockett, M. H.

2014-06-14

We present scaling laws for absolute cross sections for non-statistical fragmentation in collisions between Polycyclic Aromatic Hydrocarbons (PAH/PAH{sup +}) and hydrogen or helium atoms with kinetic energies ranging from 50 eV to 10 keV. Further, we calculate the total fragmentation cross sections (including statistical fragmentation) for 110 eV PAH/PAH{sup +} + He collisions, and show that they compare well with experimental results. We demonstrate that non-statistical fragmentation becomes dominant for large PAHs and that it yields highly reactive fragments forming strong covalent bonds with atoms (H and N) and molecules (C{sub 6}H{sub 5}). Thus nonstatistical fragmentation may be an effectivemore » initial step in the formation of, e.g., Polycyclic Aromatic Nitrogen Heterocycles (PANHs). This relates to recent discussions on the evolution of PAHNs in space and the reactivities of defect graphene structures.« less

Space Dust Collisions as a Planetary Escape Mechanism

NASA Astrophysics Data System (ADS)

Berera, Arjun

2017-12-01

It is observed that hypervelocity space dust, which is continuously bombarding Earth, creates immense momentum flows in the atmosphere. Some of this fast space dust inevitably will interact with the atmospheric system, transferring energy and moving particles around, with various possible consequences. This paper examines, with supporting estimates, the possibility that by way of collisions the Earth-grazing component of space dust can facilitate planetary escape of atmospheric particles, whether they are atoms and molecules that form the atmosphere or larger-sized particles. An interesting outcome of this collision scenario is that a variety of particles that contain telltale signs of Earth's organic story, including microbial life and life-essential molecules, may be "afloat" in Earth's atmosphere. The present study assesses the capability of this space dust collision mechanism to propel some of these biological constituents into space.

Radiative-emission analysis in charge-exchange collisions of O6 + with argon, water, and methane

NASA Astrophysics Data System (ADS)

Leung, Anthony C. K.; Kirchner, Tom

2017-04-01

Processes of electron capture followed by Auger and radiative decay were investigated in slow ion-atom and -molecule collisions. A quantum-mechanical analysis which utilizes the basis generator method within an independent electron model was carried out for collisions of O 6 + with Ar, H2O , and CH4 at impact energies of 1.17 and 2.33 keV/amu. At these impact energies, a closure approximation in the spectral representation of the Hamiltonian for molecules was found to be necessary to yield reliable results. Total single-, double-, and triple-electron-capture cross sections obtained show good agreement with previous measurements and calculations using the classical trajectory Monte Carlo method. The corresponding emission spectra from single capture for each collision system are in satisfactory agreement with previous calculations.

[Study on X-ray powder diffraction of various structured zinc titanate prepared by the method of direct precipitation].

PubMed

Guo, Jian; Wang, Zhi-hua; Tao, Dong-liang; Guo, Guang-sheng

2007-05-01

Zinc titanate powders were prepared from Ti(SO4)2, Zn(NO3)2 x (6)H2O and (NH4)2CO3 by the method of direct precipitation. The effects of reaction conditions on the structure of zinc titanate were studied. The sample was analyzed by means of XRD and TG-DTA. The structure of zinc titanate was affected by the reaction subsequence of the formation of titanic acid and zinc carbonate. In the reaction system where titanic acid was generated earlier, collision reaction occurred between the generated zinc carbonate molecule and the surrounding titanic acid molecule. When titanic acid was generated earlier and precipitant (NH4)2CO3 was sufficient, Zn2Ti3O8 was obtained because of the sufficient collision reaction and superfluous titanic acid. In the reaction system where zinc carbonate was generated earlier, collision reaction occurred between the generated titanic acid molecule and the surrounding zinc carbonate molecule. When zinc carbonate was generated earlier and precipitant (NH4)2CO3 was sufficient, Zn2TiO4 was obtained because of the sufficient collision reaction and superfluous zinc carbonate. In addition, the kinds and structure of the production were affected by the dosage of precipitant and the reaction temperature. Zn2Ti3O8 or Zn2TiO4 could be obtained easier when using more precipitant or higher reaction temperature which could cause more sufficient collision reaction. ZnTiO3 could be obtained under the conditions of less precipitant and lower reaction temperature.

O2-O2 and O2-N2 collision-induced absorption mechanisms unravelled

NASA Astrophysics Data System (ADS)

Karman, Tijs; Koenis, Mark A. J.; Banerjee, Agniva; Parker, David H.; Gordon, Iouli E.; van der Avoird, Ad; van der Zande, Wim J.; Groenenboom, Gerrit C.

2018-05-01

Collision-induced absorption is the phenomenon in which interactions between colliding molecules lead to absorption of light, even for transitions that are forbidden for the isolated molecules. Collision-induced absorption contributes to the atmospheric heat balance and is important for the electronic excitations of O2 that are used for remote sensing. Here, we present a theoretical study of five vibronic transitions in O2-O2 and O2-N2, using analytical models and numerical quantum scattering calculations. We unambiguously identify the underlying absorption mechanism, which is shown to depend explicitly on the collision partner—contrary to textbook knowledge. This explains experimentally observed qualitative differences between O2-O2 and O2-N2 collisions in the overall intensity, line shape and vibrational dependence of the absorption spectrum. It is shown that these results can be used to discriminate between conflicting experimental data and even to identify unphysical results, thus impacting future experimental studies and atmospheric applications.

Sympathetic cooling of polyatomic molecules with S-state atoms in a magnetic trap.

PubMed

Tscherbul, T V; Yu, H-G; Dalgarno, A

2011-02-18

We present a rigorous theoretical study of low-temperature collisions of polyatomic molecular radicals with (1)S(0) atoms in the presence of an external magnetic field. Accurate quantum scattering calculations based on ab initio and scaled interaction potentials show that collision-induced spin relaxation of the prototypical organic molecule CH(2)(X(3)B(1)) (methylene) and nine other triatomic radicals in cold (3)He gas occurs at a slow rate, demonstrating that cryogenic buffer-gas cooling and magnetic trapping of these molecules is feasible with current technology. Our calculations further suggest that it may be possible to create ultracold gases of polyatomic molecules by sympathetic cooling with alkaline-earth atoms in a magnetic trap.

Impulsive Collision Dynamics of CO Super Rotors from an Optical Centrifuge.

PubMed

Murray, Matthew J; Ogden, Hannah M; Toro, Carlos; Liu, Qingnan; Mullin, Amy S

2016-11-18

We report state-resolved collision dynamics for CO molecules prepared in an optical centrifuge and measured with high-resolution transient IR absorption spectroscopy. Time-resolved polarization-sensitive measurements of excited CO molecules in the J=29 rotational state reveal that the oriented angular momentum of CO rotors is relaxed by impulsive collisions. The translational energy gains for molecules in the initial plane of rotation are threefold larger than for randomized angular momentum orientations, indicating the presence of anisotropic kinetic energy. The transient data show enhanced population for CO molecules in the initial plane of rotation immediately following the optical centrifuge pulse. A comparison with previous CO 2 super rotor studies illustrates the behavior of molecular gyroscopes; spatial reorientation of CO 2 J=76 rotors takes substantially longer than that for CO J=29 rotors, despite similarities in classical rotational period and rotational energy gap. High-resolution transient IR absorption measurements of the CO J=29-39 rotational states show that the collisional depopulation rates increase with J quantum number. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Imaging chemical reactions - 3D velocity mapping

NASA Astrophysics Data System (ADS)

Chichinin, A. I.; Gericke, K.-H.; Kauczok, S.; Maul, C.

Visualising a collision between an atom or a molecule or a photodissociation (half-collision) of a molecule on a single particle and single quantum level is like watching the collision of billiard balls on a pool table: Molecular beams or monoenergetic photodissociation products provide the colliding reactants at controlled velocity before the reaction products velocity is imaged directly with an elaborate camera system, where one should keep in mind that velocity is, in general, a three-dimensional (3D) vectorial property which combines scattering angles and speed. If the processes under study have no cylindrical symmetry, then only this 3D product velocity vector contains the full information of the elementary process under study.

A general method for controlling and resolving rotational orientation of molecules in molecule-surface collisions

PubMed Central

Godsi, Oded; Corem, Gefen; Alkoby, Yosef; Cantin, Joshua T.; Krems, Roman V.; Somers, Mark F.; Meyer, Jörg; Kroes, Geert-Jan; Maniv, Tsofar; Alexandrowicz, Gil

2017-01-01

The outcome of molecule–surface collisions can be modified by pre-aligning the molecule; however, experiments accomplishing this are rare because of the difficulty of preparing molecules in aligned quantum states. Here we present a general solution to this problem based on magnetic manipulation of the rotational magnetic moment of the incident molecule. We apply the technique to the scattering of H2 from flat and stepped copper surfaces. We demonstrate control of the molecule's initial quantum state, allowing a direct comparison of differences in the stereodynamic scattering from the two surfaces. Our results show that a stepped surface exhibits a much larger dependence of the corrugation of the interaction on the alignment of the molecule than the low-index surface. We also demonstrate an extension of the technique that transforms the set-up into an interferometer, which is sensitive to molecular quantum states both before and after the scattering event. PMID:28480890

Molecular Growth Inside of Polycyclic Aromatic Hydrocarbon Clusters Induced by Ion Collisions.

PubMed

Delaunay, Rudy; Gatchell, Michael; Rousseau, Patrick; Domaracka, Alicja; Maclot, Sylvain; Wang, Yang; Stockett, Mark H; Chen, Tao; Adoui, Lamri; Alcamí, Manuel; Martín, Fernando; Zettergren, Henning; Cederquist, Henrik; Huber, Bernd A

2015-05-07

The present work combines experimental and theoretical studies of the collision between keV ion projectiles and clusters of pyrene, one of the simplest polycyclic aromatic hydrocarbons (PAHs). Intracluster growth processes induced by ion collisions lead to the formation of a wide range of new molecules with masses larger than that of the pyrene molecule. The efficiency of these processes is found to strongly depend on the mass and velocity of the incoming projectile. Classical molecular dynamics simulations of the entire collision process-from the ion impact (nuclear scattering) to the formation of new molecular species-reproduce the essential features of the measured molecular growth process and also yield estimates of the related absolute cross sections. More elaborate density functional tight binding calculations yield the same growth products as the classical simulations. The present results could be relevant to understand the physical chemistry of the PAH-rich upper atmosphere of Saturn's moon Titan.

The effect of electron collisions on rotational populations of cometary water

NASA Technical Reports Server (NTRS)

Xie, Xingfa; Mumma, Michael J.

1992-01-01

The e-H2O collisional rate for exciting rotational transitions in cometary water is evaluated for conditions found in Comet Halley during the Giotto spacecraft encounter. In the case of the 0(00)-1(11) rotational transition, the e-H2O collisional rate exceeds that for excitation by neutral-neutral collisions at distances exceeding 3000 km from the cometary nucleus. The estimates are based on theoretical and experimental studies of e-H2O collisions, on ion and electron parameters acquired in situ by instruments on the Giotto and Vega spacecraft, and on results obtained from models of the cometary ionosphere. Thus, the rotational temperature of the water molecule in the intermediate coma may be controlled by collisions with electrons rather than with neutral molecules, and the rotational temperature retrieved from high-resolution IR spectra of water in Comet Halley may reflect electron temperatures rather than neutral gas temperatures in the intermediate coma.

Trajectory study of supercollision relaxation in highly vibrationally excited pyrazine and CO2.

PubMed

Li, Ziman; Sansom, Rebecca; Bonella, Sara; Coker, David F; Mullin, Amy S

2005-09-01

Classical trajectory calculations were performed to simulate state-resolved energy transfer experiments of highly vibrationally excited pyrazine (E(vib) = 37,900 cm(-1)) and CO(2), which were conducted using a high-resolution transient infrared absorption spectrometer. The goal here is to use classical trajectories to simulate the supercollision energy transfer pathway wherein large amounts of energy are transferred in single collisions in order to compare with experimental results. In the trajectory calculations, Newton's laws of motion are used for the molecular motion, isolated molecules are treated as collections of harmonic oscillators, and intermolecular potentials are formed by pairwise Lennard-Jones potentials. The calculations qualitatively reproduce the observed energy partitioning in the scattered CO(2) molecules and show that the relative partitioning between bath rotation and translation is dependent on the moment of inertia of the bath molecule. The simulations show that the low-frequency modes of the vibrationally excited pyrazine contribute most to the strong collisions. The majority of collisions lead to small DeltaE values and primarily involve single encounters between the energy donor and acceptor. The large DeltaE exchanges result from both single impulsive encounters and chattering collisions that involve multiple encounters.

Fragmentation of tetrahydrofuran molecules by H(+), C(+), and O(+) collisions at the incident energy range of 25-1000 eV.

PubMed

Wasowicz, Tomasz J; Pranszke, Bogusław

2015-01-29

We have studied fragmentation processes of the gas-phase tetrahydrofuran (THF) molecules in collisions with the H(+), C(+), and O(+) cations. The collision energies have been varied between 25 and 1000 eV and thus covered a velocity range from 10 to 440 km/s. The following excited neutral fragments of THF have been observed: the atomic hydrogen H(n), n = 4-9, carbon atoms in the 2p3s (1)P1, 2p4p (1)D2, and 2p4p (3)P states and vibrationally and rotationally excited diatomic CH fragments in the A(2)Δ and B(2)Σ(-) states. Fragmentation yields of these excited fragments have been measured as functions of the projectile energy (velocity). Our results show that the fragmentation mechanism depends on the projectile cations and is dominated by electron transfer from tetrahydrofuran molecules to cations. It has been additionally hypothesized that in the C(+)+THF collisions a [C-C4H8O](+) complex is formed prior to dissociation. The possible reaction channels involved in fragmentation of THF under the H(+), C(+), and O(+) cations impact are also discussed.

Translational Entanglement and Teleportation of Matter Wavepackets by Collisions and Half-Collisions

NASA Astrophysics Data System (ADS)

Fisch, L.; Tal, A.; Kurizki, G.

To date, the translationally-entangled state originally proposed by Einstein, Podolsky and Rosen (EPR) in 1935 has not been experimentally realized for massive particles. Opatrný and Kurizki [Phys. Rev. Lett. 86, 3180 (2000)] have suggested the creation of a position- and momentum-correlated, i.e., translationally-entangled, pair of particles approximating the EPR state by dissociation of cold diatomic molecules, and further manipulation of the EPR pair effecting matter-wave teleportation. Here we aim at setting the principles of and quantifying translational entanglement by collisions and half-collisions. In collisions, the resonance width s and the initial phase-space distributions are shown to determine the degree of post-collisional momentum entanglement. Half-collisions (dissociation) are shown to yield different types of approximate EPR states. We analyse a feasible realization of translational EPR entanglement and teleportation via cold-molecule Raman dissociation and subsequent collisions, resolving both practical and conceptual difficulties it has faced so far: How to avoid entanglement loss due to the wavepacket spreading of the dissociation fragments? How to measure both position and momentum correlations of the dissociation fragments with sufficient accuracy to verify their EPR correlations? How to reliably perform two-particle (Bell) position and momentum measurements on one of the fragments and the wavepacket to be teleported?

Negative ion formation in potassium-nitromethane collisions.

PubMed

Antunes, R; Almeida, D; Martins, G; Mason, N J; Garcia, G; Maneira, M J P; Nunes, Y; Limão-Vieira, P

2010-10-21

Ion-pair formation in gaseous nitromethane (CH(3)NO(2)) induced by electron transfer has been studied by investigating the products of collisions between fast potassium atoms and nitromethane molecules using a crossed molecular-beam technique. The negative ions formed in such collisions were analysed using time-of-flight mass spectroscopy. The six most dominant product anions are NO(2)(-), O(-), CH(3)NO(2)(-), OH(-), CH(2)NO(2)(-) and CNO(-). By using nitromethane-d(3) (CD(3)NO(2)), we found that previous mass 17 amu assignment to O(-) delayed fragment, is in the present experiment may be unambiguously assigned to OH(-). The formation of CH(2)NO(2)(-) may be explained in terms of dissociative electron attachment to highly vibrationally excited molecules.

Spectroscopy and Chemistry of Cold Molecules

NASA Astrophysics Data System (ADS)

Momose, Takamasa

2012-06-01

Molecules at low temperatures are expected to behave quite differently from those at high temperatures because pronounced quantum effects emerge from thermal averages. Even at 10 K, a significant enhancement of reaction cross section is expected due to tunneling and resonance effects. Chemistry at this temperature is very important in order to understand chemical reactions in interstellar molecular clouds. At temperatures lower than 1 K, collisions and intermolecular interactions become qualitatively different from those at high temperatures because of the large thermal de Broglie wavelength of molecules. Collisions at these temperatures must be treated as the interference of molecular matter waves, but not as hard sphere collisions. A Bose-Einstein condensate is a significant state of matter as a result of coherent matter wave interaction. Especially, dense para-H_2 molecules are predicted to become a condensate even around 1 K. A convenient method to investigate molecules around 1 K is to dope molecules in cold matrices. Among various matrices, quantum hosts such as solid para-H_2 and superfluid He nano-droplets have been proven to be an excellent host for high-resolution spectroscopy. Rovibrational motion of molecules in these quantum hosts is well quantized on account of the weak interactions and the softness of quantum environment. The linewidths of infrared spectra of molecules in the quantum hosts are extremely narrow compared with those in other matrices. The sharp linewidths allow us to resolve fine spectral structures originated in subtle interactions between guest and host molecules. In this talk, I will describe how the splitting and lineshape of high-resolution spectra of molecules in quantum hosts give us new information on the static and dynamical interactions of molecules in quantum medium. The topics include dynamical response of superfluid environment upon rotational excitation, and possible superfluid phase of para-H_2 clusters. I will also describe our current efforts to make free cold molecules for the study of cold chemistry.

Physical re-examination of parameters on a molecular collisions-based diffusion model for diffusivity prediction in polymers.

PubMed

Ohashi, Hidenori; Tamaki, Takanori; Yamaguchi, Takeo

2011-12-29

Molecular collisions, which are the microscopic origin of molecular diffusive motion, are affected by both the molecular surface area and the distance between molecules. Their product can be regarded as the free space around a penetrant molecule defined as the "shell-like free volume" and can be taken as a characteristic of molecular collisions. On the basis of this notion, a new diffusion theory has been developed. The model can predict molecular diffusivity in polymeric systems using only well-defined single-component parameters of molecular volume, molecular surface area, free volume, and pre-exponential factors. By consideration of the physical description of the model, the actual body moved and which neighbor molecules are collided with are the volume and the surface area of the penetrant molecular core. In the present study, a semiempirical quantum chemical calculation was used to calculate both of these parameters. The model and the newly developed parameters offer fairly good predictive ability. © 2011 American Chemical Society

Gaussian process model for extrapolation of scattering observables for complex molecules: From benzene to benzonitrile

NASA Astrophysics Data System (ADS)

Cui, Jie; Li, Zhiying; Krems, Roman V.

2015-10-01

We consider a problem of extrapolating the collision properties of a large polyatomic molecule A-H to make predictions of the dynamical properties for another molecule related to A-H by the substitution of the H atom with a small molecular group X, without explicitly computing the potential energy surface for A-X. We assume that the effect of the -H →-X substitution is embodied in a multidimensional function with unknown parameters characterizing the change of the potential energy surface. We propose to apply the Gaussian Process model to determine the dependence of the dynamical observables on the unknown parameters. This can be used to produce an interval of the observable values which corresponds to physical variations of the potential parameters. We show that the Gaussian Process model combined with classical trajectory calculations can be used to obtain the dependence of the cross sections for collisions of C6H5CN with He on the unknown parameters describing the interaction of the He atom with the CN fragment of the molecule. The unknown parameters are then varied within physically reasonable ranges to produce a prediction uncertainty of the cross sections. The results are normalized to the cross sections for He — C6H6 collisions obtained from quantum scattering calculations in order to provide a prediction interval of the thermally averaged cross sections for collisions of C6H5CN with He.

Methylation effects in state resolved quenching of highly vibrationally excited azabenzenes (Evib˜38 500 cm-1). I. Collisions with water

NASA Astrophysics Data System (ADS)

Elioff, Michael S.; Fang, Maosen; Mullin, Amy S.

2001-10-01

To investigate the role of molecular structure in collisions that quench highly vibrationally excited molecules, we have performed state resolved transient infrared absorption studies of energy gain in a number of rotational levels of H2O(000) resulting from collisions of water with vibrationally excited 2-methylpyridine (2-picoline) and 2,6-dimethylpyridine (2,6-lutidine) in a low-pressure gas-phase environment at 298 K. Vibrationally excited methylpyridines were prepared with ˜38 500 cm-1 of internal energy using 266 nm ultraviolet excitation to an S1 electronic state followed by rapid radiationless decay to the S0 electronic state. Collisions that populate rotationally excited states of H2O(000) were investigated with infrared absorption by monitoring the appearance of individual rotational states of H2O(000) with energies between 1000 and 2000 cm-1. Rotational state distributions for recoiling water molecules were characterized by Boltzmann temperatures of Trot=590±90 K for quenching of hot picoline and Trot=490±80 K for lutidine quenching. Doppler-broadened transient absorption line profiles show that the scattered H2O(000) molecules have laboratory-frame translational energy distributions corresponding to Ttrans≈600 K for deactivation of picoline and Ttrans≈590 K for lutidine. Energy transfer rate constant measurements indicate that rotational excitation of H2O(000) with Evib>1000 cm-1 occurs for one in 31 picoline/water collisions and one in 17 lutidine/water collisions. Comparison with earlier quenching studies on pyrazine [M. Fraelich, M. S. Elioff, and A. S. Mullin, J. Phys. Chem. 102, 9761 (1998)] and pyridine [M. S. Elioff, M. Fraelich, R. L. Sansom, and A. S. Mullin, J. Chem. Phys. 111, 3517 (1999)] indicate that, for the same initial internal energy in the hot donor, the extent of rotational excitation in water is diminished as the number of vibrational modes in the donor increases. The energy transfer probability for this pathway exhibits opposite behavior, with the larger donor molecules being more likely to excite the high energy rotations in water. These results are interpreted using a statistical description of the high energy donors and highlight the role of low frequency vibrational modes in the vibrationally hot donor molecules. A Fermi's golden rule approach is successful at explaining differences in the observed scattering dynamics for the various donor molecules.

Rotational excitation of HCN by para- and ortho-H₂.

PubMed

Vera, Mario Hernández; Kalugina, Yulia; Denis-Alpizar, Otoniel; Stoecklin, Thierry; Lique, François

2014-06-14

Rotational excitation of the hydrogen cyanide (HCN) molecule by collisions with para-H2(j = 0, 2) and ortho-H2(j = 1) is investigated at low temperatures using a quantum time independent approach. Both molecules are treated as rigid rotors. The scattering calculations are based on a highly correlated ab initio 4-dimensional (4D) potential energy surface recently published. Rotationally inelastic cross sections among the 13 first rotational levels of HCN were obtained using a pure quantum close coupling approach for total energies up to 1200 cm(-1). The corresponding thermal rate coefficients were computed for temperatures ranging from 5 to 100 K. The HCN rate coefficients are strongly dependent on the rotational level of the H2 molecule. In particular, the rate coefficients for collisions with para-H2(j = 0) are significantly lower than those for collisions with ortho-H2(j = 1) and para-H2(j = 2). Propensity rules in favor of even Δj transitions were found for HCN in collisions with para-H2(j = 0) whereas propensity rules in favor of odd Δj transitions were found for HCN in collisions with H2(j ⩾ 1). The new rate coefficients were compared with previously published HCN-para-H2(j = 0) rate coefficients. Significant differences were found due the inclusion of the H2 rotational structure in the scattering calculations. These new rate coefficients will be crucial to improve the estimation of the HCN abundance in the interstellar medium.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Marlow, W.H.

An aerosol here is understood to be a two-component system comprised of gaseous and condensed phases with the characteristic that the condensed phase is not an equilibrium subsystem. In contrast to the usual definitions based upon geometrical or mechanical variables, this quasi-thermodynamic formulation is framed to emphasize the dynamical behavior of aerosols by allowing for coagulation and other aerosol evolutionary processes as natural consequences of the interactions and state variables appropriate to the system. As will become clear later, it also provides a point of departure for distinguishing aerosol particles from unstable gas-phase cluster systems. The question of accommodation inmore » particle collisions must be addressed as a prelude to the discussion of the role of long-range forces. Microscopic reversibility is frequently assumed for molecular collisions with either molecules or solid surfaces. In the case of aerosol collisions, the implication of this assumption is that collisions are elastic, which is contrary to the evidence from coagulation experiments and the conventional operational assumption of sticking upon collision. Gay and Berne have performed computer simulations of the collision of two clusters consisting of a total of 135 molecules interacting via Lennard-Jones potentials. That work showed that complete accommodation, accompanied by overall heating of the unified cluster, occurred. Since heating represents an irreversible degradation of the kinetic energy of the collision, the hamiltonian of the two-cluster system should be considered as dissipative and therefore microscopic reversibility does not apply.« less

Influence of resonant collisions on the self-broadening of acetylene

NASA Astrophysics Data System (ADS)

Lehmann, Kevin K.

2017-03-01

Iwakuni et al. [Phys. Rev. Lett. 117, 143902 (2016)] have reported an ortho-para alternation of ˜10% in the self pressure broadening coefficients for ro-vibrational lines of the C2H2 transitions in the ν1+ν3 C-H (local mode) overtone band near 197 THz (1.52 μm). These authors attributed this effect to the contribution of resonant collisions, where the rotational energy change of one molecule is exactly compensated by the rotational energy change of its collision partner. Resonant collisions are known to be important in the case of self pressure broadening of highly polar molecules, such as HCN, but have not previously been invoked in the case of nonpolar molecules, such as acetylene, where the long range potential is dominated by the quadrupole-quadrupole electrostatic interaction. In the present work, the simple semiclassical Anderson-theory approach is used to estimate the rates of C2H2-C2H2 rotationally inelastic collisions and these used to predict pressure broadening rates, ignoring other contributions to the broadening, which should not have resonant enhancements. It is found that exactly resonant collisions do not make a major contribution to the broadening and these calculations predict an ortho-para alternation of the pressure broadening coefficients far below what was inferred by Iwakuni et al. The present results are consistent with a large body of published work that reported self-broadening coefficients of C2H2 ro-vibrational transitions that found negligible dependence on the vibrational transition and no even-odd alternation, even for Q and S branch transitions where any such effect is predicted to be much larger than for the P and R branch transitions studied by Iwakuni et al.

Half collision resonance phenomena in molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maximo Garcia-Sucre; Raseev, G.; Ross, S.C.

1991-01-01

The Escuela Latinoamericana de Fisica (ELAF) is a series of meeting s that for 28 years has played an important role in research-level teaching of physics in Latin America. This book contains the proceedings of ELAF 90 which was held at the Instituto Venezolano de Investigaciones Cientificas (IVIC) in Caracas, Venezuela from July 23 to August 3, 1990, as part of the commemoration of the 30th anniversary of IVIC. In contrast to previous ELAF's that were of general scope, ELAF 90 centered on a particular subject matter: Half Collisional Resonance Phenomena in Molecules, Experimental and Theoretical Approaches. The term Halfmore » Collision'' refers to the fragmentation of a molecular system following is excitation by light. The lack of an incident fragmentation of a molecular system following is excitation by light. The lack of an incident particle (other than the photon) in the fragmentation process is what leads to the term. The purpose of this volume is to present current results in the experimental and theoretical study of half collisions and also to include pedagogical papers at an introductory or intermediate level. The contributions are grouped into several sections; light sources; ionization; dissociation-experimental; dissociation-theory; competition between ionization and dissociation; and particle-molecule collisions.« less

ITFITS model for vibration--translation energy partitioning in atom-- polyatomic molecule collisions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shobatake, K.; Rice, S.A.; Lee, Y.T.

1973-09-01

A model for vibration-translation energy partitioning in the collinear collision of an atom and an axially symmetric polyatonaic molecule is proposed. The model is based on an extension of the ideas of Mahan and Heidrich, Wilson, and Rapp. Comparison of energy transfers computed from classical trajesctory calculations and the model proposed indicate good agreement when the mass of the free atom is small relative to the mass of the bound atom it strikes. The agreement is less satisfactory when that mass ratio becomes large. (auth)

The spontaneous synchronized dance of pairs of water molecules

NASA Astrophysics Data System (ADS)

Roncaratti, Luiz F.; Cappelletti, David; Pirani, Fernando

2014-03-01

Molecular beam scattering experiments have been performed to study the effect of long-range anisotropic forces on the collision dynamics of two small polar molecules. The main focus of this paper is on water, but also ammonia and hydrogen sulphide molecules have been investigated, and some results will be anticipated. The intermolecular distances mainly probed are of the order of 1 nm and therefore much larger than the molecular dimensions. In particular, we have found that the natural electric field gradient, generated by different spatial orientations of the permanent electric dipoles, is able to promote the transformation of free rotations into coupled pendular states, letting the molecular partners involved in the collision complex swinging to and fro around the field direction. This long-ranged concerted motion manifested itself as large increases of the magnitude of the total integral cross section. The experimental findings and the theoretical treatment developed to shed light on the details of the process suggest that the transformation from free rotations to pendular states depends on the rotational level of both molecules, on the impact parameter, on the relative collision velocity, on the dipole moment product and occurs in the time scale of picoseconds. The consequences of this intriguing phenomenon may be important for the interpretation and, in perspective, for the control of elementary chemical and biological processes, given by polar molecules, ions, and free radicals, occurring in several environments under various conditions.

Lasers '81

DOE Office of Scientific and Technical Information (OSTI.GOV)

Collins, C.B.

1982-01-01

Progress in lasers is discussed. The subjects addressed include: excimer lasers, surface spectroscopy, modern laser spectroscopy, free electron lasers, cavities and propagation, lasers in medicine, X-ray and gamma ray lasers, laser spectroscopy of small molecules and clusters, optical bistability, excitons, nonlinear optics in the X-ray and gamma ray regions, collective atomic phenomena, tunable IR lasers, far IR/submillimeter lasers, and laser-assisted collisions. Also treated are: special applications, multiphoton processes in atoms and small molecules, nuclear pumped lasers, material processing and applications, polarization, high energy lasers, laser chemistry, IR molecular lasers, laser applications of collision and dissociation phenomena, solid state laser materials,more » phase conjugation, advances in laser technology for fusion, metal vapor lasers, picosecond phenomena, laser ranging and geodesy, and laser photochemistry of complex molecules.« less

Ion mobilities in diatomic gases: measurement versus prediction with non-specular scattering models.

PubMed

Larriba, Carlos; Hogan, Christopher J

2013-05-16

Ion/electrical mobility measurements of nanoparticles and polyatomic ions are typically linked to particle/ion physical properties through either application of the Stokes-Millikan relationship or comparison to mobilities predicted from polyatomic models, which assume that gas molecules scatter specularly and elastically from rigid structural models. However, there is a discrepancy between these approaches; when specular, elastic scattering models (i.e., elastic-hard-sphere scattering, EHSS) are applied to polyatomic models of nanometer-scale ions with finite-sized impinging gas molecules, predictions are in substantial disagreement with the Stokes-Millikan equation. To rectify this discrepancy, we developed and tested a new approach for mobility calculations using polyatomic models in which non-specular (diffuse) and inelastic gas-molecule scattering is considered. Two distinct semiempirical models of gas-molecule scattering from particle surfaces were considered. In the first, which has been traditionally invoked in the study of aerosol nanoparticles, 91% of collisions are diffuse and thermally accommodating, and 9% are specular and elastic. In the second, all collisions are considered to be diffuse and accommodating, but the average speed of the gas molecules reemitted from a particle surface is 8% lower than the mean thermal speed at the particle temperature. Both scattering models attempt to mimic exchange between translational, vibrational, and rotational modes of energy during collision, as would be expected during collision between a nonmonoatomic gas molecule and a nonfrozen particle surface. The mobility calculation procedure was applied considering both hard-sphere potentials between gas molecules and the atoms within a particle and the long-range ion-induced dipole (polarization) potential. Predictions were compared to previous measurements in air near room temperature of multiply charged poly(ethylene glycol) (PEG) ions, which range in morphology from compact to highly linear, and singly charged tetraalkylammonium cations. It was found that both non-specular, inelastic scattering rules lead to excellent agreement between predictions and experimental mobility measurements (within 5% of each other) and that polarization potentials must be considered to make correct predictions for high-mobility particles/ions. Conversely, traditional specular, elastic scattering models were found to substantially overestimate the mobilities of both types of ions.

Observation of Resonant Effects in Ultracold Collisions between Heteronuclear Feshbach Molecules

NASA Astrophysics Data System (ADS)

Ye, Xin; Wang, Fudong; Zhu, Bing; Guo, Mingyang; Lu, Bo; Wang, Dajun

2016-05-01

Magnetic field dependent dimer-dimer collisional losses are studied with ultracold 23 Na87 Rb Feshbach molecules. By ramping the magnetic field across the 347.8 G inter-species Feshbach resonance and removing residual atoms with a magnetic field gradient, ~ 8000 pure NaRb Feshbach molecules with a temperature below 1 μK are produced. By holding the pure molecule sample in a crossed optical dipole trap and measuring the time-dependent loss curves under different magnetic fields near the Feshbach resonance, the dimer-dimer loss rates with respect to the atomic scattering length a are mapped out. We observe a resonant feature at around a = 600a0 and a rising tail at above a = 1600a0 . This behavior resembles previous theoretical works on homonuclear Feshbach molecule, where resonant effects between dimer-dimer collisions tied to tetramer bound states were predicted. Our work shows the possibility of exploring four-body physics within a heteronuclear system. We are supported by Hong Kong RGC General Research Fund no. CUHK403813.

Electron Impact Excitation-Ionization of Molecules

NASA Astrophysics Data System (ADS)

Ali, Esam Abobakr A.

In the last few decades, the study of atomic collisions by electron-impact has made significant advances. The most difficult case to study is electron impact ionization of molecules for which many approximations have to be made and the validity of these approximations can only be checked by comparing with experiment. In this thesis, I have examined the Molecular three-body distorted wave (M3DW) or Molecular four-body distorted wave (M4DW) approximations for electron-impact ionization. These models use a fully quantum mechanical approach where all particles are treated quantum mechanically and the post collision interaction (PCI) is treated to all orders of perturbation. These electron impact ionization collisions play central roles in the physics and chemistry of upper atmosphere, biofuel, the operation of discharges and lasers, radiation induced damage in biological material like damage to DNA by secondary electrons, and plasma etching processes. For the M3DW model, I will present results for electron impact single ionization of small molecules such as Water, Ethane, and Carbon Dioxide and the much larger molecules Tetrahydrofuran, phenol, furfural, 1-4 Benzoquinone. I will also present results for the four-body problem in which there are two target electrons involved in the collision. M4DW results will be presented for dissociative excitation-ionization of orientated D2. I will show that M4DW calculations using a variational wave function for the ground state that included s- and p- orbital states give better agreement to the experimental measurements than a ground state approximated as a product of two 1s-type Dyson orbitals.

Gaussian process model for extrapolation of scattering observables for complex molecules: From benzene to benzonitrile

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cui, Jie; Krems, Roman V.; Li, Zhiying

2015-10-21

We consider a problem of extrapolating the collision properties of a large polyatomic molecule A–H to make predictions of the dynamical properties for another molecule related to A–H by the substitution of the H atom with a small molecular group X, without explicitly computing the potential energy surface for A–X. We assume that the effect of the −H →−X substitution is embodied in a multidimensional function with unknown parameters characterizing the change of the potential energy surface. We propose to apply the Gaussian Process model to determine the dependence of the dynamical observables on the unknown parameters. This can bemore » used to produce an interval of the observable values which corresponds to physical variations of the potential parameters. We show that the Gaussian Process model combined with classical trajectory calculations can be used to obtain the dependence of the cross sections for collisions of C{sub 6}H{sub 5}CN with He on the unknown parameters describing the interaction of the He atom with the CN fragment of the molecule. The unknown parameters are then varied within physically reasonable ranges to produce a prediction uncertainty of the cross sections. The results are normalized to the cross sections for He — C{sub 6}H{sub 6} collisions obtained from quantum scattering calculations in order to provide a prediction interval of the thermally averaged cross sections for collisions of C{sub 6}H{sub 5}CN with He.« less

Control of Rotational Energy and Angular Momentum Orientation with an Optical Centrifuge

NASA Astrophysics Data System (ADS)

Ogden, Hannah M.; Murray, Matthew J.; Mullin, Amy S.

2017-04-01

We use an optical centrifuge to trap and spin molecules to an angular frequency of 30 THz with oriented angular momenta and extremely high rotational energy and then investigate their subsequent collision dynamics with transient high resolution IR spectroscopy. The optical centrifuge is formed by combining oppositely-chirped pulses of 800 nm light, and overlapping them spatially and temporally. Polarization-sensitive Doppler-broadened line profiles characterize the anisotropic kinetic energy release of the super rotor molecules, showing that they behave like molecular gyroscopes. Studies are reported for collisions of CO2 super rotors with CO2, He and Ar. These studies reveal how mass, velocity and rotational adiabaticity impact the angular momentum relaxation and reorientation. Quantum scattering calculations provide insight into the J-specific collision cross sections that control the relaxation. NSF-CHE 105 8721.

Processes of energy deposition by heavy-particle and electron impact. Final progress report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Salop, A.; Smith, F.T.

1978-04-18

Progress is reported in three areas of reasearch during the present period: K-shell ionization in high energy collisions of heavy ions with light target atoms using the sudden (Magnus) approximation, K-L level matching phenomena associated with K-shell vacancy production in heavy-ion collisions, and studies of low energy collisions of electrons with molecules using semi-classical perturbation theory. A brief discussion of each of these activities is given.

Structural Characterization of Unsaturated Phosphatidylcholines Using Traveling Wave Ion Mobility Spectrometry

PubMed Central

Kim, Hugh I.; Kim, Hyungjun; Pang, Eric S.; Ryu, Ernest K.; Beegle, Luther W.; Loo, Joseph A.; Goddard, William A.; Kanik, Isik

2009-01-01

A number of phosphatidylcholine (PC) cations spanning a mass range of 400 to 1000 Da are investigated using electrospray ionization mass spectrometry coupled with traveling wave ion mobility spectrometry (TWIMS). A high correlation between mass and mobility is demonstrated with saturated phosphatidylcholine cations in N2. A significant deviation from this mass-mobility correlation line is observed for the unsaturated PC cation. We found that the double bond in the acyl chain causes a 5% reduction in drift time. The drift time is reduced at a rate of ~1% for each additional double bond. Theoretical collision cross sections of PC cations exhibit good agreement with experimentally evaluated values. Collision cross sections are determined using the recently derived relationship between mobility and drift time in TWIMS stacked ring ion guide (SRIG) and compared to estimate collision cross-sections using empiric calibration method. Computational analysis was performed using the modified trajectory (TJ) method with nonspherical N2 molecules as the drift gas. The difference between estimated collision cross-sections and theoretical collision cross-sections of PC cations is related to the sensitivity of the PC cation collision cross-sections to the details of the ion-neutral interactions. The origin of the observed correlation and deviation between mass and mobility of PC cations is discussed in terms of the structural rigidity of these molecules using molecular dynamic simulations. PMID:19764704

Studies of rotationally inelastic collisions of NaK and NaCs with Ar and He perturbers

NASA Astrophysics Data System (ADS)

Jones, J.; Faust, C.; Richter, K.; Wolfe, C. M.; Ashman, S.; Malenda, R. F.; Weiser, P.; Carlus, S.; Fragale, A.; Hickman, A. P.; Huennekens, J.

2013-05-01

We report studies of rotationally inelastic collisions of Ar and He atoms with the molecules NaK and NaCs prepared in various ro-vibrational levels of the A1Σ+ electronic state. We use laser induced fluorescence (LIF) and polarization labeling (PL) spectroscopy in a pump-probe, two step excitation process. The pump excites the molecule to a ro-vibrational level (v , J) in the A state. The probe laser is scanned over transitions to the 31 Π state in NaK or the 53 Π state in NaCs. In addition to strong direct lines, we observe weak satellite lines that arise from collision-induced transitions of the A state level (v , J) to (v , J + ΔJ) . The ratio of intensities of the satellite line to the direct line in LIF and PL yields information about population and orientation transfer. Preliminary results show a strong propensity for collisions with ΔJ =even for NaK; the propensity is larger for He than for Ar. Collisions of NaCs with He show a similar propensity, but collisions of NaCs with Ar do not. Theoretical calculations are also underway. For He-NaK, we have completed potential surface calculations using GAMESS and coupled channel scattering calculations of rotational energy transfer and transfer of orientation. Work supported by NSF and XSEDE.

Electron correlations and pre-collision in the re-collision picture of high harmonic generation

NASA Astrophysics Data System (ADS)

Mašín, Zdeněk; Harvey, Alex G.; Spanner, Michael; Patchkovskii, Serguei; Ivanov, Misha; Smirnova, Olga

2018-07-01

We discuss the seminal three-step model and the re-collision picture in the context of high harmonic generation in molecules. In particular, we stress the importance of multi-electron correlation during the first and the third of the three steps of the process: (1) the strong-field ionization and (3) the recombination. We point out how an accurate account of multi-electron correlations during the third recombination step allows one to gauge the importance of pre-collision: the term coined by Eberly (n.d. private communication) to describe unusual pathways during the first, ionization, step.

Division B Commission 14 Working Group: Collision Processes

NASA Astrophysics Data System (ADS)

Peach, Gillian; Dimitrijevic, Milan S.; Barklem, Paul S.

2016-04-01

Since our last report (Peach & Dimitrijević 2012), a large number of new publications on the results of research in atomic and molecular collision processes and spectral line broadening have been published. Due to the limited space available, we have only included work of importance for astrophysics. Additional relevant papers, not included in this report, can be found in the databases at the web addresses provided in Section 6. Elastic and inelastic collisions between electrons, atoms, ions, and molecules are included, as well as charge transfer in collisions between heavy particles which can be very important.

The spontaneous synchronized dance of pairs of water molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Roncaratti, Luiz F.; Instituto de Física, Universidade de Brasília, 70910-900 Brasília; Cappelletti, David, E-mail: david.cappelletti@unipg.it

2014-03-28

Molecular beam scattering experiments have been performed to study the effect of long-range anisotropic forces on the collision dynamics of two small polar molecules. The main focus of this paper is on water, but also ammonia and hydrogen sulphide molecules have been investigated, and some results will be anticipated. The intermolecular distances mainly probed are of the order of 1 nm and therefore much larger than the molecular dimensions. In particular, we have found that the natural electric field gradient, generated by different spatial orientations of the permanent electric dipoles, is able to promote the transformation of free rotations into coupledmore » pendular states, letting the molecular partners involved in the collision complex swinging to and fro around the field direction. This long-ranged concerted motion manifested itself as large increases of the magnitude of the total integral cross section. The experimental findings and the theoretical treatment developed to shed light on the details of the process suggest that the transformation from free rotations to pendular states depends on the rotational level of both molecules, on the impact parameter, on the relative collision velocity, on the dipole moment product and occurs in the time scale of picoseconds. The consequences of this intriguing phenomenon may be important for the interpretation and, in perspective, for the control of elementary chemical and biological processes, given by polar molecules, ions, and free radicals, occurring in several environments under various conditions.« less

Ion collision-induced chemistry in pure and mixed loosely bound clusters of coronene and C60 molecules.

PubMed

Domaracka, Alicja; Delaunay, Rudy; Mika, Arkadiusz; Gatchell, Michael; Zettergren, Henning; Cederquist, Henrik; Rousseau, Patrick; Huber, Bernd A

2018-05-23

Ionization, fragmentation and molecular growth have been studied in collisions of 22.5 keV He2+- or 3 keV Ar+-projectiles with pure loosely bound clusters of coronene (C24H12) molecules or with loosely bound mixed C60-C24H12 clusters by using mass spectrometry. The heavier and slower Ar+ projectiles induce prompt knockout-fragmentation - C- and/or H-losses - from individual molecules and highly efficient secondary molecular growth reactions before the clusters disintegrate on picosecond timescales. The lighter and faster He2+ projectiles have a higher charge and the main reactions are then ionization by ions that are not penetrating the clusters. This leads mostly to cluster fragmentation without molecular growth. However, here penetrating collisions may also lead to molecular growth but to a much smaller extent than with 3 keV Ar+. Here we present fragmentation and molecular growth mass distributions with 1 mass unit resolution, which reveals that the same numbers of C- and H-atoms often participate in the formation and breaking of covalent bonds inside the clusters. We find that masses close to those with integer numbers of intact coronene molecules, or with integer numbers of both intact coronene and C60 molecules, are formed where often one or several H-atoms are missing or have been added on. We also find that super-hydrogenated coronene is formed inside the clusters.

New parameter-free polarization potentials in low-energy positron collisions

NASA Technical Reports Server (NTRS)

Jain, Ashok

1990-01-01

The polarization potential plays a decisive role in shaping up the cross sections in low energy positron collisions with atoms and molecules. However, its inclusion without involving any adjustable parameter, is still a challenge. Various other techniques employed so far for positron collisions are summarized, and a new, nonadjustable and very simple form of the polarization potential for positron-atom (molecule) collisions below the threshold of positronium formation is discussed. This new recently proposed potential is based on the correlation energy of a single positron in a homogeneous electron gas. The correlation energy was calculated by solving the Schrodinger equation of the positron-electron system and fitted to an analytical form in various ranges of the density parameter. In the outside region, the correlation energy is joined smoothly with the correct asymptotic form. This new positron correlation polarization (PCOP) potential was tested on several atomic and molecular targets such as the Ar, CO, and CH4. The results on the total and differential cross sections on these targets are shown along with the experimental data where available.

The atom-molecule reaction D plus H2 yields HD plus H studied by molecular beams

NASA Technical Reports Server (NTRS)

Geddes, J.; Krause, H. F.; Fite, W. L.

1972-01-01

Collisions between deuterium atoms and hydrogen molecules were studied in a modulated crossed beam experiment. The relative signal intensity and the signal phase for the product HD from reactive collisions permitted determination of both the angular distribution and HD mean velocity as a function of angle. From these a relative differential reactive scattering cross section in center-of-mass coordinates was deduced. The experiment indicates that reactively formed HD which has little or no internal excitation departs from the collision anisotropically, with maximum amplitude 180 deg from the direction of the incident D beam in center-of-mass coordinates, which shows that the D-H-H reacting configuration is short-lived compared to its rotation time. Non reactive scattering of D by H2 was used to assign absolute values to the differential reactive scattering cross sections.

EUV emission spectra in collisions of highly charged tantalum ions with nitrogen and oxygen molecules

NASA Astrophysics Data System (ADS)

Tanuma, Hajime; Numadate, Naoki; Uchikura, Yoshiyuki; Shimada, Kento; Akutsu, Takuto; Long, Elaine; O'Sullivan, Gerry

2017-10-01

We have performed ion beam collision experiments using multiply charged tantalum ions and observed EUV (extreme ultra-violet) emission spectra in collisions of ions with molecular targets, N2 and O2. Broad UTAs (un-resolved transition arrays) from multiply charged Ta ions were observed, and the mean wavelengths of the UTAs shifted and became shorter at higher charge statea of Ta ions. These UTAs may be attributed to the 4f-5d and 4f-5g transitions. Not only the UTA emission from incident ions, but also the sharp emission lines from multiply charged fragment atomic ions were observed. Production of temporary highly charged molecular ions, their kinetic energy and fragmentation processes have been investigated with coincident detection technique. However, the observation of emission from the fragments might be for the first time. The formation mechanisms of the multiply charged fragment atomic ions from target molecules are discussed.

UKRmol: a low-energy electron- and positron-molecule scattering suite

NASA Astrophysics Data System (ADS)

Carr, J. M.; Galiatsatos, P. G.; Gorfinkiel, J. D.; Harvey, A. G.; Lysaght, M. A.; Madden, D.; Mašín, Z.; Plummer, M.; Tennyson, J.; Varambhia, H. N.

2012-03-01

We describe the UK computational implementation of the R-matrix method for the treatment of electron and positron scattering from molecules. Recent developments in the UKRmol suite are detailed together with the collision processes it is enabling us to treat.

Rotational excitation of HCN by para- and ortho-H{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vera, Mario Hernández, E-mail: marhvera@gmail.com; InSTEC, Quinta de Los Molinos, Plaza, La Habana 10600; Kalugina, Yulia

Rotational excitation of the hydrogen cyanide (HCN) molecule by collisions with para-H{sub 2}( j = 0, 2) and ortho-H{sub 2}( j = 1) is investigated at low temperatures using a quantum time independent approach. Both molecules are treated as rigid rotors. The scattering calculations are based on a highly correlated ab initio 4-dimensional (4D) potential energy surface recently published. Rotationally inelastic cross sections among the 13 first rotational levels of HCN were obtained using a pure quantum close coupling approach for total energies up to 1200 cm{sup −1}. The corresponding thermal rate coefficients were computed for temperatures ranging from 5 to 100 K.more » The HCN rate coefficients are strongly dependent on the rotational level of the H{sub 2} molecule. In particular, the rate coefficients for collisions with para-H{sub 2}( j = 0) are significantly lower than those for collisions with ortho-H{sub 2}( j = 1) and para-H{sub 2}( j = 2). Propensity rules in favor of even Δj transitions were found for HCN in collisions with para-H{sub 2}( j = 0) whereas propensity rules in favor of odd Δj transitions were found for HCN in collisions with H{sub 2}( j ⩾ 1). The new rate coefficients were compared with previously published HCN-para-H{sub 2}( j = 0) rate coefficients. Significant differences were found due the inclusion of the H{sub 2} rotational structure in the scattering calculations. These new rate coefficients will be crucial to improve the estimation of the HCN abundance in the interstellar medium.« less

Near-resonant rotational energy transfer in HCl–H{sub 2} inelastic collisions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lanza, Mathieu; Lique, François, E-mail: francois.lique@univ-lehavre.fr; Kalugina, Yulia

2014-02-14

We present a new four-dimensional (4D) potential energy surface for the HCl–H{sub 2} van der Waals system. Both molecules were treated as rigid rotors. Potential energy surface was obtained from electronic structure calculations using a coupled cluster with single, double, and perturbative triple excitations method. The four atoms were described using the augmented correlation-consistent quadruple zeta basis set and bond functions were placed at mid-distance between the HCl and H{sub 2} centers of mass for a better description of the van der Waals interaction. The global minimum is characterized by the well depth of 213.38 cm{sup −1} corresponding to themore » T-shape structure with H{sub 2} molecule on the H side of the HCl molecule. The dissociation energies D{sub 0} are 34.7 cm{sup −1} and 42.3 cm{sup −1} for the complex with para- and ortho-H{sub 2}, respectively. These theoretical results obtained using our new PES are in good agreement with experimental values [D. T. Anderson, M. Schuder, and D. J. Nesbitt, Chem. Phys. 239, 253 (1998)]. Close coupling calculations of the inelastic integral rotational cross sections of HCl in collisions with para-H{sub 2} and ortho-H{sub 2} were performed at low and intermediate collisional energies. Significant differences exist between para- and ortho-H{sub 2} results. The strongest collision-induced rotational HCl transitions are the transitions with Δj = 1 for collisions with both para-H{sub 2} and ortho-H{sub 2}. Rotational relaxation of HCl in collision with para-H{sub 2} in the rotationally excited states j = 2 is dominated by near-resonant energy transfer.« less

Electric manipulation of ultracold polar ^40K^87Rb molecules in a magnetic field

NASA Astrophysics Data System (ADS)

Quéméner, Goulven; Bohn, John

2009-05-01

Ultracold fermionic polar molecules of ^40K^87Rb in their absolute rovibronic ground state (v=0,n=0,^1σ) have been created recently [1] in a magnetic trap and open new perspectives to create fermionic degenerate gases of polar molecules. To achieve this goal, it is very important to understand the collisional properties of such molecules under magnetic and electric fields. In our presentation, we investigate ground state fermionic ^40K^87Rb + ^40K^87Rb collisions in the presence of a magnetic field and explore the possibility to control these collisions when an electric field is applied. We will explore the main physical processes that can lead to such manipulation. This problem is complicated by the Zeeman and Stark splitting of all levels of the polar molecules and by the possibility of forming ^40K2 + ^87Rb2 chemical products. 1 - K.-K. Ni, S. Ospelkaus, M. H. G. de Miranda, A. Pe'er, B. Neyenhuis, J. J. Zirbel, S. Kotochigova, P. S. Julienne, D. S. Jin, and J. Ye, Science 322, 231 (2008).

Production, Manipulation, and Applications of Ultracold Polar Molecules

DTIC Science & Technology

2015-04-30

molecules, cooling, trapping, photoassociation, feshbach resonances, quantum simulation , ultracold collisions, ultracold chemistry, optical lattices...been a multitude of less predictable outcomes: special quantum information processing schemes, uses of entanglement such a spin-squeezing for better...field seeing states to high-field-seeking states (and back) at key points in the magnetic field. The molecules spontaneously emit photons as they are

Low-Energy Collisions of Protonated Enantiopure Amino Acids with Chiral Target Gases

NASA Astrophysics Data System (ADS)

Kulyk, K.; Rebrov, O.; Ryding, M.; Thomas, R. D.; Uggerud, E.; Larsson, M.

2017-12-01

Here we report on the gas-phase interactions between protonated enantiopure amino acids ( l- and d-enantiomers of Met, Phe, and Trp) and chiral target gases [( R)- and ( S)-2-butanol, and ( S)-1-phenylethanol] in 0.1-10.0 eV low-energy collisions. Two major processes are seen to occur over this collision energy regime, collision-induced dissociation and ion-molecule complex formation. Both processes were found to be independent of the stereo-chemical composition of the interacting ions and targets. These data shed light on the currently debated mechanisms of gas-phase chiral selectivity by demonstrating the inapplicability of the three-point model to these interactions, at least under single collision conditions. [Figure not available: see fulltext.

Selected bibliography on atomic collisions: Data collections, bibliographies, review articles, books, and papers of particular tutorial value

DOE Office of Scientific and Technical Information (OSTI.GOV)

McDaniel, E.W.; Flannery, M.R.; Thomas, E.W.

This bibliography deals mainly with binary and ternary collisions involving electrons, photons, and heavy particles (i.e., atoms, molecules, and ions). The energy range covered for each kind of collision is such that the interactions might be described as electronic, atomic, or chemical--higher-energy collisions involving nuclear forces are not treated. Also covered are particle and photon impact on surfaces, the passage of particles and radiation through bulk matter, and transport phenomena in gases. Practically all of the references cited are data compilations, other bibliographies, review articles, or books. The main objective is to provide easy access to atomic collision data, althoughmore » some references are included principally for their tutorial value.« less

Magnetic Trapping and Coherent Control of Laser-Cooled Molecules

NASA Astrophysics Data System (ADS)

Williams, H. J.; Caldwell, L.; Fitch, N. J.; Truppe, S.; Rodewald, J.; Hinds, E. A.; Sauer, B. E.; Tarbutt, M. R.

2018-04-01

We demonstrate coherent microwave control of the rotational, hyperfine, and Zeeman states of ultracold CaF molecules, and the magnetic trapping of these molecules in a single, selectable quantum state. We trap about 5 ×103 molecules for almost 2 s at a temperature of 70 (8 ) μ K and a density of 1.2 ×105 cm-3. We measure the state-specific loss rate due to collisions with background helium.

The FEM-R-Matrix Approach: Use of Mixed Finite Element and Gaussian Basis Sets for Electron Molecule Collisions

NASA Technical Reports Server (NTRS)

Thuemmel, Helmar T.; Huo, Winifred M.; Langhoff, Stephen R. (Technical Monitor)

1995-01-01

For the calculation of electron molecule collision cross sections R-matrix methods automatically take advantage of the division of configuration space into an inner region (I) bounded by radius tau b, where the scattered electron is within the molecular charge cloud and the system is described by an correlated Configuration Interaction (CI) treatment in close analogy to bound state calculations, and an outer region (II) where the scattered electron moves in the long-range multipole potential of the target and efficient analytic methods can be used for solving the asymptotic Schroedinger equation plus boundary conditions.

Scattering of water from the glycerol liquid-vacuum interface

NASA Technical Reports Server (NTRS)

Benjamin, I.; Wilson, M. A.; Pohorille, A.; Nathanson, G. M.

1995-01-01

Molecular dynamics calculations of the scattering of D2O from the glycerol surface at different collision energies are reported. The results for the trapping probabilities and energy transfer are in good agreement with experiments. The calculations demonstrate that the strong attractive forces between these two strongly hydrogen bonding molecules have only a minor effect on the initial collision dynamics. The trapping probability is influenced to a significant extent by the repulsive hard sphere-like initial encounter with the corrugated surface and, only at a later stage, by the efficiency of energy flow in the multiple interactions between the water and the surface molecules.

Sympathetic Cooling of Molecular Ions in Selected Rotational and Vibrational States Produced by Threshold Photoionization

NASA Astrophysics Data System (ADS)

Tong, Xin; Winney, Alexander H.; Willitsch, Stefan

2010-10-01

We present a new method for the generation of rotationally and vibrationally state-selected, translationally cold molecular ions in ion traps. Our technique is based on the state-selective threshold photoionization of neutral molecules followed by sympathetic cooling of the resulting ions with laser-cooled calcium ions. Using N2+ ions as a test system, we achieve >90% selectivity in the preparation of the ground rovibrational level and state lifetimes on the order of 15 minutes limited by collisions with background-gas molecules. The technique can be employed to produce a wide range of apolar and polar molecular ions in the ground and excited rovibrational states. Our approach opens up new perspectives for cold quantum-controlled ion-molecule-collision studies, frequency-metrology experiments with state-selected molecular ions and molecular-ion qubits.

Positronium collisions with molecular nitrogen

NASA Astrophysics Data System (ADS)

Wilde, R. S.; Fabrikant, I. I.

2018-05-01

For many atomic and molecular targets positronium (Ps) scattering looks very similar to electron scattering if total scattering cross sections are plotted as functions of the projectile velocity. Recently this similarity was observed for the resonant scattering by the N2 molecule. For correct treatment of Ps-molecule scattering incorporation of the exchange interaction and short-range correlations is of paramount importance. In the present work we have used a free-electron-gas model to describe these interactions in collisions of Ps with the N2 molecule. The results agree reasonably well with the experiment, but the position of the resonance is somewhat shifted towards lower energies, probably due to the fixed-nuclei approximation employed in the calculations. The partial-wave analysis of the resonant peak shows that its composition is more complex than in the case of e -N2 scattering.

Selectivity in the inelastic rotational scattering of D2 and HD molecules from graphite: Similarities and differences respect to the H2 case

NASA Astrophysics Data System (ADS)

Rutigliano, Maria; Pirani, Fernando

2018-03-01

The inelastic scattering of D2 and HD molecules impinging on a graphite surface in well-defined initial roto-vibrational states has been studied by using the computational setup recently developed to characterize important selectivities in the molecular dynamics occurring at the gas-surface interface. In order to make an immediate comparison of determined elastic and inelastic scattering probabilities, we considered for D2 and HD molecules the same initial states, as well as the same collision energy range, previously selected for the investigation of H2 behaviour. The analysis of the back-scattered molecules shows that, while low-lying initial vibrational states are preserved, the medium-high initial ones give rise to final states covering the complete ladder of vibrational levels, although with different probability for the various cases investigated. Moreover, propensities in the formation of the final rotational states are found to depend strongly on the initial ones, on the collision energy, and on the isotopologue species.

A spectroscopist's view of energy states, energy transfers, and chemical reactions.

PubMed

Moore, C Bradley

2007-01-01

This chapter describes a research career beginning at Berkeley in 1960, shortly after Sputnik and the invention of the laser. Following thesis work on vibrational spectroscopy and the chemical reactivity of small molecules, we studied vibrational energy transfers in my own lab. Collision-induced transfers among vibrations of a single molecule, from one molecule to another, and from vibration to rotation and translation were elucidated. My research group also studied the competition between vibrational relaxation and chemical reaction for potentially reactive collisions with one molecule vibrationally excited. Lasers were used to enrich isotopes by the excitation of a predissociative transition of a selected isotopomer. We also tested the hypotheses of transition-state theory for unimolecular reactions of ketene, formaldehyde, and formyl fluoride by (a) resolving individual molecular eigenstates above a dissociation threshold, (b) locating vibrational levels at the transition state, (c) observing quantum resonances in the barrier region for motion along a reaction coordinate, and (d) studying energy release to fragments.

Electron scattering on molecules: search for semi-empirical indications

NASA Astrophysics Data System (ADS)

Fedus, Kamil; Karwasz, Grzegorz P.

2017-06-01

Reliable cross-sections for electron-molecule collisions are urgently needed for numerical modeling of various processes important from technological point of view. Unfortunately, a significant progress in theory and experiment over the last decade is not usually accompanied by the convergence of cross-sections measured at different laboratories and calculated with different methods. Moreover the most advanced contemporary theories involve such large basis sets and complicated equations that they are not easily applied to each specific molecule for which data are needed. For these reasons the search for semi-empirical indications in angular and energy dependencies of scattering cross-section becomes important. In this paper we make a brief review of the applicability of the Born-dipole approximation for elastic, rotational, vibrational and ionization processes that can occur during electron-molecule collisions. We take into account the most recent experimental findings as the reference points. Contribution to the Topical Issue "Atomic and Molecular Data and Their Applications", edited by Gordon W.F. Drake, Jung-Sik Yoon, Daiji Kato, and Grzegorz Karwasz.

Configuration-specific kinetic theory applied to an ideal binary gas mixture.

PubMed

Wiseman, Floyd L

2006-10-05

This paper is the second in a two-part series dealing with the configuration-specific analyses for molecular collision events of hard, spherical molecules at thermal equilibrium. The first paper analyzed a single-component system, and the reader is referred to it for the fundamental concepts. In this paper, the expressions for the configuration-specific collision frequencies and the average line-of-centers collision angles and speeds are derived for an ideal binary gas mixture. The analyses show that the average line-of-centers quantities are all dependent upon the ratio of the masses of the two components, but not upon molecular size. Of course, the configuration-specific collision frequencies do depend on molecular size. The expression for the overall binary collision frequency is a simple sum of the configuration-specific collision frequencies and is identical to the conventional expression.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Richard, P.

The study of inelastic collision phenomena with highly charged projectile ions and the interpretation of spectral features resulting from these collisions remain as the major focal points in the atomic physics research at the J.R. Macdonald Laboratory, Kansas State University, Manhattan, Kansas. The title of the research project, ``Atomic Physics with Highly Charged Ions,`` speaks to these points. The experimental work in the past few years has divided into collisions at high velocity using the primary beams from the tandem and LINAC accelerators and collisions at low velocity using the CRYEBIS facility. Theoretical calculations have been performed to accurately describemore » inelastic scattering processes of the one-electron and many-electron type, and to accurately predict atomic transition energies and intensities for x rays and Auger electrons. Brief research summaries are given for the following: (1) electron production in ion-atom collisions; (2) role of electron-electron interactions in two-electron processes; (3) multi-electron processes; (4) collisions with excited, aligned, Rydberg targets; (5) ion-ion collisions; (6) ion-molecule collisions; (7) ion-atom collision theory; and (8) ion-surface interactions.« less

Metastability of isoformyl ions in collisions with helium and hydrogen. [in interstellar molecular clouds

NASA Technical Reports Server (NTRS)

Green, S.

1984-01-01

The stability of HOC(+) ions under conditions in interstellar molecular clouds is considered. In particular, the possibility that collisions with helium or hydrogen will induce isomerization to the stable HCO(+) form is examined theoretically. Portions of the electronic potential energy surfaces for interaction with He and H atoms are obtained from standard quantum mechanical calculations. Collisions with He atoms are found to be totally ineffective for inducing isomerization. Collisions with H atoms are found to be ineffective at low interstellar temperatures owing to a small (about 500 K) barrier in the entrance channel; at higher temperatures where this barrier can be overcome, however, collisions with hydrogen atoms do result in conversion to the stable HCO(+) form. Although detailed calculations are not presented, it is argued that low-energy collisions with H2 molecules are also ineffective in destroying the metastable ion.

Ion-polycyclic aromatic hydrocarbon collisions: kinetic energy releases for specific fragmentation channels

NASA Astrophysics Data System (ADS)

Reitsma, G.; Zettergren, H.; Boschman, L.; Bodewits, E.; Hoekstra, R.; Schlathölter, T.

2013-12-01

We report on 30 keV He2 + collisions with naphthalene (C10H8) molecules, which leads to very extensive fragmentation. To unravel such complex fragmentation patterns, we designed and constructed an experimental setup, which allows for the determination of the full momentum vector by measuring charged collision products in coincidence in a recoil ion momentum spectrometer type of detection scheme. The determination of fragment kinetic energies is found to be considerably more accurate than for the case of mere coincidence time-of-flight spectrometers. In fission reactions involving two cationic fragments, typically kinetic energy releases of 2-3 eV are observed. The results are interpreted by means of density functional theory calculations of the reverse barriers. It is concluded that naphthalene fragmentation by collisions with keV ions clearly is much more violent than the corresponding photofragmentation with energetic photons. The ion-induced naphthalene fragmentation provides a feedstock of various small hydrocarbonic species of different charge states and kinetic energy, which could influence several molecule formation processes in the cold interstellar medium and facilitates growth of small hydrocarbon species on pre-existing polycyclic aromatic hydrocarbons.

Magnetic trapping of cold bromine atoms.

PubMed

Rennick, C J; Lam, J; Doherty, W G; Softley, T P

2014-01-17

Magnetic trapping of bromine atoms at temperatures in the millikelvin regime is demonstrated for the first time. The atoms are produced by photodissociation of Br2 molecules in a molecular beam. The lab-frame velocity of Br atoms is controlled by the wavelength and polarization of the photodissociation laser. Careful selection of the wavelength results in one of the pair of atoms having sufficient velocity to exactly cancel that of the parent molecule, and it remains stationary in the lab frame. A trap is formed at the null point between two opposing neodymium permanent magnets. Dissociation of molecules at the field minimum results in the slowest fraction of photofragments remaining trapped. After the ballistic escape of the fastest atoms, the trapped slow atoms are lost only by elastic collisions with the chamber background gas. The measured loss rate is consistent with estimates of the total cross section for only those collisions transferring sufficient kinetic energy to overcome the trapping potential.

Threshold collision-induced dissociation of diatomic molecules: a case study of the energetics and dynamics of O2- collisions with Ar and Xe.

PubMed

Ahu Akin, F; Ree, Jongbaik; Ervin, Kent M; Kyu Shin, Hyung

2005-08-08

The energetics and dynamics of collision-induced dissociation of O2- with Ar and Xe targets are studied experimentally using guided ion-beam tandem mass spectrometry. The cross sections and the collision dynamics are modeled theoretically by classical trajectory calculations. Experimental apparent threshold energies are 2.1 and 1.1 eV in excess of the thermochemical O2- bond dissociation energy for argon and xenon, respectively. Classical trajectory calculations confirm the observed threshold behavior and the dependence of cross sections on the relative kinetic energy. Representative trajectories reveal that the bond dissociation takes place on a short time scale of about 50 fs in strong direct collisions. Collision-induced dissociation is found to be remarkably restricted to the perpendicular approach of ArXe to the molecular axis of O2-, while collinear collisions do not result in dissociation. The higher collisional energy-transfer efficiency of xenon compared with argon is attributed to both mass and polarizability effects.

Laser absorption spectroscopy of water vapor confined in nanoporous alumina: wall collision line broadening and gas diffusion dynamics.

PubMed

Svensson, Tomas; Lewander, Märta; Svanberg, Sune

2010-08-02

We demonstrate high-resolution tunable diode laser absorption spectroscopy (TDLAS) of water vapor confined in nanoporous alumina. Strong multiple light scattering results in long photon pathlengths (1 m through a 6 mm sample). We report on strong line broadening due to frequent wall collisions (gas-surface interactions). For the water vapor line at 935.685 nm, the HWHM of confined molecules are about 4.3 GHz as compared to 2.9 GHz for free molecules (atmospheric pressure). Gas diffusion is also investigated, and in contrast to molecular oxygen (that moves rapidly in and out of the alumina), the exchange of water vapor is found very slow.

Laboratory observations of the photochemistry of parent molecules: A review

NASA Technical Reports Server (NTRS)

Jackson, W. M.

1976-01-01

The photochemistry of possible parent molecules of comets has been reviewed. Quantum yields for many of the primary processes are unknown. Energy partitioning among the fragments has not been extensively investigated. A few of the studies have been performed as a function of the number of collisions that the excited molecules undergo, so that possible differences that may occur in a cometary environment may be ascertained.

Investigation of energy deposited by femtosecond electron transfer in collisions using hydrated ion nanocalorimetry.

PubMed

Holm, Anne I S; Donald, William A; Hvelplund, Preben; Larsen, Mikkel K; Nielsen, Steen Brøndsted; Williams, Evan R

2008-10-30

Ion nanocalorimetry is used to investigate the internal energy deposited into M (2+)(H 2O) n , M = Mg ( n = 3-11) and Ca ( n = 3-33), upon 100 keV collisions with a Cs or Ne atom target gas. Dissociation occurs by loss of water molecules from the precursor (charge retention) or by capture of an electron to form a reduced precursor (charge reduction) that can dissociate either by loss of a H atom accompanied by water molecule loss or by exclusively loss of water molecules. Formation of bare CaOH (+) and Ca (+) by these two respective dissociation pathways occurs for clusters with n up to 33 and 17, respectively. From the threshold dissociation energies for the loss of water molecules from the reduced clusters, obtained from binding energies calculated using a discrete implementation of the Thomson liquid drop model and from quantum chemistry, estimates of the internal energy deposition can be obtained. These values can be used to establish a lower limit to the maximum and average energy deposition. Not taking into account effects of a kinetic shift, over 16 eV can be deposited into Ca (2+)(H 2O) 33, the minimum energy necessary to form bare CaOH (+) from the reduced precursor. The electron capture efficiency is at least a factor of 40 greater for collisions of Ca (2+)(H 2O) 9 with Cs than with Ne, reflecting the lower ionization energy of Cs (3.9 eV) compared to Ne (21.6 eV). The branching ratio of the two electron capture dissociation pathways differs significantly for these two target gases, but the distributions of water molecules lost from the reduced precursors are similar. These results suggest that the ionization energy of the target gas has a large effect on the electron capture efficiency, but relatively little effect on the internal energy deposited into the ion. However, the different branching ratios suggest that different electronic excited states may be accessed in the reduced precursor upon collisions with these two different target gases.

The rotational excitation of the HCN and HNC molecules by H2 revisited

NASA Astrophysics Data System (ADS)

Hernández Vera, M.; Lique, F.; Dumouchel, F.; Hily-Blant, P.; Faure, A.

2017-06-01

HCN and HNC are two fundamental molecules in the dense interstellar medium. The HNC/HCN abundance ratio depends on the kinetic temperature and can be used to explore the physical and chemical conditions of star-forming regions. Modelling of HCN and HNC emissions from interstellar clouds requires to model their collisional and radiative excitations. We report the calculation of the HCN and HNC excitation rate coefficients among the first 26 rotational levels due to H2 collisions, for temperatures ranging from 5 to 500 K, using the exact close coupling and the approximate coupled states methods. We found a propensity for even Δj transitions in the case of HCN-para-H2 collisions, whereas a propensity for odd Δj transitions is observed in the case of HNC-para-H2 collisions. For collisions with ortho-H2, both molecules show a propensity rule favouring transitions with odd Δj. The rate coefficients for HCN and HNC differ significantly, showing clearly that the collisional excitation of the two isomers is different, especially for para-H2. We also evaluate the impact of these new data on the astrophysical modelling through radiative transfer calculations. It is shown that specific calculations have to be performed for the two isomers and that the HNC/HCN abundance ratio in cold molecular clouds cannot be estimated from line intensity ratio. Finally, observations of the two isotopologues H13CN and HN13C towards a sample of prestellar cores are presented, and the larger excitation temperature of HN13C is well reproduced by our excitation model.

Energy distributions of H{sup +} fragments ejected by fast proton and electron projectiles in collision with H{sub 2}O molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barros, A. L. F. de; Lecointre, J.; Luna, H.

Experimental measurements of the kinetic energy distribution spectra of H{sup +} fragment ions released during radiolysis of water molecules in collision with 20, 50, and 100 keV proton projectiles and 35, 200, 400, and 1000 eV electron projectiles are reported using a pulsed beam and drift tube time-of-flight based velocity measuring technique. The spectra show that H{sup +} fragments carrying a substantial amount of energy are released, some having energies well in excess of 20 eV. The majority of the ions lie within the 0-5 eV energy range with the proton spectra showing an almost constant profile between 1.5 andmore » 5 eV and, below this, increasing gradually with decreasing ejection energy up to the near zero energy value while the electron spectra, in contrast, show a broad maximum between 1 and 3 eV and a pronounced dip around 0.25 eV. Beyond 5 eV, both projectile spectra show a decreasing profile with the electron spectra decreasing far more rapidly than the proton spectra. Our measured spectra thus indicate that major differences are present in the collision dynamics between the proton and the electron projectiles interacting with gas phase water molecules.« less

Matter-wave entanglement and teleportation by molecular dissociation and collisions.

PubMed

Opatrný, T; Kurizki, G

2001-04-02

We propose dissociation of cold diatomic molecules as a source of atom pairs with highly correlated (entangled) positions and momenta, approximating the original quantum state introduced by Einstein, Podolsky, and Rosen (EPR) [Phys. Rev. 47, 777 (1935)]. Wave packet teleportation is shown to be achievable by its collision with one of the EPR correlated atoms and manipulation of the other atom in the pair.

Matter-Wave Entanglement and Teleportation by Molecular Dissociation and Collisions

NASA Astrophysics Data System (ADS)

Opatrný, T.; Kurizki, G.

2001-04-01

We propose dissociation of cold diatomic molecules as a source of atom pairs with highly correlated (entangled) positions and momenta, approximating the original quantum state introduced by Einstein, Podolsky, and Rosen (EPR) [Phys. Rev. 47, 777 (1935)]. Wave packet teleportation is shown to be achievable by its collision with one of the EPR correlated atoms and manipulation of the other atom in the pair.

Dynamic of negative ions in potassium-D-ribose collisions.

PubMed

Almeida, D; Ferreira da Silva, F; García, G; Limão-Vieira, P

2013-09-21

We present negative ion formation from collisions of neutral potassium atoms with D-ribose (C5H10O5), the sugar unit in the DNA/RNA molecule. From the negative ion time-of-flight (TOF) mass spectra, OH(-) is the main fragment detected in the collision range 50-100 eV accounting on average for 50% of the total anion yield. Prominence is also given to the rich fragmentation pattern observed with special attention to O(-) (16 m/z) formation. These results are in sharp contrast to dissociative electron attachment experiments. The TOF mass spectra assignments show that these channels are also observed, albeit with a much lower relative intensity. Branching ratios of the most abundant fragment anions as a function of the collision energy are obtained, allowing to establish a rationale on the collision dynamics.

The Submillimeter-wave Rotational Spectra of Interstellar Molecules

NASA Technical Reports Server (NTRS)

Herbst, Eric; DeLucia, Frank C.; Butler, R. A. H.; Winnewisser, M.; Winnewisser, G.; Fuchs, U.; Groner, P.; Sastry, K. V. L. N.

2002-01-01

We discuss past and recent progress in our long-term laboratory program concerning the submillimeter-wave rotational spectroscopy of known and likely interstellar molecules, especially those associated with regions of high-mass star formation. Our program on the use of spectroscopy to study rotationally inelastic collisions of interstellar interest is also briefly mentioned.

Ab Initio Study of Chemical Reactions of Cold SrF and CaF Molecules with Alkali-Metal and Alkaline-Earth-Metal Atoms: The Implications for Sympathetic Cooling.

PubMed

Kosicki, Maciej Bartosz; Kędziera, Dariusz; Żuchowski, Piotr Szymon

2017-06-01

We investigate the energetics of the atom exchange reaction in the SrF + alkali-metal atom and CaF + alkali-metal atom systems. Such reactions are possible only for collisions of SrF and CaF with the lithium atoms, while they are energetically forbidden for other alkali-metal atoms. Specifically, we focus on SrF interacting with Li, Rb, and Sr atoms and use ab initio methods to demonstrate that the SrF + Li and SrF + Sr reactions are barrierless. We present potential energy surfaces for the interaction of the SrF molecule with the Li, Rb, and Sr atoms in their energetically lowest-lying electronic spin states. The obtained potential energy surfaces are deep and exhibit profound interaction anisotropies. We predict that the collisions of SrF molecules in the rotational or Zeeman excited states most likely have a strong inelastic character. We discuss the prospects for the sympathetic cooling of SrF and CaF molecules using ultracold alkali-metal atoms.

The contribution of electron collisions to rotational excitations of cometary water

NASA Technical Reports Server (NTRS)

Xie, Xingfa; Mumma, Michael J.

1992-01-01

The e-H2O collisional rate for exciting rotational transitions in cometary water is evaluated for conditions found in comet Halley during the Giotto spacecraft encounter. In the case of the O(sub 00) yields 1(sub 11) rotational transition, the e-H2O collisional rate exceeds that for excitation by neutral-neutral collisions at distances exceeding 3000 km from the cometary nucleus. Thus, the rotational temperature of the water molecule in the intermediate coma may be controlled by collisions with electrons rather than with neutral collisions, and the rotational temperature retrieved from high resolution infrared spectra of water in comet Halley may reflect electron temperatures rather than neutral gas temperature in the intermediate coma.

Anisotropic mechanoresponse of energetic crystallites: a quantum molecular dynamics study of nano-collision

NASA Astrophysics Data System (ADS)

Li, Ying; Kalia, Rajiv K.; Misawa, Masaaki; Nakano, Aiichiro; Nomura, Ken-Ichi; Shimamura, Kohei; Shimojo, Fuyuki; Vashishta, Priya

2016-05-01

At the nanoscale, chemistry can happen quite differently due to mechanical forces selectively breaking the chemical bonds of materials. The interaction between chemistry and mechanical forces can be classified as mechanochemistry. An example of archetypal mechanochemistry occurs at the nanoscale in anisotropic detonating of a broad class of layered energetic molecular crystals bonded by inter-layer van der Waals (vdW) interactions. Here, we introduce an ab initio study of the collision, in which quantum molecular dynamic simulations of binary collisions between energetic vdW crystallites, TATB molecules, reveal atomistic mechanisms of anisotropic shock sensitivity. The highly sensitive lateral collision was found to originate from the twisting and bending to breaking of nitro-groups mediated by strong intra-layer hydrogen bonds. This causes the closing of the electronic energy gap due to an inverse Jahn-Teller effect. On the other hand, the insensitive collisions normal to multilayers are accomplished by more delocalized molecular deformations mediated by inter-layer interactions. Our nano-collision studies provide a much needed atomistic understanding for the rational design of insensitive energetic nanomaterials and the detonation synthesis of novel nanomaterials.At the nanoscale, chemistry can happen quite differently due to mechanical forces selectively breaking the chemical bonds of materials. The interaction between chemistry and mechanical forces can be classified as mechanochemistry. An example of archetypal mechanochemistry occurs at the nanoscale in anisotropic detonating of a broad class of layered energetic molecular crystals bonded by inter-layer van der Waals (vdW) interactions. Here, we introduce an ab initio study of the collision, in which quantum molecular dynamic simulations of binary collisions between energetic vdW crystallites, TATB molecules, reveal atomistic mechanisms of anisotropic shock sensitivity. The highly sensitive lateral collision was found to originate from the twisting and bending to breaking of nitro-groups mediated by strong intra-layer hydrogen bonds. This causes the closing of the electronic energy gap due to an inverse Jahn-Teller effect. On the other hand, the insensitive collisions normal to multilayers are accomplished by more delocalized molecular deformations mediated by inter-layer interactions. Our nano-collision studies provide a much needed atomistic understanding for the rational design of insensitive energetic nanomaterials and the detonation synthesis of novel nanomaterials. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08769d

Classical scattering calculations for diatomic molecules: A general procedure and application to the microwave spectrum O2

NASA Technical Reports Server (NTRS)

Mingelgrin, U.

1972-01-01

Many properties of gaseous systems such as electromagnetic absorption and emission, sound dispersion and absorption, may be elucidated if the nature of collisions between the particles in the system is understood. A procedure for the calculation of the classical trajectories of two interacting diatomic molecules is described. The dynamics of the collision will be assumed to be that of two rigid rotors moving in a specified potential. The actual outcome of a representative sample of many trajectories at 298K was computed, and the use of these values at any temperature for calculations of various molecular properties will be described. Calculations performed for the O2 microwave spectrum are given to demonstrate the use of the procedure described.

Collisions of ideal gas molecules with a rough/fractal surface. A computational study.

PubMed

Panczyk, Tomasz

2007-02-01

The frequency of collisions of ideal gas molecules (argon) with a rough surface has been studied. The rough/fractal surface was created using random deposition technique. By applying various depositions, the roughness of the surface was controlled and, as a measure of the irregularity, the fractal dimensions of the surfaces were determined. The surfaces were next immersed in argon (under pressures 2 x 10(3) to 2 x 10(5) Pa) and the numbers of collisions with these surfaces were counted. The calculations were carried out using a simplified molecular dynamics simulation technique (only hard core repulsions were assumed). As a result, it was stated that the frequency of collisions is a linear function of pressure for all fractal dimensions studied (D = 2, ..., 2.5). The frequency per unit pressure is quite complex function of the fractal dimension; however, the changes of that frequency with the fractal dimension are not strong. It was found that the frequency of collisions is controlled by the number of weakly folded sites on the surfaces and there is some mapping between the shape of adsorption energy distribution functions and this number of weakly folded sites. The results for the rough/fractal surfaces were compared with the prediction given by the Langmuir-Hertz equation (valid for smooth surface), generally the departure from the Langmuir-Hertz equation is not higher than 48% for the studied systems (i.e. for the surfaces created using the random deposition technique).

Simple model for molecular scattering

NASA Astrophysics Data System (ADS)

Mehta, Nirav; Ticknor, Christopher; Hazzard, Kaden

2017-04-01

The collisions of ultracold molecules are qualitatively different from the collisions of ultracold atoms due to the high density of bimolecular resonances near the collision energy. We present results from a simple N-channel scattering model with square-well channel potentials and constant channel couplings (inside the well) designed to reproduce essential features of chaotic molecular scattering. The potential depths and channel splittings are tuned to reproduce the appropriate density of states for the short-range bimolecular collision complex (BCC), which affords a direct comparison of the resulting level-spacing distribution to that expected from random matrix theory (RMT), namely the so-called Wigner surmise. The density of states also sets the scale for the rate of dissociation from the BCC to free molecules, as approximated by transition state theory (TST). Our model affords a semi-analytic solution for the scattering amplitude in the open channel, and a determinantal equation for the eigenenergies of the short-ranged BCC. It is likely the simplest finite-ranged scattering model that can be compared to expectations from the approximations of RMT, and TST. The validity of these approximations has implications for the many-channel Hubbard model recently developed. This research was funded in part by the National Science Foundation under Grant No. NSF PHY-1125915.

Ergodic properties of the multidimensional rayleigh gas with a semipermeable barrier

NASA Astrophysics Data System (ADS)

Erdős, L.; Tuyen, D. Q.

1990-06-01

We consider a multidimensional system consisting of a particle of mass M and radius r (molecule), surrounded by an infinite ideal gas of point particles of mass m (atoms). The molecule is confined to the unit ball and interacts with its boundary ( barrier) via elastic collision, while the atoms are not affected by the boundary. We obtain convergence to equilibrium for the molecule from almost every initial distribution on its position and velocity. Furthermore, we prove that the infinite composite system of the molecule and the atoms is Bernoulli.

Infrared absorption by molecular gases as a probe of nanoporous silica xerogel and molecule-surface collisions: Low-pressure results

NASA Astrophysics Data System (ADS)

Vander Auwera, J.; Ngo, N. H.; El Hamzaoui, H.; Capoen, B.; Bouazaoui, M.; Ausset, P.; Boulet, C.; Hartmann, J.-M.

2013-10-01

Transmission spectra of gases confined (but not adsorbed) within the pores of a 1.4-cm-thick silica xerogel sample have been recorded between 2.5 and 5 μm using a high-resolution Fourier transform spectrometer. This was done for pure CO, CO2, N2O, H2O, and CH4 at room temperature and pressures of a few hectopascals. Least-squares fits of measured absorption lines provide the optical-path lengths within the confined (LC) and free (LF) gas inside the absorption cell and the half width at half maximum ΓC of the lines of the confined gases. The values of LC and LF retrieved using numerous transitions of all studied species are very consistent. Furthermore, LC is in satisfactory agreement with values obtained from independent measurements, thus showing that reliable information on the open porosity volume can be retrieved from an optical experiment. The values of ΓC, here resulting from collisions of the molecules with the inner surfaces of the xerogel pores, are practically independent of the line for each gas and inversely proportional to the square root of the probed-molecule molar mass. This is a strong indication that, for the studied transitions, a single collision of a molecule with a pore surface is sufficient to change its rotational state. A previously proposed simple model, used for the prediction of the line shape, leads to satisfactory agreement with the observations. It also enables a determination of the average pore size, bringing information complementary to that obtained from nitrogen adsorption porosimetry.

Protein electrochemistry using graphene-based nano-assembly: an ultrasensitive electrochemical detection of protein molecules via nanoparticle-electrode collisions.

PubMed

Li, Da; Liu, Jingquan; Barrow, Colin J; Yang, Wenrong

2014-08-04

We describe a new electrochemical detection approach towards single protein molecules (microperoxidase-11, MP-11), which are attached to the surface of graphene nanosheets. The non-covalently functionalized graphene nanosheets exhibit enhanced electroactive surface area, where amplified redox current is produced when graphene nanosheets collide with the electrode.

The effect of electron collisions on rotational excitation of cometary water

NASA Technical Reports Server (NTRS)

Xie, Xingfa; Mumma, Michael J.

1991-01-01

The e-H2O collisional rate for exciting rotational transitions in cometary water is evaluated for conditions found in Comet Halley. The e-H2O collisional rate exceeds that for excitation by neutral-neutral collisions at distances exceeding 3000 km from the cometary nucleus, in the case of the O sub 00 yields 1 sub 11 transition. The estimates are based on theoretical and experimental studies of e-H2O collisions, on ion and electron parameters acquired in-situ by instruments on the Giotto and Vega spacecraft, and on results obtained from models of the cometary ionosphere. The contribution of electron collisions may explain the need for large water-water cross-sections in models which neglect the effect of electrons. The importance of electron collisions is enhanced for populations of water molecules in regions where their rotational lines are optically thick.

On ionizing shock waves

NASA Astrophysics Data System (ADS)

Kaniel, A.; Igra, O.; Ben-Dor, G.; Mond, M.

The flow field in the ionizing relaxation zone developed behind a normal shock wave in an electrically neutral, homogeneous, two temperature mixture of thermally ideal gases (molecules, atoms, ions, electrons) was numerically solved. The heat transfer between the electron gas and the other components was taken into account while all the other transport phenomena (molecular, turbulent and radiative) were neglected in the relaxation zone, since it is dominated by inelastic collisions. The threshold cross sections measured by Specht (1981), for excitation of argon by electron collisions, were used. The calculated results show good agreement with the results of the shock tube experiments presented by Glass and Liu (1978), especially in the electron avalanche region. A critical examination was made of the common assumptions regarding the average energy with which electrons are produced by atom-atom collisions and the relative effectiveness of atom-atom collisions (versus electron-atom collisions) in ionizing excited argon.

Ab Initio Study of Ultracold Polar Molecules in Optical Lattices

DTIC Science & Technology

2010-01-01

collisions of Li and alkaline-earth or rare- earth atoms, such LiSr and LiYb. Finally, we calculated the isotropic and anisotropic interaction potentials... LiSr and LiYb molecules. To the best of our knowledge, only LiMg was experimentally investigated [3], which allowed us to compare our predictions...alkaline-earth or rare-earth atoms. Interest in the LiSr and LiYb molecules stems from prospects to achieve optical Feshbach tuning of scattering properties

Energy transfer upon collision of selectively excited CO2 molecules: State-to-state cross sections and probabilities for modeling of atmospheres and gaseous flows.

PubMed

Lombardi, A; Faginas-Lago, N; Pacifici, L; Grossi, G

2015-07-21

Carbon dioxide molecules can store and release tens of kcal/mol upon collisions, and such an energy transfer strongly influences the energy disposal and the chemical processes in gases under the extreme conditions typical of plasmas and hypersonic flows. Moreover, the energy transfer involving CO2 characterizes the global dynamics of the Earth-atmosphere system and the energy balance of other planetary atmospheres. Contemporary developments in kinetic modeling of gaseous mixtures are connected to progress in the description of the energy transfer, and, in particular, the attempts to include non-equilibrium effects require to consider state-specific energy exchanges. A systematic study of the state-to-state vibrational energy transfer in CO2 + CO2 collisions is the focus of the present work, aided by a theoretical and computational tool based on quasiclassical trajectory simulations and an accurate full-dimension model of the intermolecular interactions. In this model, the accuracy of the description of the intermolecular forces (that determine the probability of energy transfer in molecular collisions) is enhanced by explicit account of the specific effects of the distortion of the CO2 structure due to vibrations. Results show that these effects are important for the energy transfer probabilities. Moreover, the role of rotational and vibrational degrees of freedom is found to be dominant in the energy exchange, while the average contribution of translations, under the temperature and energy conditions considered, is negligible. Remarkable is the fact that the intramolecular energy transfer only involves stretching and bending, unless one of the colliding molecules has an initial symmetric stretching quantum number greater than a threshold value estimated to be equal to 7.

Vibration-translation energy transfer in vibrationally excited diatomic molecules. Ph.D. Thesis - York Univ., Toronto

NASA Technical Reports Server (NTRS)

Mckenzie, R. L.

1976-01-01

A semiclassical collision model is applied to the study of energy transfer rates between a vibrationally excited diatomic molecule and a structureless atom. The molecule is modeled as an anharmonic oscillator with a multitude of dynamically coupled vibrational states. Three main aspects in the prediction of vibrational energy transfer rates are considered. The applicability of the semiclassical model to an anharmonic oscillator is first evaluated for collinear encounters. Second, the collinear semiclassical model is applied to obtain numerical predictions of the vibrational energy transfer rate dependence on the initial vibrational state quantum number. Thermally averaged vibration-translation rate coefficients are predicted and compared with CO-He experimental values for both ground and excited initial states. The numerical model is also used as a basis for evaluating several less complete but analytic models. Third, the role of rational motion in the dynamics of vibrational energy transfer is examined. A three-dimensional semiclassical collision model is constructed with coupled rotational motion included. Energy transfer within the molecule is shown to be dominated by vibration-rotation transitions with small changes in angular momentum. The rates of vibrational energy transfer in molecules with rational frequencies that are very small in comparison to their vibrational frequency are shown to be adequately treated by the preceding collinear models.

Activated recombinative desorption: A potential component in mechanisms of spacecraft glow

NASA Technical Reports Server (NTRS)

Cross, J. B.

1985-01-01

The concept of activated recombination of atomic species on surfaces can explain the production of vibrationally and translationally excited desorbed molecular species. Equilibrium statistical mechanics predicts that the molecular quantum state distributions of desorbing molecules is a function of surface temperature only when the adsorption probability is unity and independent of initial collision conditions. In most cases, the adsorption probability is dependent upon initial conditions such as collision energy or internal quantum state distribution of impinging molecules. From detailed balance, such dynamical behavior is reflected in the internal quantum state distribution of the desorbing molecule. This concept, activated recombinative desorption, may offer a common thread in proposed mechanisms of spacecraft glow. Using molecular beam techniques and equipment available at Los Alamos, which includes a high translational energy 0-atom beam source, mass spectrometric detection of desorbed species, chemiluminescence/laser induced fluorescence detection of electronic and vibrationally excited reaction products, and Auger detection of surface adsorbed reaction products, a fundamental study of the gas surface chemistry underlying the glow process is proposed.

Thermophoretic force and velocity of nanoparticles in the free molecule regime.

PubMed

Li, Zhigang; Wang, Hai

2004-08-01

We extend our previous gas-kinetic theory analysis of drag force in a uniform temperature field [Li and Wang, Phys. Rev. E. 68, 061206 (2003); 68, 061207 (2003)] to particle transport in fluids with nonuniform temperature. Formulations for drag and thermophoretic forces are proposed for nanoparticle transport in low-density gases. We specifically consider the influence of nonrigid body collision due to van der Waals or other forces between the particle and gas molecules and find that these forces play a notable role for particles a few nanometers in size. It is shown that the present formulations can be easily reduced to the classical result of Waldmann [Z. Naturforsch. A 14a, 589 (1959)] by assuming rigid body collision. From the force formulations we also obtain the equation governing the thermophoretic velocity. This velocity is found to be highly sensitive to the potential energy of interactions between gas molecules and particle, and as such Waldmann's thermophoretic velocity is not expected to be accurate for nanosized particles.

Separation and conversion dynamics of nuclear-spin isomers of gaseous methanol

PubMed Central

Sun, Zhen-Dong; Ge, Meihua; Zheng, Yujun

2015-01-01

All symmetrical molecules with non-zero nuclear spin exist in nature as nuclear-spin isomers (NSIs). However, owing to the lack of experimental information, knowledge is rare about interconversions of NSIs of gaseous molecules with torsional symmetry. Here we report our separation and conversion observations on NSI-torsion-specific transition systems of gaseous methanol from a light-induced drift experiment involving partially spatial separation of the ortho and para isomers. We find that vibrationally excited molecules of the methanol spin isomer have a smaller collision cross-section than their ground-state counterparts. Interconversion of the enriched ortho isomer with the para isomer, which is generally considered improbable, has been quantitatively studied by sensitive detections of the spectral intensities. Rather counterintuitively, this reveals that the interconversion is inhibited with increasing pressure. Our results suggest that the spin conversion mechanism in methanol is via a quantum relaxation process with the quantum Zeno effect induced by molecular collisions. PMID:25880882

Effect of collisions on photoelectron sheath in a gas

NASA Astrophysics Data System (ADS)

Sodha, Mahendra Singh; Mishra, S. K.

2016-02-01

This paper presents a study of the effect of the collision of electrons with atoms/molecules on the structure of a photoelectron sheath. Considering the half Fermi-Dirac distribution of photo-emitted electrons, an expression for the electron density in the sheath has been derived in terms of the electric potential and the structure of the sheath has been investigated by incorporating Poisson's equation in the analysis. The method of successive approximations has been used to solve Poisson's equation with the solution for the electric potential in the case of vacuum, obtained earlier [Sodha and Mishra, Phys. Plasmas 21, 093704 (2014)], being used as the zeroth order solution for the present analysis. The inclusion of collisions influences the photoelectron sheath structure significantly; a reduction in the sheath width with increasing collisions is obtained.

The effect of source temperature and collision gas in the FFR on metastable intensities in MRM studies of biomarkers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gallegos, E.J.; Bott, G.

1994-12-31

A systematic study was made of the affect of source temperature 200{degrees}C-350{degrees}C on metastable intensities in MRM (Metastable Reaction Monitoring) experiments with biological marker molecules in petroleum fractions. A similar study was made on the affect on metastable intensity with the presence of a collision gas in the FFR (First Field-free Region) of a double focusing mass spectrometer.

A cloud collision model for water maser excitation.

PubMed

Tarter, J C; Welch, W J

1986-06-01

High-velocity collisions between small, dense, neutral clouds or between a dense cloud and a dense shell can provide the energy source required to excite H2O maser emission. The radiative precursor from the surface of the collisional shock front rapidly diffuses through the cloud, heating the dust grains but leaving the H2 molecules cool. Transient maser emission occurs as the conditions for the Goldreich and Kwan "hot-dust cold-gas" maser pump scheme are realized locally within the cloud. In time the local maser action quenches due to the heating of the H2 molecules by collisions against the grains. Although this model cannot explain the very long-lived steady maser features, it is quite successful in explaining a number of the observed properties of the high-velocity features in such sources as Orion, W51, and W49. In particular, it provides a natural explanation for the rapid time variations, the narrow line widths, juxtaposition of high- and low-velocity features, and the short lifetimes which are frequently observed for the so-called high-velocity maser "bullets" thought to be accelerated by strong stellar winds.

Statistical modeling of competitive threshold collision-induced dissociation

NASA Astrophysics Data System (ADS)

Rodgers, M. T.; Armentrout, P. B.

1998-08-01

Collision-induced dissociation of (R1OH)Li+(R2OH) with xenon is studied using guided ion beam mass spectrometry. R1OH and R2OH include the following molecules: water, methanol, ethanol, 1-propanol, 2-propanol, and 1-butanol. In all cases, the primary products formed correspond to endothermic loss of one of the neutral alcohols, with minor products that include those formed by ligand exchange and loss of both ligands. The cross-section thresholds are interpreted to yield 0 and 298 K bond energies for (R1OH)Li+-R2OH and relative Li+ binding affinities of the R1OH and R2OH ligands after accounting for the effects of multiple ion-molecule collisions, internal energy of the reactant ions, and dissociation lifetimes. We introduce a means to simultaneously analyze the cross sections for these competitive dissociations using statistical theories to predict the energy dependent branching ratio. Thermochemistry in good agreement with previous work is obtained in all cases. In essence, this statistical approach provides a detailed means of correcting for the "competitive shift" inherent in multichannel processes.

Studies of electron-polyatomic-molecule collisions Applications to e-CH4

NASA Technical Reports Server (NTRS)

Lima, M. A. P.; Gibson, T. L.; Mckoy, V.; Huo, W. M.

1985-01-01

The first application of the Schwinger multichannel formulation to low-energy electron collisions with a nonlinear polyatomic target is reported. Integral and differential cross sections are obtained for e-CH4 collisions from 3 to 20 eV at the static-plus-exchange interaction level. In these studies, the exchange potential is directly evaluated and not approximated by local models. An interesting feature of the small-angle differential cross section is ascribed to polarization effects and not reproduced at the static-plus-exchange level. These differential cross sections are found to be in reasonable agreement with existing measurements at 7.5 eV and higher energies.

Surface Assisted Transient Displacement Charge Technique. II. Effect of Gases on Photoinduced Charge Transfer in Self-Assembled Monolayers

PubMed Central

Krasnoslobodtsev, Alexey V.; Smirnov, Sergei N.

2008-01-01

Surface assisted photoinduced transient displacement charge (SPTDC) technique was used to study charge transfer in self-assembled monolayers of 7-diethylaminocoumarin covalently linked to oxide surface in atmosphere of different gases. The dipole signal was found to be opposite to that in solution and dependent on the nature of gas and its pressure. The results were explained by collision-induced relaxation that impedes uninhibited tilting of molecules onto the surface. Collisions with paramagnetic oxygen induce intersystem crossing to long-lived triplet dipolar states of coumarin with the rate close to the half of that for the collision rate. PMID:16956285

DOE Office of Scientific and Technical Information (OSTI.GOV)

Croft, J. F. E.; Makrides, C.; Li, M.

A fundamental question in the study of chemical reactions is how reactions proceed at a collision energy close to absolute zero. This question is no longer hypothetical: quantum degenerate gases of atoms and molecules can now be created at temperatures lower than a few tens of nanokelvin. Here we consider the benchmark ultracold reaction between, the most-celebrated ultracold molecule, KRb and K. We map out an accurate ab initio ground-state potential energy surface of the K 2Rb complex in full dimensionality and report numerically-exact quantum-mechanical reaction dynamics. The distribution of rotationally resolved rates is shown to be Poissonian. An analysismore » of the hyperspherical adiabatic potential curves explains this statistical character revealing a chaotic distribution for the short-range collision complex that plays a key role in governing the reaction outcome.« less

Crossed beam (E--VRT) energy transfer experiment

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hertel, I.V.; Hofmann, H.; Rost, K.A.

A molecular crossed beam apparatus which has been developed to perform electronic-to-vibrational, rotational, translational (E--V,R,T) energy transfer studies is described. Its capabilities are illustrated on the basis of a number of energy transfer spectra obtained for collision systems of the type Na*+Mol(..nu..,j) ..-->..Na+Mol (..nu..',j') where Na* represents a laser excited sodium atom and Mol a diatomic or polyatomic molecule. Because of the lack of reliable dynamic theories on quenching processes, statistical approaches such as the ''linearly forced harmonic oscillator'' and ''prior distributions'' have been used to model the experimental spectra. The agreement is found to be satisfactory, so even suchmore » simple statistics may be useful to describe (E--V,R,T) energy transfer processes in collision systems with small molecules.« less

Low energy electron-molecule scattering using the R-matrix method

NASA Astrophysics Data System (ADS)

Gorfinkiel, Jimena

2014-10-01

The study of electron-molecule collisions continues to attract significant interest stimulated, in no small part, by the need for collisional data to model a number of physical environments and applied processes (e.g. the modelling of focused electron beam induced deposition and the description of the interaction of radiation with biological matter). This need for electron scattering data (cross sections but also information on the temporary negative ions, TNI, that can be formed) has motivated the renewed development of theoretical methodology and their computational implementation. I will present the latest developments in the study of low energy electron scattering from molecules and molecular clusters using the R-matrix method. Recent calculations on electron collisions with biologically relevant molecules have shed light on the formation of core-excited TNI these larger targets. The picture that emerges is much more complex than previously thought. I will discuss some examples as well as current and future developments of the methodology and software in order to provide more accurate collisional data (in particular cross sections) for bigger targets. In collaboration with Zdenek Masin, The Open University. This work was partially supported by EPSRC.

Impact fracture experiments simulating interstellar grain-grain collisions

NASA Technical Reports Server (NTRS)

Freund, Friedemann; Chang, Sherwood; Dickinson, J. Thomas

1990-01-01

Oxide and silicate grains condensing during the early phases of the formation of the solar system or in the outflow of stars are exposed to high partial pressures of the low-z elements H, C, N and O and their simple gaseous compounds. Though refractory minerals are nominally anhydrous and non-carbonate, if they crystallize in the presence of H2O, N2 and CO or CO2 gases, they dissolve traces of the gaseous components. The question arises: How does the presence of dissolved gases or gas components manifest itself when grain-grain collisions occur. What are the gases emitted when grains are shattered during a collision event. Researchers report on fracture experiments in ultrahigh vacuum (UHV, approximately less than 10 to the -8th power mbar) designed to measure (by means of a quadrupole mass spectrometer, QMS, with microns to ms time resolution) the emission of gases and vapors during and after impact (up to 1.5 sec). Two terrestrial materials were chosen which represent structural and compositional extremes: olivine (San Carlos, AZ), a densely packed Mg-Fe(2+) silicate from the upper mantle, available as 6 to 12 mm single crystals, and obsidian (Oregon), a structurally open, alkaline-SiO2-rich volcanic glass. In the olivine crystals OH- groups have been identified spectroscopically, as well as H2 molecules. Obsidian is a water-rich glass containing OH- besides H2O molecules. Olivine from the mantle often contains CO2, either as CO2-rich fluid in fluid inclusions or structurally dissolved or both. By analogy to synthetic glasses CO2 in the obsidian may be present in form of CO2 molecules in voids of molecular dimensions, or as carbonate anions, CO3(2-). No organic molecules have been detected spectroscopically in either material. Results indicate that refractory oxide/silicates which contain dissolved traces of the H2O and CO/CO2 components but no spectroscopically detectable traces of organics may release complex H-C-O (possibly H-C-N-O) molecules upon fracture, plus metal vapor. This points: (1) at complex reaction mechanisms between dissolved H2O, CO/CO2 (and N2) components within the mineral structure or during fracture, and (2) at the possibility that similar emission processes occur following grain-grain collisions in interstellar dust clouds.

Kinetics of highly vibrationally excited O2(X) molecules in inductively-coupled oxygen plasmas

NASA Astrophysics Data System (ADS)

Annušová, Adriana; Marinov, Daniil; Booth, Jean-Paul; Sirse, Nishant; Lino da Silva, Mário; Lopez, Bruno; Guerra, Vasco

2018-04-01

The high degree of vibrational excitation of O2 ground state molecules recently observed in inductively coupled plasma discharges is investigated experimentally in more detail and interpreted using a detailed self-consistent 0D global kinetic model for oxygen plasmas. Additional experimental results are presented and used to validate the model. The vibrational kinetics considers vibrational levels up to v = 41 and accounts for electron impact excitation and de-excitation (e-V), vibration-to-translation relaxation (V-T) in collisions with O2 molecules and O atoms, vibration-to-vibration energy exchanges (V-V), excitation of electronically excited states, dissociative electron attachment, and electron impact dissociation. Measurements were performed at pressures of 10–80 mTorr (1.33 and 10.67 Pa) and radio frequency (13.56 MHz) powers up to 500 W. The simulation results are compared with the absolute densities in each O2 vibrational level obtained by high sensitivity absorption spectroscopy measurements of the Schumann–Runge bands for O2(X, v = 4–18), O(3 P) atom density measurements by two-photon absorption laser induced fluorescence (TALIF) calibrated against Xe, and laser photodetachment measurements of the O‑ negative ions. The highly excited O2(X, v) distribution exhibits a shape similar to a Treanor-Gordiets distribution, but its origin lies in electron impact e-V collisions and not in V-V up-pumping, in contrast to what happens in all other molecular gases known to date. The relaxation of vibrational quanta is mainly due to V-T energy-transfer collisions with O atoms and to electron impact dissociation of vibrationally excited molecules, e+O2(X, v)→O(3P)+O(3P).

Collision Dynamics of Rydberg Atoms and Molecules at Ultralow Energies

DTIC Science & Technology

2005-12-31

body recombination between electrons, ions and neural gas atoms. We wish to study the interaction and collisions between two Rydberg atoms in the...transitions, Exact solutions of Stark mixing in atomic hydro- where Ekjn is the Levi - Civita antisymmetric symbol gen induced by the time-dependent...L and U do not close under commutation to form a Lie algebra because [Ui, Uj] = (-2g)iCijkLk, where cijk is the Levi - Civita antisymmetric symbol for

Dynamics of CO2 scattering off a perfluorinated self-assembled monolayer. Influence of the incident collision energy, mass effects, and use of different surface models.

PubMed

Nogueira, Juan J; Vázquez, Saulo A; Mazyar, Oleg A; Hase, William L; Perkins, Bradford G; Nesbitt, David J; Martínez-Núñez, Emilio

2009-04-23

The dynamics of collisions of CO2 with a perfluorinated alkanethiol self-assembled monolayer (F-SAM) on gold were investigated by classical trajectory calculations using explicit atom (EA) and united atom (UA) models to represent the F-SAM surface. The CO2 molecule was directed perpendicularly to the surface at initial collision energies of 1.6, 4.7, 7.7, and 10.6 kcal/mol. Rotational distributions of the scattered CO2 molecules are in agreement with experimental distributions determined for collisions of CO2 with liquid surfaces of perfluoropolyether. The agreement is especially good for the EA model. The role of the mass in the efficiency of the energy transfer was investigated in separate simulations in which the mass of the F atoms was replaced by either that of hydrogen or chlorine, while keeping the potential energy function unchanged. The calculations predict the observed trend that less energy is transferred to the surface as the mass of the alkyl chains increases. Significant discrepancies were found between results obtained with the EA and UA models. The UA surface leads to an enhancement of the energy transfer efficiency in comparison with the EA surface. The reason for this is in the softer structure of the UA surface, which facilitates transfer from translation to interchain vibrational modes.

Deviation from Normal Boltzmann Distribution of High-lying Energy Levels of Iron Atom Excited by Okamoto-cavity Microwave-induced Plasmas Using Pure Nitrogen and Nitrogen-Oxygen Gases.

PubMed

Wagatsuma, Kazuaki

2015-01-01

This paper describes several interesting excitation phenomena occurring in a microwave-induced plasma (MIP) excited with Okamoto-cavity, especially when a small amount of oxygen was mixed with nitrogen matrix in the composition of the plasma gas. An ion-to-atom ratio of iron, which was estimated from the intensity ratio of ion to atomic lines having almost the same excitation energy, was reduced by adding oxygen gas to the nitrogen MIP, eventually contributing to an enhancement in the emission intensities of the atomic lines. Furthermore, Boltzmann plots for iron atomic lines were observed in a wide range of the excitation energy from 3.4 to 6.9 eV, indicating that plots of the atomic lines having lower excitation energies (3.4 to 4.8 eV) were well fitted on a straight line while those having more than 5.5 eV deviated upwards from the linear relationship. This overpopulation would result from any other excitation process in addition to the thermal excitation that principally determines the Boltzmann distribution. A Penning-type collision with excited species of nitrogen molecules probably explains this additional excitation mechanism, in which the resulting iron ions recombine with captured electrons, followed by cascade de-excitations between closely-spaced excited levels just below the ionization limit. As a result, these high-lying levels might be more populated than the low-lying levels of iron atom. The ionization of iron would be caused less actively in the nitrogen-oxygen plasma than in a pure nitrogen plasma, because excited species of nitrogen molecule, which can provide the ionization energy in a collision with iron atom, are consumed through collisions with oxygen molecules to cause their dissociation. It was also observed that the overpopulation occurred to a lesser extent when oxygen gas was added to the nitrogen plasma. The reason for this was also attributed to decreased number density of the excited nitrogen species due to collisions with oxygen molecule.

Electron transfer, ionization, and excitation in atomic collisions. Progress report, June 15, 1992--June 14, 1995

DOE Office of Scientific and Technical Information (OSTI.GOV)

Winter, T.G.; Alston, S.G.

The research program of Winter and Alston addresses the fundamental processes of electron transfer, ionization, and excitation in ion-atom, ion-ion, and ion-molecule collisions. Attention is focussed on one- and two-electron systems and, more recently, quasi-one-electron systems whose electron-target-core interaction can be accurately modeled by one-electron potentials. The basic computational approaches can then be taken with few, if any, approximations, and the underlying collisional mechanisms can be more clearly revealed. Winter has focussed on intermediate collision energies (e.g., proton energies for p-He{sup +} collisions on the order of 100 kilo-electron volts), in which many electron states are strongly coupled during themore » collision and a coupled-state approach, such as a coupled-Sturmian-pseudostate approach, is appropriate. Alston has concentrated on higher collision energies (million electron-volt energies), or asymmetric collision systems, for which the coupling of the projectile is weaker with, however, many more target states being coupled together so that high-order perturbation theory is essential. Several calculations by Winter and Alston are described, as set forth in the original proposal.« less

Importance of rotational adiabaticity in collisions of CO2 super rotors with Ar and He

NASA Astrophysics Data System (ADS)

Murray, Matthew J.; Ogden, Hannah M.; Mullin, Amy S.

2018-02-01

The collision dynamics of optically centrifuged CO2 with Ar and He are reported here. The optical centrifuge produces an ensemble of CO2 molecules in high rotational states (with J ˜ 220) with oriented angular momentum. Polarization-dependent high-resolution transient IR absorption spectroscopy was used to measure the relaxation dynamics in the presence of Ar or He by probing the CO2 J = 76 and 100 states with Er o t=2306 and 3979 cm-1, respectively. The data show that He relaxes the CO2 super rotors more quickly than Ar. Doppler-broadened line profiles show that He collisions induce substantially larger rotation-to-translation energy transfer. CO2 super rotors have greater orientational anisotropy with He collisions and the anisotropy from the He collisions persists longer than with Ar. Super rotor relaxation dynamics are discussed in terms of mass effects related to classical gyroscope physics and collisional rotational adiabaticity.

Collision events between RNA polymerases in convergent transcription studied by atomic force microscopy

PubMed Central

Crampton, Neal; Bonass, William A.; Kirkham, Jennifer; Rivetti, Claudio; Thomson, Neil H.

2006-01-01

Atomic force microscopy (AFM) has been used to image, at single molecule resolution, transcription events by Escherichia coli RNA polymerase (RNAP) on a linear DNA template with two convergently aligned λpr promoters. For the first time experimentally, the outcome of collision events during convergent transcription by two identical RNAP has been studied. Measurement of the positions of the RNAP on the DNA, allows distinction of open promoter complexes (OPCs) and elongating complexes (EC) and collided complexes (CC). This discontinuous time-course enables subsequent analysis of collision events where both RNAP remain bound on the DNA. After collision, the elongating RNAP has caused the other (usually stalled) RNAP to back-track along the template. The final positions of the two RNAP indicate that these are collisions between an EC and a stalled EC (SEC) or OPC (previously referred to as sitting-ducks). Interestingly, the distances between the two RNAP show that they are not always at closest approach after ‘collision’ has caused their arrest. PMID:17012275

Protonium Formation in Collisions of Antiprotons with Hydrogen Molecules

NASA Astrophysics Data System (ADS)

Cohen, James S.

1997-04-01

The first full-dynamics calculation of barp capture by the H2 molecule has been performed using the quasiclassical Kirschbaum-Wilets method with modifications for accurate treatment of the molecular structure. It had been speculated in calculations of heavy-negative-particle (μ^-) capture by the H atom(J. S. Cohen, R. L. Martin, and W. R. Wadt, Phys. Rev. A 27), 1821 (1983). that the capture cross section for the H2 molecule might be smaller than that for the atom at very low energies (based on the absence of adiabatic ionization for the molecule) but larger at higher energies (based on the molecule having two electrons and a higher ionization potential). This speculation seemed to be borne out by a diabatic-states calculation,(G. Ya. Korenman and V. P. Popov, AIP Conference Proceedings 181, p. 145 (1989).) which showed the two cross sections crossing at a center-of-mass energy of ~8 eV. However, both the qualitative argument and that calculation neglected the molecular vibrational and rotational dynamics. The present calculations show that the molecular degrees of freedom of the target are important and that the molecular capture cross section is always larger and extends to a higher collision energy ( ~80 eV vs. ~25 eV) than the atomic cross section. The distribution of n and l quantum numbers of the captured barp will also be presented.

Universality and chaoticity in ultracold K+KRb chemical reactions

DOE PAGES

Croft, J. F. E.; Makrides, C.; Li, M.; ...

2017-07-19

A fundamental question in the study of chemical reactions is how reactions proceed at a collision energy close to absolute zero. This question is no longer hypothetical: quantum degenerate gases of atoms and molecules can now be created at temperatures lower than a few tens of nanokelvin. Here we consider the benchmark ultracold reaction between, the most-celebrated ultracold molecule, KRb and K. We map out an accurate ab initio ground-state potential energy surface of the K 2Rb complex in full dimensionality and report numerically-exact quantum-mechanical reaction dynamics. The distribution of rotationally resolved rates is shown to be Poissonian. An analysismore » of the hyperspherical adiabatic potential curves explains this statistical character revealing a chaotic distribution for the short-range collision complex that plays a key role in governing the reaction outcome.« less

Adimensional theory of shielding in ultracold collisions of dipolar rotors

NASA Astrophysics Data System (ADS)

González-Martínez, Maykel L.; Bohn, John L.; Quéméner, Goulven

2017-09-01

We investigate the electric field shielding of ultracold collisions of dipolar rotors, initially in their first rotational excited state, using an adimensional approach. We establish a map of good and bad candidates for efficient evaporative cooling based on this shielding mechanism, by presenting the ratio of elastic over quenching processes as a function of a rescaled rotational constant B ˜=B /sE3 and a rescaled electric field F ˜=d F /B . B ,d ,F ,andsE 3 are respectively the rotational constant, the full electric dipole moment of the molecules, the applied electric field, and a characteristic dipole-dipole energy. We identify two groups of bi-alkali-metal dipolar molecules. The first group, including RbCs, NaK, KCs, LiK, NaRb, LiRb, NaCs, and LiCs, is favorable with a ratio over 1000 at collision energies equal to (or even higher than) their characteristic dipolar energy. The second group, including LiNa and KRb, is not favorable. More generally, for molecules well described by Hund's case b, our adimensional study provides the conditions of efficient evaporative cooling. The range of appropriate rescaled rotational constant and rescaled field is approximately B ˜≥108 and 3.25 ≤F ˜≤3.8 , with a maximum ratio reached for F ˜≃3.4 for a given B ˜. We also discuss the importance of the electronic van der Waals interaction on the adimensional character of our study.

Observation of Vibrational Relaxation Dynamics in X(sup 3)Sigma(sup -)(sub g) Oxygen Following Stimulated Raman Excitation to the v=1 Level: Implications for the RELIEF Flow Tagging Technique

NASA Technical Reports Server (NTRS)

Diskin, Glenn S.; Lempert, Walter R.; Miles, Richard B.

1996-01-01

The vibrational relaxation of ground-state molecular oxygen (O2, X(sup 3)Sigma(sup -)(sub g)) has been observed, following stimulated Raman excitation to the first excited vibrational level (v=1). Time delayed laser-induced fluorescence probing of the ro-vibrational population distribution was used to examine the temporal relaxation behavior. In the presence of water vapor, the relaxation process is rapid, and is dominated by near-resonant vibrational energy exchange between the v=1 level of O2 and the n2 bending mode of H2O. In the absence of H2O, reequilibration proceeds via homogeneous vibrational energy transfer, in which a collision between two v=1 O2 molecules leaves one molecule in the v=2 state and the other in the v=0 state. Subsequent collisions between molecules in v=1 and v>1 result in continued transfer of population up the vibrational ladder. The implications of these results for the RELIEF flow tagging technique are discussed.

Rotationally inelastic scattering of PN by para-H2(j = 0) at low/moderate temperature

NASA Astrophysics Data System (ADS)

Najar, F.; Naouai, M.; Hanini, H. El; Jaidane, N.

2017-12-01

Calculation of the collisional rate coefficients with the most abundant species has been motivated by the desire to interpret observations of molecules in the interstellar medium. This paper will be concerned with rotational excitation of the phosphorus nitride (PN) molecule in its ground vibrational state by collisions with para-H2(j = 0). Ab intio potential energy surface for the PN-H2 van der Waals system, considering both molecules as rigid rotors, was computed via CCSD(T) method using the aug-cc-pVTZ basis sets, augmented by a bond functions placed at midway between the PN and H2 centres of mass. Cross-sections among the 40 first rotational levels of PN in collisions with para-H2(j = 0) were obtained using close coupling and coupled states calculations, for total energies up to 3000 cm- 1. Rate coefficients are presented for temperatures ranging from 5 to 300 K. A strong propensity favouring even Δj transitions is found. The comparison of the new PN-H2 rate coefficients with previously calculated PN-He rate coefficients shows that significant differences exist.

SENSITIVE PRESSURE GAUGE

DOEpatents

Ball, W.P.

1961-01-01

An electron multiplier device is described. It has a plurality of dynodes between an anode and cathode arranged to measure pressure, temperature, or other environmental physical conditions that proportionately iinfuences the quantity of gas molecules between the dynodes. The output current of the device is influenced by the reduction in electron multiplication at the dynodes due to energy reducing collisions of the electrons with the gas molecules between the dynodes. More particularly, the current is inversely proportional to the quantity of gas molecules, viz., the gas pressure. The device is, hence, extremely sensitive to low pressures.

Many particle spectroscopy of atoms, molecules, clusters and surfaces: international conference MPS-2016

NASA Astrophysics Data System (ADS)

Grum-Grzhimailo, Alexei N.; Popov, Yuri V.; Gryzlova, Elena V.; Solov'yov, Andrey V.

2017-07-01

The conference on Many Particle Spectroscopy of Atoms, Molecules, Clusters and Surfaces (MPS-2016) brought together near to a hundred scientists in the field of electronic, photonic, atomic and molecular collisions, and spectroscopy from around the world. We deliver an Editorial of a topical issue presenting original research results from some of the participants on both experimental and theoretical studies involving many particle spectroscopy of atoms, molecules, clusters and surfaces. Contribution to the Topical Issue "Many Particle Spectroscopy of Atoms, Molecules, Clusters and Surfaces", edited by A.N. Grum-Grzhimailo, E.V. Gryzlova, Yu.V. Popov, and A.V. Solov'yov.

Are Nonadiabatic Reaction Dynamics the Key to Novel Organosilicon Molecules? The Silicon (Si(3P))-Dimethylacetylene (C4H6(X1A1g)) System as a Case Study.

PubMed

Thomas, Aaron M; Dangi, Beni B; Yang, Tao; Kaiser, Ralf I; Lin, Lin; Chou, Tzu-Jung; Chang, Agnes H H

2018-06-06

The bimolecular gas phase reaction of ground-state silicon (Si; 3 P) with dimethylacetylene (C 4 H 6 ; X 1 A 1g ) was investigated under single collision conditions in a crossed molecular beams machine. Merged with electronic structure calculations, the data propose nonadiabatic reaction dynamics leading to the formation of singlet SiC 4 H 4 isomer(s) and molecular hydrogen (H 2 ) via indirect scattering dynamics along with intersystem crossing (ISC) from the triplet to the singlet surface. The reaction may lead to distinct energetically accessible singlet SiC 4 H 4 isomers ( 1 p8- 1 p24) in overall exoergic reaction(s) (-107 -20 +12 kJ mol -1 ). All feasible reaction products are either cyclic, carry carbene analogous silylene moieties, or carry C-Si-H or C-Si-C bonds that would require extensive isomerization from the initial collision complex(es) to the fragmenting singlet intermediate(s). The present study demonstrates the first successful crossed beams study of an exoergic reaction channel arising from bimolecular collisions of silicon, Si( 3 P), with a hydrocarbon molecule.

Rotational relaxation of CF+(X1Σ) in collision with He(1S)

NASA Astrophysics Data System (ADS)

Denis-Alpizar, O.; Inostroza, N.; Castro Palacio, J. C.

2018-01-01

The carbon monofluoride cation (CF+) has been detected recently in Galactic and extragalactic regions. Therefore, excitation rate coefficients of this molecule in collision with He and H2 are necessary for a correct interpretation of the astronomical observations. The main goal of this work is to study the collision of CF+ with He in full dimensionality at the close-coupling level and to report a large set of rotational rate coefficients. New ab initio interaction energies at the CCSD(T)/aug-cc-pv5z level of theory were computed, and a three-dimensional potential energy surface was represented using a reproducing kernel Hilbert space. Close-coupling scattering calculations were performed at collisional energies up to 1600 cm-1 in the ground vibrational state. The vibrational quenching cross-sections were found to be at least three orders of magnitude lower than the pure rotational cross-sections. Also, the collisional rate coefficients were reported for the lowest 20 rotational states of CF+ and an even propensity rule was found to be in action only for j > 4. Finally, the hyperfine rate coefficients were explored. These data can be useful for the determination of the interstellar conditions where this molecule has been detected.

Unraveling the formation of HCPH(X2A') molecules in extraterrestrial environments: crossed molecular beam study of the reaction of carbon atoms, C(3Pj), with phosphine, PH3(X1A1).

PubMed

Guo, Y; Gu, X; Zhang, F; Sun, B J; Tsai, M F; Chang, A H H; Kaiser, R I

2007-05-03

The reaction between ground state carbon atoms, C(3P(j)), and phosphine, PH3(X(1)A1), was investigated at two collision energies of 21.1 and 42.5 kJ mol(-1) using the crossed molecular beam technique. The chemical dynamics extracted from the time-of-flight spectra and laboratory angular distributions combined with ab initio calculations propose that the reaction proceeds on the triplet surface via an addition of atomic carbon to the phosphorus atom. This leads to a triplet CPH3 complex. A successive hydrogen shift forms an HCPH2 intermediate. The latter was found to decompose through atomic hydrogen emission leading to the cis/trans-HCPH(X(2)A') reaction products. The identification of cis/trans-HCPH(X(2)A') molecules under single collision conditions presents a potential pathway to form the very first carbon-phosphorus bond in extraterrestrial environments like molecular clouds and circumstellar envelopes, and even in the postplume chemistry of the collision of comet Shoemaker-Levy 9 with Jupiter.

Quenching of highly vibrationally excited pyrimidine by collisions with CO2

NASA Astrophysics Data System (ADS)

Johnson, Jeremy A.; Duffin, Andrew M.; Hom, Brian J.; Jackson, Karl E.; Sevy, Eric T.

2008-02-01

Relaxation of highly vibrationally excited pyrimidine (C4N2H4) by collisions with carbon dioxide has been investigated using diode laser transient absorption spectroscopy. Vibrationally hot pyrimidine (E'=40635cm-1) was prepared by 248-nm excimer laser excitation, followed by rapid radiationless relaxation to the ground electronic state. The nascent rotational population distribution (J=58-80) of the 0000 ground state of CO2 resulting from collisions with hot pyrimidine was probed at short times following the excimer laser pulse. Doppler spectroscopy was used to measure the CO2 recoil velocity distribution for J =58-80 of the 0000 state. Rate constants and probabilities for collisions populating these CO2 rotational states were determined. The measured energy transfer probabilities, indexed by final bath state, were resorted as a function of ΔE to create the energy transfer distribution function, P(E,E'), from E'-E˜1300-7000cm-1. P(E,E') is fitted to a single exponential and a biexponential function to determine the average energy transferred in a single collision between pyrimidine and CO2 and parameters that can be compared to previously studied systems using this technique, pyrazine/CO2, C6F6/CO2, and methylpyrazine/CO2. P(E,E') parameters for these four systems are also compared to various molecular properties of the donor molecules. Finally, P(E,E') is analyzed in the context of two models, one which suggests that the shape of P(E,E') is primarily determined by the low-frequency out-of-plane donor vibrational modes and one which suggests that the shape of P(E,E') can be determined by how the donor molecule final density of states changes with ΔE.

- and Frequency-Domain Signatures of Velocity Changing Collisions in Sub-Doppler Saturation Spectra and Pressure Broadening

NASA Astrophysics Data System (ADS)

Hall, Gregory; Xu, Hong; Forthomme, Damien; Dagdigian, Paul; Sears, Trevor

2017-06-01

We have combined experimental and theoretical approaches to the competition between elastic and inelastic collisions of CN radicals with Ar, and how this competition influences time-resolved saturation spectra. Experimentally, we have measured transient, two-color sub-Doppler saturation spectra of CN radicals with an amplitude chopped saturation laser tuned to selected Doppler offsets within rotational lines of the A-X (2-0) band, while scanning a frequency modulated probe laser across the hyperfine-resolved saturation features of corresponding rotational lines of the A-X (1-0) band. A steady-state depletion spectrum includes off-resonant contributions ascribed to velocity diffusion, and the saturation recovery rates depend on the sub-Doppler detuning. The experimental results are compared with Monte Carlo solutions to the Boltzmann equation for the collisional evolution of the velocity distributions of CN radicals, combined with a pressure-dependent and speed-dependent lifetime broadening. Velocity changing collisions are included by appropriately sampling the energy resolved differential cross sections for elastic scattering of selected rotational states of CN (X). The velocity space diffusion of Doppler tagged molecules proceeds through a series of small-angle scattering events, eventually terminating in an inelastic collision that removes the molecule from the coherently driven ensemble of interest. Collision energy-dependent total cross sections and differential cross sections for elastic scattering of selected CN rotational states with Ar were computed with Hibridon quantum scattering calculations, and used for sampling in the Monte Carlo modeling. Acknowledgments: Work at Brookhaven National Laboratory was carried out under Contract No. DE-SC0012704 with the U.S. Department of Energy, Office of Science, and supported by its Division of Chemical Sciences, Geosciences and Biosciences within the Office of Basic Energy Sciences.

Quantum State-Resolved Collision Dynamics of Nitric Oxide at Ionic Liquid and Molten Metal Surfaces

NASA Astrophysics Data System (ADS)

Zutz, Amelia Marie

Detailed molecular scale interactions at the gas-liquid interface are explored with quantum state-to-state resolved scattering of a jet-cooled beam of NO(2pi1/2; N = 0) from ionic liquid and molten metal surfaces. The scattered distributions are probed via laser-induced fluorescence methods, which yield rotational and spin-orbit state populations that elucidate the dynamics of energy transfer at the gas-liquid interface. These collision dynamics are explored as a function of incident collision energy, surface temperature, scattering angle, and liquid identity, all of which are found to substantially affect the degree of rotational, electronic and vibrational excitation of NO via collisions at the liquid surface. Rotational distributions observed reveal two distinct scattering pathways, (i) molecules that trap, thermalize and eventually desorb from the surface (trapping-desorption, TD), and (ii) those that undergo prompt recoil (impulsive scattering, IS) prior to complete equilibration with the liquid surface. Thermally desorbing NO molecules are found to have rotational temperatures close to, but slightly cooler than the surface temperature, indicative of rotational dependent sticking probabilities on liquid surfaces. Nitric oxide is a radical with multiple low-lying electronic states that serves as an ideal candidate for exploring nonadiabatic state-changing collision dynamics at the gas-liquid interface, which induce significant excitation from ground (2pi1/2) to excited (2pi 3/2) spin-orbit states. Molecular beam scattering of supersonically cooled NO from hot molten metals (Ga and Au, Ts = 300 - 1400 K) is also explored, which provide preliminary evidence for vibrational excitation of NO mediated by thermally populated electron-hole pairs in the hot, conducting liquid metals. The results highlight the presence of electronically nonadiabatic effects and build toward a more complete characterization of energy transfer dynamics at gas-liquid interfaces.

Vibrational cross sections for positron scattering by nitrogen molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mazon, K. T.; Tenfen, W.; Michelin, S. E.

2010-09-15

We present a systematic study of low-energy positron collision with nitrogen molecules. Vibrational elastic and excitation cross sections are calculated using the multichannel version of the continued fractions method in the close-coupling scheme for the positron incident energy up to 20 eV. The interaction potential is treated within the static-correlation-polarization approximation. The comparison of our calculated data with existing theoretical and experimental results is encouraging.

Collisional and radiative processes in high-pressure discharge plasmas

NASA Astrophysics Data System (ADS)

Becker, Kurt H.; Kurunczi, Peter F.; Schoenbach, Karl H.

2002-05-01

Discharge plasmas at high pressures (up to and exceeding atmospheric pressure), where single collision conditions no longer prevail, provide a fertile environment for the experimental study of collisions and radiative processes dominated by (i) step-wise processes, i.e., the excitation of an already excited atomic/molecular state and by (ii) three-body collisions leading, for instance, to the formation of excimers. The dominance of collisional and radiative processes beyond binary collisions involving ground-state atoms and molecules in such environments allows for many interesting applications of high-pressure plasmas such as high power lasers, opening switches, novel plasma processing applications and sputtering, absorbers and reflectors for electromagnetic waves, remediation of pollutants and waste streams, and excimer lamps and other noncoherent vacuum-ultraviolet light sources. Here recent progress is summarized in the use of hollow cathode discharge devices with hole dimensions in the range 0.1-0.5 mm for the generation of vacuum-ultraviolet light.

Self-interaction effects on charge-transfer collisions

DOE PAGES

Quashie, Edwin E.; Saha, Bidhan C.; Andrade, Xavier; ...

2017-04-27

In this article, we investigate the role of the self-interaction error in the simulation of collisions using time-dependent density functional theory (TDDFT) and Ehrenfest dynamics. In addition, we compare many different approximations of the exchange and correlation potential, using as a test system the collision of H + + CH 4 at 30 eV. We find that semilocal approximations, like the Perdew-Burke- Ernzerhof (PBE), and even hybrid functionals, such as the Becke, 3-parameter, Lee-Yang-Parr (B3LYP), produce qualitatively incorrect predictions for the scattering of the proton. This discrepancy appears because the self-interaction error allows the electrons to jump too easily tomore » the proton, leading to radically different forces with respect to the non-self-interacting case. Lastly, from our results, we conclude that using a functional that is self-interaction free is essential to properly describing charge-transfer collisions between ions and molecules in TDDFT.« less

Collision dynamics of H+ + N2 at low energies based on time-dependent density-functional theory

NASA Astrophysics Data System (ADS)

Yu, W.; Zhang, Y.; Zhang, F. S.; Hutton, R.; Zou, Y.; Gao, C.-Z.; Wei, B.

2018-02-01

Using time-dependent density-functional theory at the level of local density approximation augmented by a self-interaction correction and coupled non-adiabatically to molecular dynamics, we study, from a theoretical perspective, scattering dynamics of the proton in collisions with the N2 molecule at 30 eV. Nine different collision configurations are employed to analyze the proton energy loss spectra, electron depletion, scattering angles and self-interaction effects. Our results agree qualitatively with the experimental data and previous theoretical calculations. The discrepancies are ascribed to the limitation of the theoretical models in use. We find that self-interaction effects can significantly influence the electron capture and the excited diatomic vibrational motion, which is in consistent with other calculations. In addition, it is found that the molecular structure can be readily retrieved from the proton energy loss spectra due to a significant momentum transfer in head-on collisions.

Ion-Molecule Reaction Dynamics

NASA Astrophysics Data System (ADS)

Meyer, Jennifer; Wester, Roland

2017-05-01

We review the recent advances in the investigation of the dynamics of ion-molecule reactions. During the past decade, the combination of single-collision experiments in crossed ion and neutral beams with the velocity map ion imaging detection technique has enabled a wealth of studies on ion-molecule reactions. These methods, in combination with chemical dynamics simulations, have uncovered new and unexpected reaction mechanisms, such as the roundabout mechanism and the subtle influence of the leaving group in anion-molecule nucleophilic substitution reactions. For this important class of reactions, as well as for many fundamental cation-molecule reactions, the information obtained with crossed-beam imaging is discussed. The first steps toward understanding micro-solvation of ion-molecule reaction dynamics are presented. We conclude with the presentation of several interesting directions for future research.

Water radiolysis by low-energy carbon projectiles from first-principles molecular dynamics

PubMed Central

Kohanoff, Jorge

2017-01-01

Water radiolysis by low-energy carbon projectiles is studied by first-principles molecular dynamics. Carbon projectiles of kinetic energies between 175 eV and 2.8 keV are shot across liquid water. Apart from translational, rotational and vibrational excitation, they produce water dissociation. The most abundant products are H and OH fragments. We find that the maximum spatial production of radiolysis products, not only occurs at low velocities, but also well below the maximum of energy deposition, reaching one H every 5 Å at the lowest speed studied (1 Bohr/fs), dissociative collisions being more significant at low velocity while the amount of energy required to dissociate water is constant and much smaller than the projectile’s energy. A substantial fraction of the energy transferred to fragments, especially for high velocity projectiles, is in the form of kinetic energy, such fragments becoming secondary projectiles themselves. High velocity projectiles give rise to well-defined binary collisions, which should be amenable to binary approximations. This is not the case for lower velocities, where multiple collision events are observed. H secondary projectiles tend to move as radicals at high velocity, as cations when slower. We observe the generation of new species such as hydrogen peroxide and formic acid. The former occurs when an O radical created in the collision process attacks a water molecule at the O site. The latter when the C projectile is completely stopped and reacts with two water molecules. PMID:28267804

Rotational excitation of symmetric top molecules by collisions with atoms: Close coupling, coupled states, and effective potential calculations for NH3-He

NASA Technical Reports Server (NTRS)

Green, S.

1976-01-01

The formalism for describing rotational excitation in collisions between symmetric top rigid rotors and spherical atoms is presented both within the accurate quantum close coupling framework and also the coupled states approximation of McGuire and Kouri and the effective potential approximation of Rabitz. Calculations are reported for thermal energy NH3-He collisions, treating NH3 as a rigid rotor and employing a uniform electron gas (Gordon-Kim) approximation for the intermolecular potential. Coupled states are found to be in nearly quantitative agreement with close coupling results while the effective potential method is found to be at least qualitatively correct. Modifications necessary to treat the inversion motion in NH3 are discussed.

Cross section data sets for electron collisions with H2, O2, CO, CO2, N2O and H2O

NASA Astrophysics Data System (ADS)

Anzai, K.; Kato, H.; Hoshino, M.; Tanaka, H.; Itikawa, Y.; Campbell, L.; Brunger, M. J.; Buckman, S. J.; Cho, H.; Blanco, F.; Garcia, G.; Limão-Vieira, P.; Ingólfsson, O.

2012-02-01

We review earlier cross section data sets for electron-collisions with H2, O2, CO, CO2, H2O and N2O, updated here by experimental results for their electronic states. Based on our recent measurements of differential cross sections for the electronic states of those molecules, integral cross sections (ICSs) are derived by applying a generalized oscillator strength analysis and then assessed against theory (BE f-scaling [Y.-K. Kim, J. Chem. Phys. 126, 064305 (2007)]). As they now represent benchmark electronic state cross sections, those ICSs for the above molecules are added into the original cross section sets taken from the data reviews for H2, O2, CO2 and H2O (the Itikawa group), and for CO and N2O (the Zecca group).

Differentiation of regioisomeric aromatic ketocarboxylic acids by atmospheric pressure chemical ionization CAD tandem mass spectrometry in a linear quadrupole ion trap mass spectrometer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Amundson, Lucas M.; Owen, Ben C.; Gallardo, Vanessa A.

2011-01-01

Positive-mode atmospheric pressure chemical ionization tandem mass spectrometry (APCI-MS n ) was tested for the differentiation of regioisomeric aromatic ketocarboxylic acids. Each analyte forms exclusively an abundant protonated molecule upon ionization via positive-mode APCI in a commercial linear quadrupole ion trap (LQIT) mass spectrometer. Energy-resolved collision-activated dissociation (CAD) experiments carried out on the protonated analytes revealed fragmentation patterns that varied based on the location of the functional groups. Unambiguous differentiation between the regioisomers was achieved in each case by observing different fragmentation patterns, different relative abundances of ion-molecule reaction products, or different relative abundances of fragment ions formed at differentmore » collision energies. The mechanisms of some of the reactions were examined by H/D exchange reactions and molecular orbital calculations.« less

A structural examination and collision cross section database for over 500 metabolites and xenobiotics using drift tube ion mobility spectrometry† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c7sc03464d

PubMed Central

Zheng, Xueyun; Aly, Noor A.; Zhou, Yuxuan; Dupuis, Kevin T.; Bilbao, Aivett; Paurus, Vanessa L.; Orton, Daniel J.; Wilson, Ryan; Payne, Samuel H.; Smith, Richard D.

2017-01-01

The confident identification of metabolites and xenobiotics in biological and environmental studies is an analytical challenge due to their immense dynamic range, vast chemical space and structural diversity. Ion mobility spectrometry (IMS) is widely used for small molecule analyses since it can separate isomeric species and be easily coupled with front end separations and mass spectrometry for multidimensional characterizations. However, to date IMS metabolomic and exposomic studies have been limited by an inadequate number of accurate collision cross section (CCS) values for small molecules, causing features to be detected but not confidently identified. In this work, we utilized drift tube IMS (DTIMS) to directly measure CCS values for over 500 small molecules including primary metabolites, secondary metabolites and xenobiotics. Since DTIMS measurements do not need calibrant ions or calibration like some other IMS techniques, they avoid calibration errors which can cause problems in distinguishing structurally similar molecules. All measurements were performed in triplicate in both positive and negative polarities with nitrogen gas and seven different electric fields, so that relative standard deviations (RSD) could be assessed for each molecule and structural differences studied. The primary metabolites analyzed to date have come from key metabolism pathways such as glycolysis, the pentose phosphate pathway and the tricarboxylic acid cycle, while the secondary metabolites consisted of classes such as terpenes and flavonoids, and the xenobiotics represented a range of molecules from antibiotics to polycyclic aromatic hydrocarbons. Different CCS trends were observed for several of the diverse small molecule classes and when urine features were matched to the database, the addition of the IMS dimension greatly reduced the possible number of candidate molecules. This CCS database and structural information are freely available for download at http://panomics.pnnl.gov/metabolites/ with new molecules being added frequently. PMID:29568436

EDITORIAL: Focus on Cold and Ultracold Molecules FOCUS ON COLD AND ULTRACOLD MOLECULES

NASA Astrophysics Data System (ADS)

Carr, Lincoln D.; Ye, Jun

2009-05-01

Cold and ultracold molecules are the next wave of ultracold physics, giving rise to an exciting array of scientific opportunities, including many body physics for novel quantum phase transitions, new states of matter, and quantum information processing. Precision tests of fundamental physical laws benefit from the existence of molecular internal structure with exquisite control. The study of novel collision and reaction dynamics will open a new chapter of quantum chemistry. Cold molecules bring together researchers from a variety of fields, including atomic, molecular, and optical physics, chemistry and chemical physics, quantum information science and quantum simulations, condensed matter physics, nuclear physics, and astrophysics, a truly remarkable synergy of scientific explorations. For the past decade there have been steady advances in direct cooling techniques, from buffer-gas cooling to cold molecular beams to electro- and magneto-molecular decelerators. These techniques have allowed a large variety of molecules to be cooled for pioneering studies. Recent amazing advances in experimental techniques combining the ultracold and the ultraprecise have furthermore brought molecules to the point of quantum degeneracy. These latter indirect cooling techniques magnetically associate atoms from a Bose-Einstein condensate and/or a quantum degenerate Fermi gas, transferring at 90% efficiency highly excited Fano-Feshbach molecules, which are on the order of 10 000 Bohr radii in size, to absolute ground state molecules just a few Bohr across. It was this latter advance, together with significant breakthroughs in internal state manipulations, which inspired us to coordinate this focus issue now, and is the reason why we say the next wave of ultracold physics has now arrived. Whether directly or indirectly cooled, heteronuclear polar molecules offer distinct new features in comparison to cold atoms, while sharing all of their advantages (purity, high coherence, controllability, tunable interactions, no disorder, etc). First, they are more easily manipulated because of the strong response of their electric dipole moment to external electric fields, DC or AC. The electric dipole moment also creates the new aspect of long range interactions. Second, they have a rich internal structure, with vibrational and rotational states, fine or hyperfine structure, and Ω- or Λ-doublets. This internal structure allows for wonderful new possibilities in areas such as precision measurement and exquisite control of system dynamics. Therefore, although this focus issue contains a few articles on homonuclear molecules, more complex molecules such as benzene, and even a contribution on atomic chromium, which has a significant magnetic dipole moment, our main focus is on the heteronuclear polar case. This focus issue explores both direct and indirect cooling of mainly polar molecules, and the theory to support and inspire these advances. Thirty-eight research groups have contributed original work, and there are two review articles to complement these advances: the first covers cold and ultracold molecules broadly from few body to many body physics, including foundational theory, the technology to make them, and their scientific applications. The second is on the search for time variation of fundamental constants. The former review, which is comprehensive in nature, concludes with a list of open questions. This sets the tone for the focus issue, namely, openness, innovation, and possibility, an emphasis for which New Journal of Physics, an open-access journal of the highest quality, is especially fitted. Focus on Cold and Ultracold Molecules Contents Cold and ultracold molecules: science, technology and applications Lincoln D Carr, David DeMille, Roman V Krems and Jun Ye Ultracold molecules: new probes on the variation of fundamental constants Cheng Chin, V V Flambaum and M G Kozlov Probing the unitarity limit at low laser intensities Philippe Pellegrini and Robin Côté Single-photon molecular cooling Edvardas Narevicius, S Travis Bannerman and Mark G Raizen Quantum simulations of extended Hubbard models with dipolar crystals M Ortner, A Micheli, G Pupillo and P Zoller Collisional and molecular spectroscopy in an ultracold Bose-Bose mixture G Thalhammer, G Barontini, J Catani, F Rabatti, C Weber, A Simoni, F Minardi and M Inguscio Multi-channel modelling of the formation of vibrationally cold polar KRb molecules Svetlana Kotochigova, Eite Tiesinga and Paul S Julienne Formation of ultracold, highly polar X1Σ+ NaCs molecules C Haimberger, J Kleinert, P Zabawa, A Wakim and N P Bigelow Quantum polarization spectroscopy of correlations in attractive fermionic gases T Roscilde, M Rodríguez, K Eckert, O Romero-Isart, M Lewenstein, E Polzik and A Sanpera Inelastic semiclassical collisions in cold dipolar gases Michael Cavagnero and Catherine Newell Quasi-universal dipolar scattering in cold and ultracold gases J L Bohn, M Cavagnero and C Ticknor Stark deceleration of lithium hydride molecules S K Tokunaga, J M Dyne, E A Hinds and M R Tarbutt Molecular vibrational cooling by optical pumping with shaped femtosecond pulses D Sofikitis, S Weber, A Fioretti, R Horchani, M Allegrini, B Chatel, D Comparat and P Pillet Deeply bound ultracold molecules in an optical lattice Johann G Danzl, Manfred J Mark, Elmar Haller, Mattias Gustavsson, Russell Hart, Andreas Liem, Holger Zellmer and Hanns-Christoph Nägerl Toward the production of quantum degenerate bosonic polar molecules, 41K87Rb K Aikawa, D Akamatsu, J Kobayashi, M Ueda, T Kishimoto and S Inouye Influence of a Feshbach resonance on the photoassociation of LiCs J Deiglmayr, P Pellegrini, A Grochola, M Repp, R Côté, O Dulieu, R Wester and M Weidemüller The kinematic cooling of molecules with laser-cooled atoms Ken Takase, Larry A Rahn, David W Chandler and Kevin E Strecker Coherent collapses of dipolar Bose-Einstein condensates for different trap geometries J Metz, T Lahaye, B Fröhlich, A Griesmaier, T Pfau, H Saito, Y Kawaguchi and M Ueda High-energy-resolution molecular beams for cold collision studies L P Parazzoli, N Fitch, D S Lobser and H J Lewandowski Collisional effects in the formation of cold guided beams of polar molecules M Motsch, C Sommer, M Zeppenfeld, L D van Buuren, P W H Pinkse and G Rempe Towards sympathetic cooling of large molecules: cold collisions between benzene and rare gas atoms P Barletta, J Tennyson and P F Barker Efficient formation of ground-state ultracold molecules via STIRAP from the continuum at a Feshbach resonance Elena Kuznetsova, Marko Gacesa, Philippe Pellegrini, Susanne F Yelin and Robin Côté Emergent timescales in entangled quantum dynamics of ultracold molecules in optical lattices M L Wall and L D Carr Rotational state resolved photodissociation spectroscopy of translationally and vibrationally cold MgH+ ions: toward rotational cooling of molecular ions K Højbjerre, A K Hansen, P S Skyt, P F Staanum and M Drewsen Collective transverse cavity cooling of a dense molecular beam Thomas Salzburger and Helmut Ritsch A Stark decelerator on a chip Samuel A Meek, Horst Conrad and Gerard Meijer Deceleration of molecules by dipole force potential: a numerical simulation Susumu Kuma and Takamasa Momose Ultracold molecules: vehicles to scalable quantum information processing Kathy-Anne Brickman Soderberg, Nathan Gemelke and Cheng Chin Magnetic field modification of ultracold molecule-molecule collisions T V Tscherbul, Yu V Suleimanov, V Aquilanti and R V Krems Spectroscopy of 39K85Rb triplet excited states using ultracold a 3Σ+ state molecules formed by photoassociation J T Kim, D Wang, E E Eyler, P L Gould and W C Stwalley Pumping vortex into a Bose-Einstein condensate of heteronuclear molecules Z F Xu, R Q Wang and L You Intense atomic and molecular beams via neon buffer-gas cooling David Patterson, Julia Rasmussen and John M Doyle Dynamical properties of dipolar Fermi gases T Sogo, L He, T Miyakawa, S Yi, H Lu and H Pu Collisions of bosonic ultracold polar molecules in microwave traps Alexander V Avdeenkov Cold TiO(X3Δ)-He collisions Mei-Ju Lu and Jonathan D Weinstein Investigation of dephasing rates in an interacting Rydberg gas U Raitzsch, R Heidemann, H Weimer, B Butscher, P Kollmann, R Löw, H P Büchler and T Pfau Impact of electric fields on highly excited rovibrational states of polar dimers Rosario González-Férez and Peter Schmelcher Phase transition from straight into twisted vortex lines in dipolar Bose-Einstein condensates M Klawunn and L Santos Stimulating the production of deeply bound RbCs molecules with laser pulses: the role of spin-orbit coupling in forming ultracold molecules Subhas Ghosal, Richard J Doyle, Christiane P Koch and Jeremy M Hutson Sensitive measurement of mp/me variance using vibrational transition frequencies of cold molecules Masatoshi Kajita

Space shuttle contamination due to backflow from control motor exhaust

NASA Technical Reports Server (NTRS)

Robertson, S. J.; Chan, S. T. K.; Lee, A. L.

1976-01-01

Spacecraft contamination of the space shuttle orbiter and accompanying Spacelab payloads is studied. The scattering of molecules from the vernier engines and flash evaporator nozzle after impingement on the orbiter wing surfaces, and the backflow of molecules out of the flash evaporator nozzle plume flow field due to intermolecular collisions in the plume are the problems discussed. A method was formulated for dealing with these problems, and detailed results are given.

Electronic excitation of Na due to low-energy He collisions

NASA Astrophysics Data System (ADS)

Lin, C. Y.; Liebermann, H. P.

2005-05-01

In warm astrophysical environments electron collisions are the primary mechanism for thermalizing the internal energy of ambient atoms and molecules. However, in cool stellar and planetary atmospheres, the electron abundance is extremely low so that thermalization is only possible through collisions of the dominant neutral species, H2, He, and H. Typically, the neutral cross sections are much smaller than those due to electrons, so that the level populations of the atmospheric constituents may display departures from equilibrium. Unfortunately, these cross sections are generally not available for collision energies typical of stellar/planetary environments. In this work, we investigate the electronic excitation of Na due to collisions with He for energies near and just above threshold. The calculations are performed with the quantum-mechanical molecular-orbital close-coupling method utilizing ab initio adiabatic potential curves and nonadiabatic radial and rotational coupling matrix elements obtained from multireference single- and double- excitation configuration interaction approach. State-to-state cross sections and rate coefficients will be presented and compared with other theoretical and experimental data where available.

Interactions between nitrogen and oxygen molecules studied by gas-phase NMR spectroscopy

NASA Astrophysics Data System (ADS)

Garbacz, Piotr; Misiak, Maria; Jackowski, Karol

2018-05-01

Gas-phase 14N and 15N NMR studies of nitrogen and synthetic air pressurized up to 300 bar were performed. It was found that the magnetic shielding of an isolated N2 molecule, σ0(N) = -63.4(2) ppm, is in good agreement with the results of ab initio calculations. The binary N2-O2 interactions contribute to shielding an order of the magnitude larger than the N2-N2 pairs. For nitrogen the three body collisions become observable by NMR for pressure higher than 200 bar and the appropriate coefficient can be practically assigned to the interaction between one molecule of N2 and a pair of O2 molecules.

Viscosity of high-temperature iodine

NASA Technical Reports Server (NTRS)

Kang, Steve H.; Kunc, Joseph A.

1991-01-01

The viscosity coefficient of iodine in the temperature range 500 - 3000 K is calculated. Because of the low dissociation energy of the I2 molecules, the dissociation degree of the gas increases quickly with temperature, and I + I2 and I + I collisions must be taken into account in calculation of viscosity at temperatures greater than 1000 deg. Several possible channels for atom-atom interaction are considered, and the resulting collision integrals are averaged over all the important channels. It is also shown that the rigid-sphere model is inaccurate in predictions of the viscosity.

Collisional excitation of intersteller molecules: Ammonia

NASA Technical Reports Server (NTRS)

Green, S.

1981-01-01

Theoretical rate constants are presented for excitation of NH3 by collisions with He. The lowest 22 levels of ortho-NH3 and the lowest 16 levels of para-NH3 are considered at kinetic temperatures of 15 to 300 K.

Solvent effects on the Raman spectra of the isolated carbon-hydrogen stretches of cyclohexane-d11: A molecular dynamics simulation study of liquid and supercritical solvation

NASA Astrophysics Data System (ADS)

Frankland, Sarah-Jane Victoria

Molecular dynamics simulations of solvent effects on the Raman spectra of isotopically isolated C-H stretches of cyclohexane-d11 were performed in liquids and supercritical CO2. The red spectral shifts from the gas phase origin were derived three different ways: (1) from the Lennard-Jones force on the normal coordinate of the vibration; (2) from this force with an additional term to account for the polarizabilily change on excitation, and (3) as an empirical difference potential between the v = 0 and v = 1 state of the hydrogen atom involved in the vibration. Model 3 was successfully parametrized to reproduce the experimental spectral shifts and linewidths. The simulated lineshapes from these models were homogeneously broadened from gas to liquid densities primarily by collisions of nearby solvent molecules with the solute. Both the simulations and isolated binary collision theory showed the density dependence of the linewidth to be related to that of the collision rate. Two additional projects were done which use Monte-Carlo algorithms involving two molecules. In the first project 1:1 complexes of solute and solvent were formed at the potential surface minima such that the geometries of conformers, energies of formation, and electronic spectral shifts could be studied. Complexes between 7- azaindole, indole, carbazole, and 1-azacarbazole and hydrogen-bonding solvents were most stable when the solvent was hydrogen-bonded at the solute N-H site. The energies of formation compared well with values obtained from ab initio calculations. Complexes of coumarins 102 and 153 and fluorinated alcohols showed the more stable conformers to have the alcohols bound at the coumarin carbonyl group. In the second project, one solvent molecule was randomly placed around the solute molecule in order to simplify bulk liquid simulation to only two molecules. This approximation was rised to show that the dynamic Stokes shift of coumarin 153 in over 30 solvents correlates with the permanent charge distribution of the solvent.

Application of the R-matrix method to photoionization of molecules.

PubMed

Tashiro, Motomichi

2010-04-07

The R-matrix method has been used for theoretical calculation of electron collision with atoms and molecules for long years. The method was also formulated to treat photoionization process, however, its application has been mostly limited to photoionization of atoms. In this work, we implement the R-matrix method to treat molecular photoionization problem based on the UK R-matrix codes. This method can be used for diatomic as well as polyatomic molecules, with multiconfigurational description for electronic states of both target neutral molecule and product molecular ion. Test calculations were performed for valence electron photoionization of nitrogen (N(2)) as well as nitric oxide (NO) molecules. Calculated photoionization cross sections and asymmetry parameters agree reasonably well with the available experimental results, suggesting usefulness of the method for molecular photoionization.

Collison-Induced Absorption of Oxygen Molecule as Studied by High Sensitivity Spectroscopy

NASA Astrophysics Data System (ADS)

Kashihara, Wataru; Shoji, Atsushi; Kawai, Akio

2017-06-01

Oxygen dimol is transiently generated when two oxygen molecules collide. At this short period, the electron clouds of molecules are distorted and some forbidden transition electronic transitions become partially allowed. This transition is called CIA (Collision-induced absorption). There are several CIA bands appearing in the spectral region from UV to near IR. Absorption of solar radiation by oxygen dimol is a small but significant part of the total budget of incoming shortwave radiation. However, a theory predicting the lineshape of CIA is still under developing. In this study, we measured CIA band around 630 nm that is assigned to optical transition, a^{1}Δ_{g}(v=0):a^{1}Δ_{g}(v=0)-X^{3}Σ_{g}^{-}(v=0):X^{3}Σ_{g}^{-}(v=0) of oxygen dimol. CRDS(Cavity Ring-down Spectroscopy) was employed to measure weak absorption CIA band of oxygen. Laser beam around 630 nm was generated by a dye laser that was pumped by a YAG Laser. Multiple reflection of the probe light was performed within a vacuum chamber that was equipped with two high reflective mirrors. We discuss the measured line shape of CIA on the basis of collision pair model.

Electron scattering by molecules. II - Experimental methods and data

NASA Technical Reports Server (NTRS)

Trajmar, S.; Chutjian, A.; Register, D. F.

1983-01-01

Experimental techniques for measuring electron-molecule collision cross sections are briefly summarized. A survey of the available experimental cross section data is presented. The emphasis here is on elastic scattering, rotational, vibrational and electronic excitations, total electron scattering, and momentum transfer in the few eV to few hundred eV impact energy range. Reference is made to works concerned with high energy electron scattering, innershell and multi-electron excitations, conicidence methods and electron scattering in laser fields.

Unifying the rotational and permutation symmetry of nuclear spin states: Schur-Weyl duality in molecular physics.

PubMed

Schmiedt, Hanno; Jensen, Per; Schlemmer, Stephan

2016-08-21

In modern physics and chemistry concerned with many-body systems, one of the mainstays is identical-particle-permutation symmetry. In particular, both the intra-molecular dynamics of a single molecule and the inter-molecular dynamics associated, for example, with reactive molecular collisions are strongly affected by selection rules originating in nuclear-permutation symmetry operations being applied to the total internal wavefunctions, including nuclear spin, of the molecules involved. We propose here a general tool to determine coherently the permutation symmetry and the rotational symmetry (associated with the group of arbitrary rotations of the entire molecule in space) of molecular wavefunctions, in particular the nuclear-spin functions. Thus far, these two symmetries were believed to be mutually independent and it has even been argued that under certain circumstances, it is impossible to establish a one-to-one correspondence between them. However, using the Schur-Weyl duality theorem we show that the two types of symmetry are inherently coupled. In addition, we use the ingenious representation-theory technique of Young tableaus to represent the molecular nuclear-spin degrees of freedom in terms of well-defined mathematical objects. This simplifies the symmetry classification of the nuclear wavefunction even for large molecules. Also, the application to reactive collisions is very straightforward and provides a much simplified approach to obtaining selection rules.

Unifying the rotational and permutation symmetry of nuclear spin states: Schur-Weyl duality in molecular physics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schmiedt, Hanno; Schlemmer, Stephan; Jensen, Per, E-mail: jensen@uni-wuppertal.de

In modern physics and chemistry concerned with many-body systems, one of the mainstays is identical-particle-permutation symmetry. In particular, both the intra-molecular dynamics of a single molecule and the inter-molecular dynamics associated, for example, with reactive molecular collisions are strongly affected by selection rules originating in nuclear-permutation symmetry operations being applied to the total internal wavefunctions, including nuclear spin, of the molecules involved. We propose here a general tool to determine coherently the permutation symmetry and the rotational symmetry (associated with the group of arbitrary rotations of the entire molecule in space) of molecular wavefunctions, in particular the nuclear-spin functions. Thusmore » far, these two symmetries were believed to be mutually independent and it has even been argued that under certain circumstances, it is impossible to establish a one-to-one correspondence between them. However, using the Schur-Weyl duality theorem we show that the two types of symmetry are inherently coupled. In addition, we use the ingenious representation-theory technique of Young tableaus to represent the molecular nuclear-spin degrees of freedom in terms of well-defined mathematical objects. This simplifies the symmetry classification of the nuclear wavefunction even for large molecules. Also, the application to reactive collisions is very straightforward and provides a much simplified approach to obtaining selection rules.« less

Precipitation of energetic neutral atoms and induced non-thermal escape fluxes from the Martian atmosphere

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lewkow, N. R.; Kharchenko, V.

2014-08-01

The precipitation of energetic neutral atoms, produced through charge exchange collisions between solar wind ions and thermal atmospheric gases, is investigated for the Martian atmosphere. Connections between parameters of precipitating fast ions and resulting escape fluxes, altitude-dependent energy distributions of fast atoms and their coefficients of reflection from the Mars atmosphere, are established using accurate cross sections in Monte Carlo (MC) simulations. Distributions of secondary hot (SH) atoms and molecules, induced by precipitating particles, have been obtained and applied for computations of the non-thermal escape fluxes. A new collisional database on accurate energy-angular-dependent cross sections, required for description of themore » energy-momentum transfer in collisions of precipitating particles and production of non-thermal atmospheric atoms and molecules, is reported with analytic fitting equations. Three-dimensional MC simulations with accurate energy-angular-dependent cross sections have been carried out to track large ensembles of energetic atoms in a time-dependent manner as they propagate into the Martian atmosphere and transfer their energy to the ambient atoms and molecules. Results of the MC simulations on the energy-deposition altitude profiles, reflection coefficients, and time-dependent atmospheric heating, obtained for the isotropic hard sphere and anisotropic quantum cross sections, are compared. Atmospheric heating rates, thermalization depths, altitude profiles of production rates, energy distributions of SH atoms and molecules, and induced escape fluxes have been determined.« less

Quantum-mechanical transport equation for atomic systems.

NASA Technical Reports Server (NTRS)

Berman, P. R.

1972-01-01

A quantum-mechanical transport equation (QMTE) is derived which should be applicable to a wide range of problems involving the interaction of radiation with atoms or molecules which are also subject to collisions with perturber atoms. The equation follows the time evolution of the macroscopic atomic density matrix elements of atoms located at classical position R and moving with classical velocity v. It is quantum mechanical in the sense that all collision kernels or rates which appear have been obtained from a quantum-mechanical theory and, as such, properly take into account the energy-level variations and velocity changes of the active (emitting or absorbing) atom produced in collisions with perturber atoms. The present formulation is better suited to problems involving high-intensity external fields, such as those encountered in laser physics.

Distance geometry protocol to generate conformations of natural products to structurally interpret ion mobility-mass spectrometry collision cross sections.

PubMed

Stow, Sarah M; Goodwin, Cody R; Kliman, Michal; Bachmann, Brian O; McLean, John A; Lybrand, Terry P

2014-12-04

Ion mobility-mass spectrometry (IM-MS) allows the separation of ionized molecules based on their charge-to-surface area (IM) and mass-to-charge ratio (MS), respectively. The IM drift time data that is obtained is used to calculate the ion-neutral collision cross section (CCS) of the ionized molecule with the neutral drift gas, which is directly related to the ion conformation and hence molecular size and shape. Studying the conformational landscape of these ionized molecules computationally provides interpretation to delineate the potential structures that these CCS values could represent, or conversely, structural motifs not consistent with the IM data. A challenge in the IM-MS community is the ability to rapidly compute conformations to interpret natural product data, a class of molecules exhibiting a broad range of biological activity. The diversity of biological activity is, in part, related to the unique structural characteristics often observed for natural products. Contemporary approaches to structurally interpret IM-MS data for peptides and proteins typically utilize molecular dynamics (MD) simulations to sample conformational space. However, MD calculations are computationally expensive, they require a force field that accurately describes the molecule of interest, and there is no simple metric that indicates when sufficient conformational sampling has been achieved. Distance geometry is a computationally inexpensive approach that creates conformations based on sampling different pairwise distances between the atoms within the molecule and therefore does not require a force field. Progressively larger distance bounds can be used in distance geometry calculations, providing in principle a strategy to assess when all plausible conformations have been sampled. Our results suggest that distance geometry is a computationally efficient and potentially superior strategy for conformational analysis of natural products to interpret gas-phase CCS data.

Distance Geometry Protocol to Generate Conformations of Natural Products to Structurally Interpret Ion Mobility-Mass Spectrometry Collision Cross Sections

PubMed Central

2015-01-01

Ion mobility-mass spectrometry (IM-MS) allows the separation of ionized molecules based on their charge-to-surface area (IM) and mass-to-charge ratio (MS), respectively. The IM drift time data that is obtained is used to calculate the ion-neutral collision cross section (CCS) of the ionized molecule with the neutral drift gas, which is directly related to the ion conformation and hence molecular size and shape. Studying the conformational landscape of these ionized molecules computationally provides interpretation to delineate the potential structures that these CCS values could represent, or conversely, structural motifs not consistent with the IM data. A challenge in the IM-MS community is the ability to rapidly compute conformations to interpret natural product data, a class of molecules exhibiting a broad range of biological activity. The diversity of biological activity is, in part, related to the unique structural characteristics often observed for natural products. Contemporary approaches to structurally interpret IM-MS data for peptides and proteins typically utilize molecular dynamics (MD) simulations to sample conformational space. However, MD calculations are computationally expensive, they require a force field that accurately describes the molecule of interest, and there is no simple metric that indicates when sufficient conformational sampling has been achieved. Distance geometry is a computationally inexpensive approach that creates conformations based on sampling different pairwise distances between the atoms within the molecule and therefore does not require a force field. Progressively larger distance bounds can be used in distance geometry calculations, providing in principle a strategy to assess when all plausible conformations have been sampled. Our results suggest that distance geometry is a computationally efficient and potentially superior strategy for conformational analysis of natural products to interpret gas-phase CCS data. PMID:25360896

Theoretical Investigation of Kinetic Processes in Small Radicals of Importance in Combustion

DOE Office of Scientific and Technical Information (OSTI.GOV)

Alexander, Millard; Dagdigian, Paul J.

Our group studies inelastic and reactive collisions of small molecules, focusing on radicals important in combustion environments. The goal is the better understanding of kinetic processes that may be difficult to access experimentally. An essential component is the accurate determination and fitting of potential energy surfaces (PESs). After fitting the ab initio points to obtain global PESs, we treat the dynamics using time-independent (close-coupling) methods. Cross sections and rate constants for collisions of are determined with our Hibridon program suite . We have studied energy transfer (rotationally, vibrationally, and/or electronically inelastic) in small hydrocarbon radicals (CH 2 and CH 3)more » and the CN radical. We have made a comparison with experimental measurements of relevant rate constants for collisions of these radicals. Also, we have calculated accurate transport properties using state-of-the-art PESs and to investigate the sensitivity to these parameters in 1-dimensional flame simulations. Of particular interest are collision pairs involving the light H atom.« less

Fast quantifying collision strength index of ethylene-vinyl acetate copolymer coverings on the fields based on near infrared hyperspectral imaging techniques

PubMed Central

Chen, Y. M.; Lin, P.; He, Y.; He, J. Q.; Zhang, J.; Li, X. L.

2016-01-01

A novel strategy based on the near infrared hyperspectral imaging techniques and chemometrics were explored for fast quantifying the collision strength index of ethylene-vinyl acetate copolymer (EVAC) coverings on the fields. The reflectance spectral data of EVAC coverings was obtained by using the near infrared hyperspectral meter. The collision analysis equipment was employed to measure the collision intensity of EVAC materials. The preprocessing algorithms were firstly performed before the calibration. The algorithms of random frog and successive projection (SP) were applied to extracting the fingerprint wavebands. A correlation model between the significant spectral curves which reflected the cross-linking attributions of the inner organic molecules and the degree of collision strength was set up by taking advantage of the support vector machine regression (SVMR) approach. The SP-SVMR model attained the residual predictive deviation of 3.074, the square of percentage of correlation coefficient of 93.48% and 93.05% and the root mean square error of 1.963 and 2.091 for the calibration and validation sets, respectively, which exhibited the best forecast performance. The results indicated that the approaches of integrating the near infrared hyperspectral imaging techniques with the chemometrics could be utilized to rapidly determine the degree of collision strength of EVAC. PMID:26875544

Ultracold collisions between Rb atoms and a Sr+ ion

NASA Astrophysics Data System (ADS)

Meir, Ziv; Sikorsky, Tomas; Ben-Shlomi, Ruti; Dallal, Yehonatan; Ozeri, Roee

2015-05-01

In last decade, a novel field emerged, in which ultracold atoms and ions in overlapping traps are brought into interaction. In contrast to the short ranged atom-atom interaction which scales as r-6, atom-ion potential persists for hundreds of μm's due to its lower power-law scaling - r-4. Inelastic collisions between the consistuents lead to spin and charge transfer and also to molecule formation. Elastic collisions control the energy transfer between the ion and the atoms. The study of collisions at the μK range has thus far been impeded by the effect of the ion's micromotion which limited collision energy to mK scale. Unraveling this limit will allow to investigate few partial wave and even S-wave collisions. Our system is capable of trapping Sr+ ions and Rb and Sr atoms and cooling them to their quantum ground state. Atoms and ions are trapped and cooled in separate chambers. Then, the atoms are transported using an optical conveyer belt to overlap the ions. In contrast to other experiments in this field where the atoms are used to sympathetic cool the ion, our system is also capable of ground state cooling the ion before immersing it into the atom cloud. By this method, we would be able to explore heating and cooling dynamics in the ultracold regime.

High-resolution internal state control of ultracold 23Na87Rb molecules

NASA Astrophysics Data System (ADS)

Guo, Mingyang; Ye, Xin; He, Junyu; Quéméner, Goulven; Wang, Dajun

2018-02-01

We report the full internal state control of ultracold 23Na87Rb molecules, including vibrational, rotational, and hyperfine degrees of freedom. Starting from a sample of weakly bound Feshbach molecules, we realize the creation of molecules in single hyperfine levels of both the rovibrational ground and excited states with a high-efficiency and high-resolution stimulated Raman adiabatic passage. This capability brings broad possibilities for investigating ultracold polar molecules with different chemical reactivities and interactions with a single molecular species. Moreover, starting from the rovibrational and hyperfine ground state, we achieve rotational and hyperfine control with one- and two-photon microwave spectroscopy to reach levels not accessible by the stimulated Raman transfer. The combination of these two techniques results in complete control over the internal state of ultracold polar molecules, which paves the way to study state-dependent molecular collisions and state-controlled chemical reactions.

Physics with Cold Molecules Using Buffer Gas Cooling: Precision Measurement, Collisions, and Laser Cooling

NASA Astrophysics Data System (ADS)

Hutzler, Nicholas R.; Doyle, John M.

2014-06-01

Cryogenic buffer gas cooled beams and cells can be used to study many species, from atoms and polar molecules to biomolecules. We report on recent applications of this technique to improve the limit on the electron electric dipole moment [1], load polar molecules into a magnetic trap through optical pumping [2], perform chirally sensitive microwave spectroscopy on polyatomic molecules [3], progress towards magneto-optical trapping of polar molecules [4], and studies of atom-molecule sticking [5]. [1] The ACME Collaboration: J. Baron et al., Science 343, p. 269 (2014) [2] B. Hemmerling et al., arXiv:1310.2669, to appear in Phys. Rev. Lett. [3] D. Patterson, M. Schnell, & J. M. Doyle, Nature 497, p. 475 (2013) [4] H. Lu et al., arXiv:1310.3239, to appear in New. J. Phys. [5] J. Piskorski et al., under preparation

Ozone Depletion, UVB and Atmospheric Chemistry

NASA Technical Reports Server (NTRS)

Stolarski, Richard S.

1999-01-01

The primary constituents of the Earth's atmosphere are molecular nitrogen and molecular oxygen. Ozone is created when ultraviolet light from the sun photodissociates molecular oxygen into two oxygen atoms. The oxygen atoms undergo many collisions but eventually combine with a molecular oxygen to form ozone (O3). The ozone molecules absorb ultraviolet solar radiation, primarily in the wavelength region between 200 and 300 nanometers, resulting in the dissociation of ozone back into atomic oxygen and molecular oxygen. The oxygen atom reattaches to an O2 molecule, reforming ozone which can then absorb another ultraviolet photon. This sequence goes back and forth between atomic oxygen and ozone, each time absorbing a uv photon, until the oxygen atom collides with and ozone molecule to reform two oxygen molecules.

Building one molecule from a reservoir of two atoms

NASA Astrophysics Data System (ADS)

Liu, L. R.; Hood, J. D.; Yu, Y.; Zhang, J. T.; Hutzler, N. R.; Rosenband, T.; Ni, K.-K.

2018-05-01

Chemical reactions typically proceed via stochastic encounters between reactants. Going beyond this paradigm, we combined exactly two atoms in a single, controlled reaction. The experimental apparatus traps two individual laser-cooled atoms [one sodium (Na) and one cesium (Cs)] in separate optical tweezers and then merges them into one optical dipole trap. Subsequently, photoassociation forms an excited-state NaCs molecule. The discovery of previously unseen resonances near the molecular dissociation threshold and measurement of collision rates are enabled by the tightly trapped ultracold sample of atoms. As laser-cooling and trapping capabilities are extended to more elements, the technique will enable the study of more diverse, and eventually more complex, molecules in an isolated environment, as well as synthesis of designer molecules for qubits.

Specific Effects of Oxygen Molecule and Plasma on Thin-Film Growth of Y-Ba-Cu-O and Bi-Sr-(Ca)-Cu-O Systems

NASA Astrophysics Data System (ADS)

Endo, Tamio; Horie, Munehiro; Hirate, Naoki; Itoh, Katsutoshi; Yamada, Satoshi; Tada, Masaki; Itoh, Ken-ichi; Sugiyama, Morihiro; Sano, Shinji; Watabe, Kinji

1998-07-01

Thin films of a-oriented YBa2Cu3Ox (YBCO), Ca-doped c-oriented Bi2(Sr,Ca)2CuOx and nondoped c-oriented Bi2Sr2CuOx (Bi2201) were prepared at low temperatures by ion beam sputtering with supply of oxygen molecules or plasma. The plasma enhances crystal growth of the a-YBCO and Ca-doped Bi2201 phases. This can be interpreted in terms of their higher surface energies. The growth and quality of nondoped Bi2201 are improved with the supply of oxygen molecules. This particular result could be interpreted by the collision process between the oxygen molecules and the sputtered particles.

Rotational relaxation of fluoromethane molecules in low-temperature collisions with buffer-gas helium

NASA Astrophysics Data System (ADS)

Li, Xingjia; Xu, Liang; Yin, Yanning; Xu, Supeng; Xia, Yong; Yin, Jianping

2016-06-01

We propose a method to study the rotational relaxation of polar molecules [here taking fluoromethane (CH3F ) as an example] in collisions with 3.5 K buffer-gas helium (He) atoms by using an electrostatic guiding technique. The dependence of the guiding signal of CH3F on the injected He flux and the dependence of the guiding efficiency of CH3F on its rotational temperature are investigated both theoretically and experimentally. By comparing the experimental and simulated results, we find that the translational and rotational temperatures of the buffer-gas cooled CH3F molecules can reach to about 5.48 and 0.60 K, respectively, and the ratio between the translational and average rotational collisional cross sections of CH3F -He is γ =σt/σr=36.49 ±6.15 . In addition, the slowing, cooling, and boosting effects of the molecular beam with different injected He fluxes are also observed and their forming conditions are investigated in some detail. Our study shows that our proposed method can not only be used to measure the translational and rotational temperatures of the buffer-gas cooled molecules, but also to measure the ratio of the translational collisional cross section to the average rotational collisional cross section, and even to measure the average rotational collisional cross section when the translational collisional cross section is measured by fitting the lifetime of molecule signal to get a numerical solution from the diffusion equation of buffer-gas He atoms in the cell.

Collision induced dissociation of protonated N-nitrosodimethylamine by ion trap mass spectrometry: Ultimate carcinogens in gas phase

NASA Astrophysics Data System (ADS)

Kulikova, Natalia; Baker, Michael; Gabryelski, Wojciech

2009-12-01

Collision induced dissociation of protonated N-nitrosodimethylamine (NDMA) and isotopically labeled N-nitrosodimethyl-d6-amine (NDMA-d6) was investigated by sequential ion trap mass spectrometry to establish mechanisms of gas phase reactions leading to intriguing products of this potent carcinogen. The fragmentation of (NDMA + H+) occurs via two dissociation pathways. In the alkylation pathway, homolytic cleavage of the N-O bond of N-dimethyl, N'-hydroxydiazenium ion generates N-dimethyldiazenium distonic ion which reacts further by a CH3 radical loss to form methanediazonium ion. Both methanediazonium ion and its precursor are involved in ion/molecule reactions. Methanediazonium ion showed to be capable of methylating water and methanol molecules in the gas phase of the ion trap and N-dimethyldiazenium distonic ion showed to abstract a hydrogen atom from a solvent molecule. In the denitrosation pathway, a tautomerization of N-dimethyl, N'-hydroxydiazenium ion to N-nitrosodimethylammonium intermediate ion results in radical cleavage of the N-N bond of the intermediate ion to form N-dimethylaminium radical cation which reacts further through [alpha]-cleavage to generate N-methylmethylenimmonium ion. Although the reactions of NDMA in the gas phase are different to those for enzymatic conversion of NDMA in biological systems, each activation method generates the same products. We will show that collision induced dissociation of N-nitrosodiethylamine (NDEA) and N-nitrosodipropylamine (NDPA) is also a feasible approach to gain information on formation, stability, and reactivity of alkylating agents originating from NDEA and NDPA. Investigating such biologically relevant, but highly reactive intermediates in the condensed phase is hampered by the short life-times of these transient species.

Computational Study of Electron-Molecule Collisions Related to Low-Temperature Plasmas.

NASA Astrophysics Data System (ADS)

Huo, Winifred M.

1997-10-01

Computational study of electron-molecule collisions not only complements experimental measurements, but can also be used to investigate processes not readily accessible experimentally. A number of ab initio computational methods are available for this type of calculations. Here we describe a recently developed technique, the finite element Z-matrix method. Analogous to the R-matrix method, it partitions the space into regions and employs real matrix elements. However, unlike the implementation of the R-matrix method commonly used in atomic and molecular physics,(C. J. Gillan, J. Tennyson, and P. G. Burke, Chapter 10 in Computational Methods for Electron-Molecule Collisions), W. M. Huo and F. A. Gianturco, Editors, Plenum, New York (1995), p. 239. the Z-matrix method is fully variational.(D. Brown and J. C. Light, J. Chem. Phys. 101), 3723 (1994). In the present implementation, a mixed basis of finite elements and Gaussians is used to represent the continuum electron, thus offering full flexibility without imposing fixed boundary conditions. Numerical examples include the electron-impact dissociation of N2 via the metastable A^3Σ_u^+ state, a process which may be important in the lower thermosphere, and the dissociation of the CF radical, a process of interest to plasma etching. To understand the dissociation pathways, large scale quantum chemical calculations have been carried out for all target states which dissociate to the lowest five limits in the case of N_2, and to the lowest two limits in the case of CF. For N_2, the structural calculations clearly show the preference for predissociation if the initial state is the ground X^1Σ_g^+ state, but direct dissociation appears to be preferable if the initial state is the A^3Σ_u^+ state. Multi-configuration SCF target functions are used in the collisional calculation,

Spectroscopic Constants for Selected Homonuclear Diatomic Molecules. Volume 2. K through Z

DTIC Science & Technology

1976-02-16

in Active Nitrogen, Part 1. - Mercury Hg(63P1)," J. Chem. Soc. Faraday Trans, II 68, 2023-30 R. S. Hickman and L. Liang, "Comment...and G. M. Skardis, "Quenching of Mercury -Sensitized Fluorescence in Sodium induced in Collisions With N2 Molecules, " Can. J. Phys. 51...34 Nature 210, 1034-5 (67. 87) N. Basco and A. E. Pearson, "Reactions of Sulphur Atoms in Presence of Carbon Disulphide, Carbonyl Sulphide and

Test measurement on ion-molecule reactions in a ringelectrode ion trap

NASA Astrophysics Data System (ADS)

Savic, I.; Lukic, S. R.; Guth, I.; Gerlich, D.

2006-05-01

Very recently a new experimental setup has been developed allowing studies of astrophysically relevant collisions between neutral atoms and small pure carbon molecules from one side and ions from the other side and first results are obtained (Savić et al., 2005). The ions are stored in a radio- frequency (rf) ring-electrode trap and during reaction time exposed to the effusive carbon beam. In this paper, one of the final tests of the experimental setup is presented.

Unifying diffusion and seepage for nonlinear gas transport in multiscale porous media

NASA Astrophysics Data System (ADS)

Song, Hongqing; Wang, Yuhe; Wang, Jiulong; Li, Zhengyi

2016-09-01

We unify the diffusion and seepage process for nonlinear gas transport in multiscale porous media via a proposed new general transport equation. A coherent theoretical derivation indicates the wall-molecule and molecule-molecule collisions drive the Knudsen and collective diffusive fluxes, and constitute the system pressure across the porous media. A new terminology, nominal diffusion coefficient can summarize Knudsen and collective diffusion coefficients. Physical and numerical experiments show the support of the new formulation and provide approaches to obtain the diffusion coefficient and permeability simultaneously. This work has important implication for natural gas extraction and greenhouse gases sequestration in geological formations.

Collisions involving antiprotons and antihydrogen: an overview

NASA Astrophysics Data System (ADS)

Jonsell, S.

2018-03-01

I give an overview of experimental and theoretical results for antiproton and antihydrogen scattering with atoms and molecules (in particular H, He). At low energies (>1 keV) there are practically no experimental data available. Instead I compare the results from different theoretical calculations, of various degrees of sophistication. At energies up to a few tens of eV, I focus on simple approximations that give reasonably accurate results, as these allow quick estimates of collision rates without embarking on a research project. This article is part of the Theo Murphy meeting issue `Antiproton physics in the ELENA era'.

Simulations of Ground and Space-Based Oxygen Atom Experiments

NASA Technical Reports Server (NTRS)

Finchum, A. (Technical Monitor); Cline, J. A.; Minton, T. K.; Braunstein, M.

2003-01-01

A low-earth orbit (LEO) materials erosion scenario and the ground-based experiment designed to simulate it are compared using the direct-simulation Monte Carlo (DSMC) method. The DSMC model provides a detailed description of the interactions between the hyperthermal gas flow and a normally oriented flat plate for each case. We find that while the general characteristics of the LEO exposure are represented in the ground-based experiment, multi-collision effects can potentially alter the impact energy and directionality of the impinging molecules in the ground-based experiment. Multi-collision phenomena also affect downstream flux measurements.

On the possibility of negative activation energies in bimolecular reactions

NASA Technical Reports Server (NTRS)

Jaffe, R. L.

1978-01-01

The temperature dependence of the rate constants for model reacting systems was studied to understand some recent experimental measurements which imply the existence of negative activation energies. A collision theory model and classical trajectory calculations are used to demonstrate that the reaction probability can vary inversely with collision energy for bimolecular reactions occurring on attractive potential energy surfaces. However, this is not a sufficient condition to ensure that the rate constant has a negative temperature dependence. On the basis of these calculations, it seems unlikely that a true bimolecular reaction between neutral molecules will have a negative activation energy.

Understanding the quantum nature of low-energy C(3P j ) + He inelastic collisions.

PubMed

Bergeat, Astrid; Chefdeville, Simon; Costes, Michel; Morales, Sébastien B; Naulin, Christian; Even, Uzi; Kłos, Jacek; Lique, François

2018-05-01

Inelastic collisions that occur between open-shell atoms and other atoms or molecules, and that promote a spin-orbit transition, involve multiple interaction potentials. They are non-adiabatic by nature and cannot be described within the Born-Oppenheimer approximation; in particular, their theoretical modelling becomes very challenging when the collision energies have values comparable to the spin-orbit splitting. Here we study inelastic collisions between carbon in its ground state C( 3 P j=0 ) and helium atoms-at collision energies in the vicinity of spin-orbit excitation thresholds (~0.2 and 0.5 kJ mol -1 )-that result in spin-orbit excitation to C( 3 P j=1 ) and C( 3 P j=2 ). State-to-state integral cross-sections are obtained from crossed-beam experiments with a beam source that provides an almost pure beam of C( 3 P j=0 ) . We observe very good agreement between experimental and theoretical results (acquired using newly calculated potential energy curves), which validates our characterization of the quantum dynamical resonances that are observed. Rate coefficients at very low temperatures suitable for chemical modelling of the interstellar medium are also calculated.

Understanding the quantum nature of low-energy C(3Pj) + He inelastic collisions

NASA Astrophysics Data System (ADS)

Bergeat, Astrid; Chefdeville, Simon; Costes, Michel; Morales, Sébastien B.; Naulin, Christian; Even, Uzi; Kłos, Jacek; Lique, François

2018-05-01

Inelastic collisions that occur between open-shell atoms and other atoms or molecules, and that promote a spin-orbit transition, involve multiple interaction potentials. They are non-adiabatic by nature and cannot be described within the Born-Oppenheimer approximation; in particular, their theoretical modelling becomes very challenging when the collision energies have values comparable to the spin-orbit splitting. Here we study inelastic collisions between carbon in its ground state C(3Pj=0) and helium atoms—at collision energies in the vicinity of spin-orbit excitation thresholds ( 0.2 and 0.5 kJ mol-1)—that result in spin-orbit excitation to C(3Pj=1) and C(3Pj=2). State-to-state integral cross-sections are obtained from crossed-beam experiments with a beam source that provides an almost pure beam of C(3Pj=0) . We observe very good agreement between experimental and theoretical results (acquired using newly calculated potential energy curves), which validates our characterization of the quantum dynamical resonances that are observed. Rate coefficients at very low temperatures suitable for chemical modelling of the interstellar medium are also calculated.

Rotationally inelastic collisions of He and Ar with NaK: Theory and Experiment

NASA Astrophysics Data System (ADS)

Richter, K.; Price, T. J.; Jones, J.; Faust, C.; Hickman, A. P.; Huennekens, J.; Malenda, R. F.; Ross, A. J.; Harker, H.; Crozet, P.; Forrey, R. C.

2015-05-01

Rotationally inelastic collisions of NaK A1Σ+ molecules with He and Ar are studied. At Lehigh, we use pump-probe polarization labeling (PL) and laser-induced fluorescence (LIF) spectroscopy. At Lyon, Fourier transform (FT)-resolved LIF spectra are recorded. In both cases, the pump laser excites a particular ro-vibrational level A1Σ+ (v , J). We observe strong direct lines corresponding to transitions from the (v , J) level pumped, and weak satellite lines corresponding to transitions from collisionally-populated levels (v ,J' = J + ΔJ). The ratios of satellite to direct line intensities in LIF and PL yield population and orientation transfer information. A strong propensity for ΔJ = even transitions is observed for both He and Ar perturbers. In the FT fluorescence experiment we also observe v-changing collisions. Ab initio potential surface and scattering calculations are underway for collisions in the A1Σ+ and X1Σ+ states. For He-NaK we have calculated potential surfaces using GAMESS and carried out coupled channel scattering calculations of transfer of population, orientation, and alignment. Calculations of v-changing collision cross sections are also in progress. Work supported by NSF, XSEDE and CNRS (PICS).

Comparative stereodynamics in molecule-atom and molecule-molecule rotational energy transfer: NO(A{sup 2}Σ{sup +}) + He and D{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luxford, Thomas F. M.; Sharples, Thomas R.; McKendrick, Kenneth G.

2016-08-28

We present a crossed molecular beam scattering study, using velocity-map ion-imaging detection, of state-to-state rotational energy transfer for NO(A{sup 2}Σ{sup +}) in collisions with the kinematically identical colliders He and D{sub 2}. We report differential cross sections and angle-resolved rotational angular momentum polarization moments for transfer of NO(A, v = 0, N = 0, j = 0.5) to NO(A, v = 0, N′ = 3, 5-12) in collisions with He and D{sub 2} at respective average collision energies of 670 cm{sup −1} and 663 cm{sup −1}. Quantum scattering calculations on a literature ab initio potential energy surface for NO(A)-He [J.more » Kłos et al., J. Chem. Phys. 129, 244303 (2008)] yield near-quantitative agreement with the experimental differential scattering cross sections and good agreement with the rotational polarization moments. This confirms that the Kłos et al. potential is accurate within the experimental collisional energy range. Comparison of the experimental results for NO(A) + D{sub 2} and He collisions provides information on the hitherto unknown NO(A)-D{sub 2} potential energy surface. The similarities in the measured scattering dynamics of NO(A) imply that the general form of the NO(A)-D{sub 2} potential must be similar to that calculated for NO(A)-He. A consistent trend for the rotational rainbow maximum in the differential cross sections for NO(A) + D{sub 2} to peak at more forward angles than those for NO(A) + He is consistent with the NO(A)-D{sub 2} potential being more anisotropic with respect to NO(A) orientation. No evidence is found in the experimental measurements for coincident rotational excitation of the D{sub 2}, consistent with the potential having low anisotropy with respect to D{sub 2}. The NO(A) + He polarization moments deviate systematically from the predictions of a hard-shell, kinematic-apse scattering model, with larger deviations as N′ increases, which we attribute to the shallow gradient of the anisotropic repulsive NO(A)-He potential energy surface.« less

Measurement of the velocity of neutral fragments by the "correlated ion and neutral time of flight" method combined with "velocity-map imaging"

NASA Astrophysics Data System (ADS)

Berthias, F.; Feketeová, L.; Della Negra, R.; Dupasquier, T.; Fillol, R.; Abdoul-Carime, H.; Farizon, B.; Farizon, M.; Märk, T. D.

2017-08-01

In the challenging field of imaging molecular dynamics, a novel method has been developed and implemented that allows the measurement of the velocity of neutral fragments produced in collision induced dissociation experiments on an event-by-event basis. This has been made possible by combining a correlated ion and neutral time of flight method with a velocity map imaging technique. This new method relies on a multiparametric correlated detection of the neutral and charged fragments from collision induced dissociation on one single detector. Its implementation on the DIAM device (Device for irradiation of biomolecular clusters) (Dispositif d'Irradiation d'Agrégats bioMoléculaires) allowed us to measure the velocity distribution of water molecules evaporated from collision induced dissociation of mass- and energy-selected protonated water clusters.

A permanent magnet trap for buffer gas cooled atoms and molecules

NASA Astrophysics Data System (ADS)

Nohlmans, D.; Skoff, S. M.; Hendricks, R. J.; Segal, D. M.; Sauer, B. E.; Hinds, E. A.; Tarbutt, M. R.

2013-05-01

Cold molecules are set to provide a wealth of new science compared to their atomic counterparts. Here we want to present preliminary results for cooling and trapping atoms/molecules in a permanent magnetic trap. By replacing the conventional buffer gas cell with an arrangement of permanent magnets, we will be able to trap a fraction of the molecules right where they are cooled. For this purpose we have designed a quadrupole trap using NdFeB magnets, which has a trap depth of 0.4 K for molecules with a magnetic moment of 1 μB. Cold helium gas is pulsed into the trap region by a solenoid valve and the atoms/molecules are subsequently ablated into this and cooled via elastic collisions, leaving a fraction of them trapped. This new set-up is currently being tested with lithium atoms as they are easier to make. After having optimised the trapping and detection processes, we will use the same trap for YbF molecules.

Observation of anisotropic interactions between metastable atoms and target molecules by two-dimensional collisional ionization electron spectroscopy

NASA Astrophysics Data System (ADS)

Kishimoto, Naoki; Ohno, Koichi

Excited metastable atoms colliding with target molecules can sensitively probe outer properties of molecules by chemi-ionization (Penning ionization) from molecular orbitals in the outer region, since metastable atoms cannot penetrate into the repulsive interaction wall around the molecules. By means of two-dimensional measurements using kinetic energy analysis of electrons combined with a velocity-resolved metastable beam, one can obtain information on the anisotropic interaction between the colliding particles without any control of orientation or alignment of target molecules. We have developed a classical trajectory method to calculate the collision energy dependence of partial ionization cross-sections (CEDPICS) on the anisotropic interaction potential energy surface, which has enabled us to study stereodynamics between metastable atoms and target molecules as well as the spatial distribution of molecular orbitals and electron ejection functions which have a relation with entrance and exit channels of the reaction. Based on the individual CEDPICS, the electronic structure of molecules can also be elucidated.

Very strong Rydberg atom scattering in K(12p)-CH3NO2 collisions: Role of transient ion pair formation

NASA Astrophysics Data System (ADS)

Kelley, M.; Buathong, S.; Dunning, F. B.

2017-05-01

Collisions between K(12p) Rydberg atoms and CH3NO2 target molecules are studied. Whereas CH3NO2 can form long-lived valence-bound CH3NO2-ions, the data provide no evidence for production of long-lived K+⋯ CH3NO2 - ion pair states. Rather, the data show that collisions result in unusually strong Rydberg atom scattering. This behavior is attributed to ion-ion scattering resulting from formation of transient ion pair states through transitions between the covalent K(12p) + CH3NO2 and ionic K+ + (dipole bound) CH3NO2-terms in the quasimolecule formed during collisions. The ion-pair states are destroyed through rapid dissociation of the CH3NO2 - ions induced by the field of the K+ core ion, the detached electron remaining bound to the K+ ion in a Rydberg state. Analysis of the experimental data shows that ion pair lifetimes ≳10 ps are sufficient to account for the present observations. The present results are consistent with recent theoretical predictions that Rydberg collisions with CH3NO2 will result in strong collisional quenching. The work highlights a new mechanism for Rydberg atom scattering that could be important for collisions with other polar targets. For purposes of comparison, results obtained following K(12p)-SF6 collisions are also included.

Non-thermal escape of molecular hydrogen from Mars

NASA Astrophysics Data System (ADS)

Gacesa, M.; Zhang, P.; Kharchenko, V.

2012-05-01

We present a detailed theoretical analysis of non-thermal escape of molecular hydrogen from Mars induced by collisions with hot atomic oxygen from the Martian corona. To accurately describe the energy transfer in O + H2(v, j) collisions, we performed extensive quantum-mechanical calculations of state-to-state elastic, inelastic, and reactive cross sections. The escape flux of H2 molecules was evaluated using a simplified 1D column model of the Martian atmosphere with realistic densities of atmospheric gases and hot oxygen production rates for low solar activity conditions. An average intensity of the non-thermal escape flux of H2 of 1.9 × 105 cm-2s-1 was obtained considering energetic O atoms produced in dissociative recombinations of O2+ ions. Predicted ro-vibrational distribution of the escaping H2 was found to contain a significant fraction of higher rotational states. While the non-thermal escape rate was found to be lower than Jeans rate for H2 molecules, the non-thermal escape rates of HD and D2 are significantly higher than their respective Jeans rates. The accurate evaluation of the collisional escape flux of H2 and its isotopes is important for understanding non-thermal escape of molecules from Mars, as well as for the formation of hot H2 Martian corona. The described molecular ejection mechanism is general and expected to contribute to atmospheric escape of H2 and other light molecules from planets, satellites, and exoplanetary bodies.

Applicability of the Child-Langmuir laws versions for describing the glow discharge cathode sheath in CO2

NASA Astrophysics Data System (ADS)

Lisovskiy, Valeriy; Krol, Hennadii; Osmayev, Ruslan; Yegorenkov, Vladimir

2016-09-01

This work is devoted to the determination of the law that may be applicable to the description of the cathode sheath in CO2. To this end three versions of the Child-Langmuir law have been considered - a collision free one (for the ions moving through a cathode sheath without collisions with gas molecules) as well as two collision- related versions- one for a constant mean free path of positive ions and one for a constant mobility of positive ions. The current-voltage characteristics and the cathode sheath thickness of the glow discharge in carbon oxide have been simultaneously measured in the pressure range from 0.05 to 1 Torr and with the discharge current values up to 80 mA. The inter-electrode distance has been chosen such that the discharge consists only of the cathode sheath and a small portion of the negative glow, i.e. the experiments have been performed in short tubes. In this case the voltage drop across the cathode sheath is equal approximately to the voltage drop across the electrodes. In the whole range of the discharge conditions we have studied the cathode sheath characteristics are found to obey correctly only to the Child-Langmuir law version with a constant ion mobility. The reason for this phenomenon may be related with a significant conversion of carbon dioxide molecules.

An evaluation of collision models in the Method of Moments for rarefied gas problems

NASA Astrophysics Data System (ADS)

Emerson, David; Gu, Xiao-Jun

2014-11-01

The Method of Moments offers an attractive approach for solving gaseous transport problems that are beyond the limit of validity of the Navier-Stokes-Fourier equations. Recent work has demonstrated the capability of the regularized 13 and 26 moment equations for solving problems when the Knudsen number, Kn (where Kn is the ratio of the mean free path of a gas to a typical length scale of interest), is in the range 0.1 and 1.0-the so-called transition regime. In comparison to numerical solutions of the Boltzmann equation, the Method of Moments has captured both qualitatively, and quantitatively, results of classical test problems in kinetic theory, e.g. velocity slip in Kramers' problem, temperature jump in Knudsen layers, the Knudsen minimum etc. However, most of these results have been obtained for Maxwell molecules, where molecules repel each other according to an inverse fifth-power rule. Recent work has incorporated more traditional collision models such as BGK, S-model, and ES-BGK, the latter being important for thermal problems where the Prandtl number can vary. We are currently investigating the impact of these collision models on fundamental low-speed problems of particular interest to micro-scale flows that will be discussed and evaluated in the presentation. Engineering and Physical Sciences Research Council under Grant EP/I011927/1 and CCP12.

Rotationally inelastic collisions of H2+ ions with He buffer gas: Computing cross sections and rates

NASA Astrophysics Data System (ADS)

Hernández Vera, Mario; Gianturco, F. A.; Wester, R.; da Silva, H.; Dulieu, O.; Schiller, S.

2017-03-01

We present quantum calculations for the inelastic collisions between H2+ molecules, in rotationally excited internal states, and He atoms. This work is motivated by the possibility of experiments in which the molecular ions are stored and translationally cooled in an ion trap and a He buffer gas is added for deactivation of the internal rotational population, in particular at low (cryogenic) translational temperatures. We carry out an accurate representation of the forces at play from an ab initio description of the relevant potential energy surface, with the molecular ion in its ground vibrational state, and obtain the cross sections for state-changing rotationally inelastic collisions by solving the coupled channel quantum scattering equations. The presence of hyperfine and fine structure effects in both ortho- and para-H2+ molecules is investigated and compared to the results where such a contribution is disregarded. An analysis of possible propensity rules that may predict the relative probabilities of inelastic events involving rotational state-changing is also carried out, together with the corresponding elastic cross sections from several initial rotational states. Temperature-dependent rotationally inelastic rates are then computed and discussed in terms of relative state-changing collisional efficiency under trap conditions. The results provide the essential input data for modeling different aspects of the experimental setups which can finally produce internally cold molecular ions interacting with a buffer gas.

Pulsed rotating supersonic source for merged molecular beams

NASA Astrophysics Data System (ADS)

Sheffield, L.; Hickey, M. S.; Krasovitskiy, V.; Rathnayaka, K. D. D.; Lyuksyutov, I. F.; Herschbach, D. R.

2012-06-01

We describe a pulsed rotating supersonic beam source, evolved from an ancestral device [M. Gupta and D. Herschbach, J. Phys. Chem. A 105, 1626 (2001)]. The beam emerges from a nozzle near the tip of a hollow rotor which can be spun at high-speed to shift the molecular velocity distribution downward or upward over a wide range. Here we consider mostly the slowing mode. Introducing a pulsed gas inlet system, cryocooling, and a shutter gate eliminated the main handicap of the original device in which continuous gas flow imposed high background pressure. The new version provides intense pulses, of duration 0.1-0.6 ms (depending on rotor speed) and containing ˜1012 molecules at lab speeds as low as 35 m/s and ˜1015 molecules at 400 m/s. Beams of any molecule available as a gas can be slowed (or speeded); e.g., we have produced slow and fast beams of rare gases, O2, Cl2, NO2, NH3, and SF6. For collision experiments, the ability to scan the beam speed by merely adjusting the rotor is especially advantageous when using two merged beams. By closely matching the beam speeds, very low relative collision energies can be attained without making either beam very slow.

Pulsed rotating supersonic source for merged molecular beams

NASA Astrophysics Data System (ADS)

Sheffield, Les; Hickey, Mark; Krasovitskiy, Vitaliy; Rathnayaka, Daya; Lyuksyutov, Igor; Herschbach, Dudley

2012-10-01

We continue the characterization of a pulsed rotating supersonic beam source. The original device was described by M. Gupta and D. Herschbach, J. Phys. Chem. A 105, 1626 (2001). The beam emerges from a nozzle near the tip of a hollow rotor which can be spun at high-speed to shift the molecular velocity distribution downward or upward over a wide range. Here we consider mostly the slowing mode. Introducing a pulsed gas inlet system, and a shutter gate eliminate the main handicap of the original device in which continuous gas flow imposed high background pressure. The new version provides intense pulses, of duration 0.1--0.6 ms (depending on rotor speed) and containing ˜10^12 molecules at lab speeds as low as 35 m/s and ˜10^15 molecules at 400 m/s. Beams of any molecule available as a gas can be slowed (or speeded); e.g., we have produced slow and fast beams of rare gases, O2, NO2, NH3, and SF6. For collision experiments, the ability to scan the beam speed by merely adjusting the rotor is especially advantageous when using two merged beams. By closely matching the beam speeds, very low relative collision energies can be attained without making either beam very slow.

Elastic collisions of low-energy electrons with SiY4 (Y = Cl, Br, I) molecules

NASA Astrophysics Data System (ADS)

Bettega, M. H. F.

2011-11-01

We employed the Schwinger multichannel method to compute elastic integral, differential, and momentum transfer cross sections for low-energy electron collisions with SiY4 (Y = Cl, Br, I) molecules. The calculations were carried out in the static-exchange and static-exchange plus polarization approximations for energies up to 10 eV. The elastic integral cross section for SiCl4 and SiBr4, computed in the static-exchange plus polarization approximation, shows two shape resonances belonging to the T2 and E symmetries of the Td group, and for SiI4 shows one shape resonance belonging to the E symmetry of the Td group. The present results agree well in shape with experimental total cross sections. The positions of the resonances observed in the calculated integral cross sections are also in agreement with the experimental positions. We have found the presence of a virtual state for SiCl4 and a Ramsauer-Townsend minimum for SiI4 at 0.5 eV. The present results show that the proper inclusion of polarization effects is crucial in order to correctly describe the resonance spectra of these molecules and also to identify a Ramsauer-Townsend minimum for SiI4 and a virtual state for SiCl4.

Analyses of chlorogenic acids and related cinnamic acid derivatives from Nicotiana tabacum tissues with the aid of UPLC-QTOF-MS/MS based on the in-source collision-induced dissociation method.

PubMed

Ncube, Efficient N; Mhlongo, Msizi I; Piater, Lizelle A; Steenkamp, Paul A; Dubery, Ian A; Madala, Ntakadzeni E

2014-01-01

Chlorogenic acids (CGAs) are a class of phytochemicals that are formed as esters between different derivatives of cinnamic acid and quinic acid molecules. In plants, accumulation of these compounds has been linked to several physiological responses against various stress factors; however, biochemical synthesis differs from one plant to another. Although structurally simple, the analysis of CGA molecules with modern analytical platforms poses an analytical challenge. The objective of the study was to perform a comparison of the CGA profiles and related derivatives from differentiated tobacco leaf tissues and undifferentiated cell suspension cultures. Using an UHPLC-Q-TOF-MS/MS fingerprinting method based on the in-source collision induced dissociation (ISCID) approach, a total of 19 different metabolites with a cinnamic acid core moiety were identified. These metabolites were either present in both leaf tissue and cell suspension samples or in only one of the two plant systems. Profile differences point to underlying biochemical similarities or differences thereof. Using this method, the regio- and geometric-isomer profiles of chlorogenic acids of the two tissue types of Nicotiana tabacum were achieved. The method was also shown to be applicable for the detection of other related molecules containing a cinnamic acid core.

Combining density functional theory (DFT) and collision cross-section (CCS) calculations to analyze the gas-phase behaviour of small molecules and their protonation site isomers.

PubMed

Boschmans, Jasper; Jacobs, Sam; Williams, Jonathan P; Palmer, Martin; Richardson, Keith; Giles, Kevin; Lapthorn, Cris; Herrebout, Wouter A; Lemière, Filip; Sobott, Frank

2016-06-20

Electrospray ion mobility-mass spectrometry (IM-MS) data show that for some small molecules, two (or even more) ions with identical sum formula and mass, but distinct drift times are observed. In spite of showing their own unique and characteristic fragmentation spectra in MS/MS, no configurational or constitutional isomers are found to be present in solution. Instead the observation and separation of such ions appears to be inherent to their gas-phase behaviour during ion mobility experiments. The origin of multiple drift times is thought to be the result of protonation site isomers ('protomers'). Although some important properties of protomers have been highlighted by other studies, correlating the experimental collision cross-sections (CCSs) with calculated values has proven to be a major difficulty. As a model, this study uses the pharmaceutical compound melphalan and a number of related molecules with alternative (gas-phase) protonation sites. Our study combines density functional theory (DFT) calculations with modified MobCal methods (e.g. nitrogen-based Trajectory Method algorithm) for the calculation of theoretical CCS values. Calculated structures can be linked to experimentally observed signals, and a strong correlation is found between the difference of the calculated dipole moments of the protomer pairs and their experimental CCS separation.

Double vibrational collision-induced Raman scattering by SF{sub 6}-N{sub 2}: Beyond the point-polarizable molecule model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Verzhbitskiy, I. A.; Chrysos, M.; Kouzov, A. P.

2010-11-15

Collision-induced Raman bandshapes and zeroth-order spectral moments are calculated both for the depolarized spectrum and for the extremely weak isotropic spectrum of the SF{sub 6}({nu}{sub 1}) +N{sub 2}({nu}{sub 1}) double-Raman-scattering band. A critical comparison is made with experiments conducted recently by the authors [Phys. Rev. A 81, 012702 (2010); 81, 042705 (2010)]. The study of this transition, hitherto restricted to the model framework of two point-polarizable molecules, is now completed to incorporate effects beyond the point-molecule approximation. Whereas the extended model offers a few percent improvement in the depolarized spectrum, it reveals a huge 80% increase in the isotropic spectrummore » and its moment, owing essentially to the polarizability anisotropy of N{sub 2}. For both spectra, agreement between quantum-mechanical calculations and our experiments is found, provided that the best ab initio data for the (hyper)polarizability parameters are used. This refined study shows clearly the need to include all mechanisms and data to a high level of accuracy and allows one to decide between alternatives about difficult and controversial issues such as the intermolecular potential or the sensitive Hamaker force constants.« less

Direct photoassociation of halo molecules in ultracold 86 Sr

NASA Astrophysics Data System (ADS)

Aman, J. A.; Hill, Joshua; Killian, T. C.

2017-04-01

We investigate the creation of 1S0 +1S0 halo molecules in strontium 86 through direct photoassociation in an optical dipole trap. We drive two photon Raman transitions near-resonance with a molecular level of the 1S0 +3P1 interatomic potential as the intermediate state. This provides large Frank-Condon factors and allows us to observe resonances for the creation of halo molecules through higher order Raman processes. The halo molecule is bound by EB 85 kHz at low excitation-laser intensity, but experiments show large AC Stark shifts of the molecular binding energy. These conditions suggest that STIRAP should be very effective for improving molecular conversion efficiency. Further experiments in a 3D lattice will explore molecular lifetimes and collision rates. Travel support provided by Shell Corporation.

The role of electron transfer in DNA building blocks: Evaluation of strand breaks and their implications

NASA Astrophysics Data System (ADS)

Almeida, Diogo Alexandre Fialho de

Radiation-induced damage to biological systems, both direct and indirect processes, has increasingly come under scrutiny by the international scientific community due to recent findings that electrons are a very effective agent in damaging DNA/RNA. Indeed, much remains to be discovered regarding the exact physico-chemical processes that occur in the nascent stages of DNA/RNA damage by incident radiation. However, it is also known that electrons do not exist freely in the physiological medium, but rather solvated and/or pre-solvated states. This leads to the need for new techniques that can better explore the damaging role of "bound" electrons to DNA/RNA. The work presented in this thesis consists on the study of electron transfer in collisions of atomic species with molecules of biological relevance. In order to study these processes, two experimental setups were used. One setup consists of a crossed beam experiment where a neutral potassium beam is created and made to collide with an effusive molecular target beam. The anionic products that stem from electron transfer in potassium atom to the molecular target collisions are then extracted and time-of-flight (TOF) mass analysed. In the second setup a beam of anionic species is formed and made to collide with a molecular target. Collisions with three different anionic beams were performed (H-, O- and OH-), as well as with different simple organic molecules, by measuring the positive and negative ion fragmentation patterns with a quadrupole mass spectrometer (QMS). A comparison between these two collisional systems can greatly help to understand the underlying mechanisms of the electron transfer processes. Finally, studies of potassium collisions with sugar surrogates D-Ribose and THF were performed. These studies show very different fragmentation patterns from DEA, although in the case of THF, it is suggested that the initially accessed states are the same as in DEA. With these studies was also possible to show for the first time collision induced site and bond selectivity breaking, where the electron is transferred into a given state of the acceptor molecule and the resulting fragmentation pathways are exclusive to the initial anionic state. Furthermore, the role of the potassium cation post collisionwas explored and indeed its presence is suggested to induce at least partial suppression of auto-detachment. The implications that ensue from this degradation are analysed in the light of the obtained fragmentation patterns.

Effect of substrate thickness on ejection of phenylalanine molecules adsorbed on free-standing graphene bombarded by 10 keV C60

NASA Astrophysics Data System (ADS)

Golunski, M.; Verkhoturov, S. V.; Verkhoturov, D. S.; Schweikert, E. A.; Postawa, Z.

2017-02-01

Molecular dynamics computer simulations have been employed to investigate the effect of substrate thickness on the ejection mechanism of phenylalanine molecules deposited on free-standing graphene. The system is bombarded from the graphene side by 10 keV C60 projectiles at normal incidence and the ejected particles are collected both in transmission and reflection directions. It has been found that the ejection mechanism depends on the substrate thickness. At thin substrates mostly organic fragments are ejected by direct collisions between projectile atoms and adsorbed molecules. At thicker substrates interaction between deforming topmost graphene sheet and adsorbed molecules becomes more important. As this process is gentle and directionally correlated, it leads predominantly to ejection of intact molecules. The implications of the results to a novel analytical approach in Secondary Ion Mass Spectrometry based on ultrathin free-standing graphene substrates and a transmission geometry are discussed.

Evaporation and condensation at a liquid surface. I. Argon

NASA Astrophysics Data System (ADS)

Yasuoka, Kenji; Matsumoto, Mitsuhiro; Kataoka, Yosuke

1994-11-01

Molecular dynamics computer simulations were carried out to investigate the dynamics of evaporation and condensation for argon at the temperature of 80 and 100 K. From the decrease of the survival probability of vapor molecules, the ratio of self reflection to collision is estimated to be 12%-15%, only weakly dependent on the temperature. This suggests that argon vapor molecules are in the condition of almost complete capture, and the condensation is considered to be a barrierless process. The total ratio of reflection which is evaluated with the flux correlation of condensation and evaporation is 20% at both temperature. The difference between these two ratios of reflection is ascribed to a phenomenon that vapor molecules colliding with the surface drive out other liquid molecules. This molecule exchange at the surface is as important as the self-reflection, and the conventional picture of condensation as a unimolecular chemical reaction is not appropriate.

Ab initio dynamics and photoionization mass spectrometry reveal ion-molecule pathways from ionized acetylene clusters to benzene cation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Stein, Tamar; Bandyopadhyay, Biswajit; Troy, Tyler P.

The growth mechanism of hydrocarbons in ionizing environments, such as the interstellar medium (ISM), and some combustion conditions remains incompletely understood. Ab initio molecular dynamics (AIMD) simulations and molecular beam vacuum-UV (VUV) photoionization mass spectrometry experiments were performed to understand the ion-molecule growth mechanism of small acetylene clusters (up to hexamers). A dramatic dependence of product distribution on the ionization conditions is demonstrated experimentally and understood from simulations. The products change from reactive fragmentation products in a higher temperature, higher density gas regime toward a very cold collision-free cluster regime that is dominated by products whose empirical formula is (Cmore » 2H 2) n +, just like ionized acetylene clusters. The fragmentation products result from reactive ion- molecule collisions in a comparatively higher pressure and temperature regime followed by unimolecular decomposition. The isolated ionized clusters display rich dynamics that contain bonded C 4H 4 + and C 6H 6 + structures solvated with one or more neutral acetylene molecules. Such species contain large amounts ( > 2 eV) of excess internal energy. The role of the solvent acetylene molecules is to affect the barrier crossing dynamics in the potential energy surface (PES) between (C 2H 2) n + isomers and provide evaporative cooling to dissipate the excess internal energy and stabilize products including the aromatic ring of the benzene cation. Formation of the benzene cation is demonstrated in AIMD simulations of acetylene clusters with n > 3, as well as other metastable C 6H 6 + isomers. Lastly, these results suggest a path for aromatic ring formation in cold acetylene-rich environments such as parts of the ISM.« less

Ab initio dynamics and photoionization mass spectrometry reveal ion–molecule pathways from ionized acetylene clusters to benzene cation

PubMed Central

Stein, Tamar; Bandyopadhyay, Biswajit; Troy, Tyler P.; Fang, Yigang; Kostko, Oleg

2017-01-01

The growth mechanism of hydrocarbons in ionizing environments, such as the interstellar medium (ISM), and some combustion conditions remains incompletely understood. Ab initio molecular dynamics (AIMD) simulations and molecular beam vacuum-UV (VUV) photoionization mass spectrometry experiments were performed to understand the ion–molecule growth mechanism of small acetylene clusters (up to hexamers). A dramatic dependence of product distribution on the ionization conditions is demonstrated experimentally and understood from simulations. The products change from reactive fragmentation products in a higher temperature, higher density gas regime toward a very cold collision-free cluster regime that is dominated by products whose empirical formula is (C2H2)n+, just like ionized acetylene clusters. The fragmentation products result from reactive ion–molecule collisions in a comparatively higher pressure and temperature regime followed by unimolecular decomposition. The isolated ionized clusters display rich dynamics that contain bonded C4H4+ and C6H6+ structures solvated with one or more neutral acetylene molecules. Such species contain large amounts (>2 eV) of excess internal energy. The role of the solvent acetylene molecules is to affect the barrier crossing dynamics in the potential energy surface (PES) between (C2H2)n+ isomers and provide evaporative cooling to dissipate the excess internal energy and stabilize products including the aromatic ring of the benzene cation. Formation of the benzene cation is demonstrated in AIMD simulations of acetylene clusters with n > 3, as well as other metastable C6H6+ isomers. These results suggest a path for aromatic ring formation in cold acetylene-rich environments such as parts of the ISM. PMID:28484019

Ab initio dynamics and photoionization mass spectrometry reveal ion-molecule pathways from ionized acetylene clusters to benzene cation.

PubMed

Stein, Tamar; Bandyopadhyay, Biswajit; Troy, Tyler P; Fang, Yigang; Kostko, Oleg; Ahmed, Musahid; Head-Gordon, Martin

2017-05-23

The growth mechanism of hydrocarbons in ionizing environments, such as the interstellar medium (ISM), and some combustion conditions remains incompletely understood. Ab initio molecular dynamics (AIMD) simulations and molecular beam vacuum-UV (VUV) photoionization mass spectrometry experiments were performed to understand the ion-molecule growth mechanism of small acetylene clusters (up to hexamers). A dramatic dependence of product distribution on the ionization conditions is demonstrated experimentally and understood from simulations. The products change from reactive fragmentation products in a higher temperature, higher density gas regime toward a very cold collision-free cluster regime that is dominated by products whose empirical formula is (C 2 H 2 ) n + , just like ionized acetylene clusters. The fragmentation products result from reactive ion-molecule collisions in a comparatively higher pressure and temperature regime followed by unimolecular decomposition. The isolated ionized clusters display rich dynamics that contain bonded C 4 H 4 + and C 6 H 6 + structures solvated with one or more neutral acetylene molecules. Such species contain large amounts (>2 eV) of excess internal energy. The role of the solvent acetylene molecules is to affect the barrier crossing dynamics in the potential energy surface (PES) between (C 2 H 2 ) n + isomers and provide evaporative cooling to dissipate the excess internal energy and stabilize products including the aromatic ring of the benzene cation. Formation of the benzene cation is demonstrated in AIMD simulations of acetylene clusters with n > 3, as well as other metastable C 6 H 6 + isomers. These results suggest a path for aromatic ring formation in cold acetylene-rich environments such as parts of the ISM.

Electron collisions with the HCOOH···(H2O)n complexes (n = 1, 2) in liquid phase: the influence of microsolvation on the π* resonance of formic acid.

PubMed

Freitas, T C; Coutinho, K; Varella, M T do N; Lima, M A P; Canuto, S; Bettega, M H F

2013-05-07

We report momentum transfer cross sections for elastic collisions of low-energy electrons with the HCOOH···(H2O)n complexes, with n = 1, 2, in liquid phase. The scattering cross sections were computed using the Schwinger multichannel method with pseudopotentials in the static-exchange and static-exchange plus polarization approximations, for energies ranging from 0.5 eV to 6 eV. We considered ten different structures of HCOOH···H2O and six structures of HCOOH···(H2O)2 which were generated using classical Monte Carlo simulations of formic acid in aqueous solution at normal conditions of temperature and pressure. The aim of this work is to investigate the influence of microsolvation on the π* shape resonance of formic acid. Previous theoretical and experimental studies reported a π* shape resonance for HCOOH at around 1.9 eV. This resonance can be either more stable or less stable in comparison to the isolated molecule depending on the complex structure and the water role played in the hydrogen bond interaction. This behavior is explained in terms of (i) the polarization of the formic acid molecule due to the water molecules and (ii) the net charge of the solute. The proton donor or acceptor character of the water molecules in the hydrogen bond is important for understanding the stabilization versus destabilization of the π* resonances in the complexes. Our results indicate that the surrounding water molecules may affect the lifetime of the π* resonance and hence the processes driven by this anion state, such as the dissociative electron attachment.

Ab initio dynamics and photoionization mass spectrometry reveal ion-molecule pathways from ionized acetylene clusters to benzene cation

DOE PAGES

Stein, Tamar; Bandyopadhyay, Biswajit; Troy, Tyler P.; ...

2017-05-08

The growth mechanism of hydrocarbons in ionizing environments, such as the interstellar medium (ISM), and some combustion conditions remains incompletely understood. Ab initio molecular dynamics (AIMD) simulations and molecular beam vacuum-UV (VUV) photoionization mass spectrometry experiments were performed to understand the ion-molecule growth mechanism of small acetylene clusters (up to hexamers). A dramatic dependence of product distribution on the ionization conditions is demonstrated experimentally and understood from simulations. The products change from reactive fragmentation products in a higher temperature, higher density gas regime toward a very cold collision-free cluster regime that is dominated by products whose empirical formula is (Cmore » 2H 2) n +, just like ionized acetylene clusters. The fragmentation products result from reactive ion- molecule collisions in a comparatively higher pressure and temperature regime followed by unimolecular decomposition. The isolated ionized clusters display rich dynamics that contain bonded C 4H 4 + and C 6H 6 + structures solvated with one or more neutral acetylene molecules. Such species contain large amounts ( > 2 eV) of excess internal energy. The role of the solvent acetylene molecules is to affect the barrier crossing dynamics in the potential energy surface (PES) between (C 2H 2) n + isomers and provide evaporative cooling to dissipate the excess internal energy and stabilize products including the aromatic ring of the benzene cation. Formation of the benzene cation is demonstrated in AIMD simulations of acetylene clusters with n > 3, as well as other metastable C 6H 6 + isomers. Lastly, these results suggest a path for aromatic ring formation in cold acetylene-rich environments such as parts of the ISM.« less

Highly stable families of soliton molecules in fiber-optic systems

NASA Astrophysics Data System (ADS)

Moubissi, A.-B.; Tchofo Dinda, P.; Nse Biyoghe, S.

2018-04-01

We develop an efficient approach to the design of families of single solitons and soliton molecules most suited to a given fiber system. The obtained solitonic entities exhibit very high stability, with a robustness which allows them to propagate over thousands of kilometers and to survive collisions with other solitonic entities. Our approach enables the generation of a large number of solitonic entities, including families of single solitons and two-soliton molecules, which can be distinguished sufficiently by their respective profiles or energy levels, and so can be easily identifiable and detectable without ambiguity. We discuss the possible use of such solitonic entities as symbols of a multi-level modulation format in fiber-optic communication systems.

The "Collisions Cube" Molecular Dynamics Simulator.

ERIC Educational Resources Information Center

Nash, John J.; Smith, Paul E.

1995-01-01

Describes a molecular dynamics simulator that employs ping-pong balls as the atoms or molecules and is suitable for either large lecture halls or small classrooms. Discusses its use in illustrating many of the fundamental concepts related to molecular motion and dynamics and providing a three-dimensional perspective of molecular motion. (JRH)

Classical Trajectory Study of Collision Energy Transfer between Ne and C2H2 on a Full Dimensional Accurate Potential Energy Surface.

PubMed

Liu, Yang; Huang, Yin; Ma, Jianyi; Li, Jun

2018-02-15

Collision energy transfer plays an important role in gas phase reaction kinetics and relaxation of excited molecules. However, empirical treatments are generally adopted for the collisional energy transfer in the master equation based approach. In this work, classical trajectory approach is employed to investigate the collision energy transfer dynamics in the C 2 H 2 -Ne system. The entire potential energy surface is described as the sum of the C 2 H 2 potential and interaction potential between C 2 H 2 and Ne. It is highlighted that both parts of the entire potential are highly accurate. In particular, the interaction potential is fit to ∼41 300 configurations determined at the level of CCSD(T)-F12a/cc-pCVTZ-F12 with the counterpoise correction. Collision energy transfer dynamics are then carried out on this benchmark potential and the widely used Lennard-Jones and Buckingham interaction potentials. Energy transfers and related probability densities at different collisional energies are reported and discussed.

Scattering resonances in bimolecular collisions between NO radicals and H2 challenge the theoretical gold standard

NASA Astrophysics Data System (ADS)

Vogels, Sjoerd N.; Karman, Tijs; Kłos, Jacek; Besemer, Matthieu; Onvlee, Jolijn; van der Avoird, Ad; Groenenboom, Gerrit C.; van de Meerakker, Sebastiaan Y. T.

2018-02-01

Over the last 25 years, the formalism known as coupled-cluster (CC) theory has emerged as the method of choice for the ab initio calculation of intermolecular interaction potentials. The implementation known as CCSD(T) is often referred to as the gold standard in quantum chemistry. It gives excellent agreement with experimental observations for a variety of energy-transfer processes in molecular collisions, and it is used to calibrate density functional theory. Here, we present measurements of low-energy collisions between NO radicals and H2 molecules with a resolution that challenges the most sophisticated quantum chemistry calculations at the CCSD(T) level. Using hitherto-unexplored anti-seeding techniques to reduce the collision energy in a crossed-beam inelastic-scattering experiment, a resonance structure near 14 cm-1 is clearly resolved in the state-to-state integral cross-section, and a unique resonance fingerprint is observed in the corresponding differential cross-section. This resonance structure discriminates between two NO-H2 potentials calculated at the CCSD(T) level and pushes the required accuracy beyond the gold standard.

The effects of particle recycling on the divertor plasma: A particle-in-cell with Monte Carlo collision simulation

NASA Astrophysics Data System (ADS)

Chang, Mingyu; Sang, Chaofeng; Sun, Zhenyue; Hu, Wanpeng; Wang, Dezhen

2018-05-01

A Particle-In-Cell (PIC) with Monte Carlo Collision (MCC) model is applied to study the effects of particle recycling on divertor plasma in the present work. The simulation domain is the scrape-off layer of the tokamak in one-dimension along the magnetic field line. At the divertor plate, the reflected deuterium atoms (D) and thermally released deuterium molecules (D2) are considered. The collisions between the plasma particles (e and D+) and recycled neutral particles (D and D2) are described by the MCC method. It is found that the recycled neutral particles have a great impact on divertor plasma. The effects of different collisions on the plasma are simulated and discussed. Moreover, the impacts of target materials on the plasma are simulated by comparing the divertor with Carbon (C) and Tungsten (W) targets. The simulation results show that the energy and momentum losses of the C target are larger than those of the W target in the divertor region even without considering the impurity particles, whereas the W target has a more remarkable influence on the core plasma.

Comparative study of elastic electron collisions on the isoelectronic SiN{sub 2}, SiCO, and CSiO radicals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fujimoto, M. M.; Michelin, S. E.; Mazon, K. T.

2007-07-15

We report a theoretical study of elastic electron collisions on three isoelectronic free radicals, namely, SiNN, SiCO, and CSiO. More specifically, differential, integral, and momentum-transfer cross sections are calculated and reported in the (1-100) eV energy range. Calculations are performed at the static-exchange-polarization-absorption level of approximation. A combination of the iterative Schwinger variational method and the distorted-wave approximation is used to solve the scattering equations. Our study reveals that the calculated cross sections for the e{sup -}-SiNN and e{sup -}-SiCO collisions are very similar even at incident energies as low as 3 eV. Strong isomeric effects are also observed inmore » the calculated cross sections for e{sup -}-CSiO and e{sup -}-SiCO collisions, particularly at incident energies below 20 eV. It is believed that the position of the silicon atom being at the center or extremity of the molecules may exert important influence on the calculated cross sections.« less

Transport processes and sound velocity in vibrationally non-equilibrium gas of anharmonic oscillators

NASA Astrophysics Data System (ADS)

Rydalevskaya, Maria A.; Voroshilova, Yulia N.

2018-05-01

Vibrationally non-equilibrium flows of chemically homogeneous diatomic gases are considered under the conditions that the distribution of the molecules over vibrational levels differs significantly from the Boltzmann distribution. In such flows, molecular collisions can be divided into two groups: the first group corresponds to "rapid" microscopic processes whereas the second one corresponds to "slow" microscopic processes (their rate is comparable to or larger than that of gasdynamic parameters variation). The collisions of the first group form quasi-stationary vibrationally non-equilibrium distribution functions. The model kinetic equations are used to study the transport processes under these conditions. In these equations, the BGK-type approximation is used to model only the collision operators of the first group. It allows us to simplify derivation of the transport fluxes and calculation of the kinetic coefficients. Special attention is given to the connection between the formulae for the bulk viscosity coefficient and the sound velocity square.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Zhiying; Heller, Eric J.; Krems, Roman V.

We explore the collision dynamics of complex hydrocarbon molecules (benzene, coronene, adamantane, and anthracene) containing carbon rings in a cold buffer gas of {sup 3}He. For benzene, we present a comparative analysis of the fully classical and fully quantum calculations of elastic and inelastic scattering cross sections at collision energies between 1 and 10 cm{sup −1}. The quantum calculations are performed using the time-independent coupled channel approach and the coupled-states approximation. We show that the coupled-states approximation is accurate at collision energies between 1 and 20 cm{sup −1}. For the classical dynamics calculations, we develop an approach exploiting the rigiditymore » of the carbon rings and including low-energy vibrational modes without holonomic constraints. Our results illustrate the effect of the molecular shape and the vibrational degrees of freedom on the formation of long-lived resonance states that lead to low-temperature clustering.« less

Hypersonic panel flutter in a rarefied atmosphere

NASA Technical Reports Server (NTRS)

Resende, Hugo B.

1993-01-01

Panel flutter is a form of dynamic aeroelastic instability resulting from the interaction between motion of an aircraft structural panel and the aerodynamic loads exerted on that panel by air flowing past one of the faces. It differs from lifting surface flutter in the sense that it is not usually catastrophic, the panel's motion being limited by nonlinear membrane stresses produced by the transverse displacement. Above some critical airflow condition, the linear instability grows to a limit cycle . The present investigation studies panel flutter in an aerodynamic regime known as 'free molecule flow', wherein intermolecular collisions can be neglected and loads are caused by interactions between individual molecules and the bounding surface. After collision with the panel, molecules may be reflected specularly or reemitted in diffuse fashion. Two parameters characterize this process: the 'momentum accommodation coefficient', which is the fraction of the specularly reflected molecules; and the ratio between the panel temperature and that of the free airstream. This model is relevant to the case of hypersonic flight vehicles traveling at very high altitudes and especially for panels oriented parallel to the airstream or in the vehicle's lee. Under these conditions the aerodynamic shear stress turns out to be considerably larger than the surface pressures, and shear effects must be included in the model. This is accomplished by means of distributed longitudinal and bending loads. The former can cause the panel to buckle. In the example of a simply-supported panel, it turns out that the second mode of free vibration tends to dominate the flutter solution, which is carried out by a Galerkin analysis. Several parametric studies are presented. They include the effects of (1) temperature ratio; (2) momentum accommodation coefficient; (3) spring parameters, which are associated with how the panel is connected to adjacent structures; (4) a parameter which relates compressive end load to its value which would cause classical column buckling; (5) a parameter proportional to the pressure differential between the front and back faces; and (6) initial curvature. The research is completed by an investigation into the possibility of accounting for molecular collisions, which proves to be infeasible given the speeds of current mainframe supercomputers.

Dissociative excitation of the manganese atom quartet levels by collisions e-MnBr2

NASA Astrophysics Data System (ADS)

Smirnov, Yu M.

2017-04-01

Dissociative excitation of quartet levels of the manganese atom was studied in collisions of electrons with manganese dibromide molecules. Eighty-two cross-sections for transitions originating at odd levels and eleven cross-sections for transitions originating at even levels have been measured at an incident electron energy of 100 eV. An optical excitation function has been recorded in the electron energy range of 0-100 eV for transitions originating from 3d 64p z 4 F° levels. For the majority of transitions, a comparison of the resulting cross-section values to cross-sections produced by direct excitation is provided.

The Franck-Hertz Experiments, 1911-1914 Experimentalists in Search of a Theory. With an appendix, "On the History of our Experiments on the Energy Exchange between Slow Electrons and Atoms" by Gustav Hertz

NASA Astrophysics Data System (ADS)

Gearhart, Clayton A.

2014-09-01

In 1911, James Franck and Gustav Hertz began a collaboration to investigate the nature of collisions of slow electrons with gas molecules that led to a series of carefully planned and executed experiments, culminating in their discovery of inelastic collisions of electrons with mercury vapor atoms in 1914. This paper tells the story of their collaboration and the eventual reinterpretation of their results as a confirmation of Niels Bohr's new atomic theory, largely as a result of experiments done in North America during the Great War.

Fragmentation of amino acids induced by collisions with low-energy highly charged ions

NASA Astrophysics Data System (ADS)

Piekarski, D. G.; Maclot, S.; Domaracka, A.; Adoui, L.; Alcamí, M.; Rousseau, P.; Díaz-Tendero, S.; Huber, B. A.; Martín, F.

2014-04-01

Fragmentation of amino acids NH2-(CH2)n-COOH (n=1 glycine; n=2 β-alanine and n=3 γ-aminobutyric acid GABA) following collisions with slow highly charged ions has been studied in the gas phase by a combined experimental and theoretical approach. In the experiments, a multi-coincidence detection method was used to deduce the charge state of the molecules before fragmentation. Quantum chemistry calculations have been carried out in the basis of the density functional theory and ab initio molecular dynamics. The combination of both methodologies is essential to unambiguously unravel the different fragmentation pathways.

A far wing line shape theory and its application to the water continuum absorption in the infrared region. I

NASA Technical Reports Server (NTRS)

Ma, Q.; Tipping, R. H.

1991-01-01

The present theory for the continuous absorption that is due to the far-wing contribution of allowed lines is based on the quasistatic approximation for the far wing limit and the binary collision approximation of one absorber molecule and one bath molecule. The validity of the theory is discussed, and numerical results of the water-continuum absorption in the IR region are presented for comparison with experimental data. Good agreement is obtained for both the magnitude and temperature dependence of the absorption coefficients.

Quantum dynamics study on the binding of a positron to vibrationally excited states of hydrogen cyanide molecule

NASA Astrophysics Data System (ADS)

Takayanagi, Toshiyuki; Suzuki, Kento; Yoshida, Takahiko; Kita, Yukiumi; Tachikawa, Masanori

2017-05-01

We present computational results of vibrationally enhanced positron annihilation in the e+ + HCN/DCN collisions within a local complex potential model. Vibrationally elastic and inelastic cross sections and effective annihilation rates were calculated by solving a time-dependent complex-potential Schrödinger equation under the ab initio potential energy surface for the positron attached HCN molecule, [HCN; e+], with multi-component configuration interaction level (Kita and Tachikawa, 2014). We discuss the effect of vibrational excitation on the positron affinities from the obtained vibrational resonance features.

Stimulated emission by hybrid transitions via a heteronuclear molecule

NASA Astrophysics Data System (ADS)

Dinev, S. G.; Khadzhikhristov, G. B.; Stefanov, I. L.

1990-03-01

An atomic emission, identified as a four-wave parametric emission and stimulated by collision assisted hybrid transition via a heteronuclear molecule, is presented together with a diagram of excitation and emission for the relevant K and NaK energy levels. The cascading emission from the excited 7S or 5D levels to lower-lying atomic states is considered to be insignificant. The dependence of the red signal and the NaK fluorescence on the pump energy is investigated, and the results can be used to indicate the onset of a stimulated process.

Probing Trapped Ion Energies Via Ion-Molecule Reaction Kinetics: Fourier Transform Ion Cyclotron Resonance Mass Spectrometry

DTIC Science & Technology

1992-05-28

ORGANIZATION (if applicable) Office of Naval Research N00014-87- j - 1248 Bc. ADDRESS (City, State, and ZIP Code) 10. SOURCE OF FUNDING NUMBERS 800 N. Quincy St...RESEARCH Grant NOOO14-87- J -1248 R & T Code 4134052 TECHNICAL REPORT NO. 36 Probing Trapped Ion Energies Via Ion-Molecule Reaction Kinetics: Fourier...reactivity (for charge transfer with N2) of the higher energy J =1/2 state is approximately three times that of the J =3/2 state at collision energies

Quantum study of Eley-Rideal reaction and collision induced desorption of hydrogen atoms on a graphite surface. II. H-physisorbed case.

PubMed

Martinazzo, Rocco; Tantardini, Gian Franco

2006-03-28

Following previous investigation of collision induced (CI) processes involving hydrogen atoms chemisorbed on graphite [R. Martinazzo and G. F. Tantardini, J. Chem. Phys. 124, 124702 (2006)], the case in which the target hydrogen atom is initially physisorbed on the surface is considered here. Several adsorbate-substrate initial states of the target H atom in the physisorption well are considered, and CI processes are studied for projectile energies up to 1 eV. Results show that (i) Eley-Rideal cross sections at low collision energies may be larger than those found in the H-chemisorbed case but they rapidly decrease as the collision energy increases; (ii) product hydrogen molecules are vibrationally very excited; (iii) collision induced desorption cross sections rapidly increase, reaching saturation values greater than 10 A2; (iv) trapping of the incident atoms is found to be as efficient as the Eley-Rideal reaction at low energies and remains sizable (3-4 A2) at high energies. The latter adsorbate-induced trapping results mainly in formation of metastable hot hydrogen atoms, i.e., atoms with an excess energy channeled in the motion parallel to the surface. These atoms might contribute in explaining hydrogen formation on graphite.

Ion-neutral potential models in atmospheric pressure ion mobility time-of-flight mass spectrometry IM(tof)MS.

PubMed

Steiner, Wes E; English, William A; Hill, Herbert H

2006-02-09

The ion mobilities and their respective masses of several classes of amines (primary, secondary, and tertiary) were measured by electrospray ionization atmospheric pressure ion mobility time-of-flight mass spectrometry IM(tof)MS. The experimental data obtained were comparatively analyzed by the one-temperature kinetic theory of Chapman-Enskog. Several theoretical models were used to estimate the collision cross-sections; they include the rigid-sphere, polarization-limit, 12-6-4, and 12-4 potential models. These models were investigated to represent the interaction potentials contained within the collision integral that occurs between the polyatomic ions and the neutral drift gas molecules. The effectiveness of these collision cross-section models on predicting the mobility of these amine ions was explored. Moreover, the effects of drift gas selectivity on the reduced-mass term and in the collision cross-section term was examined. Use of a series of drift gases, namely, helium, neon, argon, nitrogen, and carbon dioxide, made it possible to distinguish between mass effects and polarizability effects. It was found that the modified 12-4 potential that compensates for the center of charge not being at the same location as the centers of mass showed improved agreement over the other collision cross-section models with respect to experimental data.

Polarization Spectroscopy and Collisions in NaK

NASA Astrophysics Data System (ADS)

Wolfe, C. M.; Ashman, S.; Huennekens, J.; Beser, B.; Bai, J.; Lyyra, A. M.

2009-05-01

We report current work to study transfer of population and orientation in collisions of NaK molecules with argon and potassium atoms using polarization labeling (PL) and laser-induced fluorescence (LIF) spectroscopy. In the PL experiment, a circularly polarized pump laser excites a specific NaK A^1&+circ;(v=16, J) <- X^1&+circ;(v=0, J±1) transition, creating an orientation (non-uniform MJ level distribution) in both levels. The linear polarized probe laser is scanned over various 3^1π(v=8, J' ±1) <- A^1&+circ;(v=16, J') transitions. The probe laser passes through a crossed linear polarizer before detection, and signal is recorded if the probe laser polarization has been modified by the vapor (which occurs when it comes into resonance with an oriented level). In addition to strong direct transitions (J' = J), we also observe weak collisional satellite lines (J' = J±n with n = 1, 2, 3, ...) indicating that orientation is transferred to adjacent rotational levels during a collision. An LIF experiment (with linear polarized pump and probe beams) gives information on the collisional transfer of population. From these data, cross sections for both processes can be determined. We experimentally distinguish collisions of NaK with argon atoms from collisions with alkali atoms.

The Approach to Equilibrium: Detailed Balance and the Master Equation

ERIC Educational Resources Information Center

Alexander, Millard H.; Hall, Gregory E.; Dagdigian, Paul J.

2011-01-01

The approach to the equilibrium (Boltzmann) distribution of populations of internal states of a molecule is governed by inelastic collisions in the gas phase and with surfaces. The set of differential equations governing the time evolution of the internal state populations is commonly called the master equation. An analytic solution to the master…

Understanding Molecular-Ion Neutral Atom Collisions for the Production of Ultracold Molecular Ions

DTIC Science & Technology

2014-02-03

SECURITY CLASSIFICATION OF: This project was superseded and replaced by another ARO-funded project of the same name, which is still continuing. The goal...cooled atoms," IOTA -COST Workshop on molecular ions, Arosa, Switzerland. 5. E.R. Hudson, "Sympathetic cooling of molecules with laser cooled

Mapped grid methods for long-range molecules and cold collisions

NASA Astrophysics Data System (ADS)

Willner, K.; Dulieu, O.; Masnou-Seeuws, F.

2004-01-01

The paper discusses ways of improving the accuracy of numerical calculations for vibrational levels of diatomic molecules close to the dissociation limit or for ultracold collisions, in the framework of a grid representation. In order to avoid the implementation of very large grids, Kokoouline et al. [J. Chem. Phys. 110, 9865 (1999)] have proposed a mapping procedure through introduction of an adaptive coordinate x subjected to the variation of the local de Broglie wavelength as a function of the internuclear distance R. Some unphysical levels ("ghosts") then appear in the vibrational series computed via a mapped Fourier grid representation. In the present work the choice of the basis set is reexamined, and two alternative expansions are discussed: Sine functions and Hardy functions. It is shown that use of a basis set with fixed nodes at both grid ends is efficient to eliminate "ghost" solutions. It is further shown that the Hamiltonian matrix in the sine basis can be calculated very accurately by using an auxiliary basis of cosine functions, overcoming the problems arising from numerical calculation of the Jacobian J(x) of the R→x coordinate transformation.

An R-matrix study of electron induced processes in BF3 plasma

NASA Astrophysics Data System (ADS)

Gupta, Dhanoj; Chakrabarti, Kalyan; Yoon, Jung-Sik; Song, Mi-Young

2017-12-01

An R-matrix formalism is used to study electron collision with the BF3 molecule using Quantemol-N, a computational system for electron molecule collisions which uses the molecular R-matrix method. Several target models are tested for BF3 in its equilibrium geometry, and the results are presented for the best model. Scattering calculations are then performed to yield resonance parameters, elastic, differential, excitation, and momentum transfer cross sections. The results for all the cross sections are compared with the experimental and theoretical data, and a good agreement is obtained. The resonances have been detected at 3.79 and 13.58 eV, with the ionization threshold being 15.7 eV. We have also estimated the absolute dissociative electron attachment (DEA) cross section for the F- ion production from BF3, which is a maiden attempt. The peak of the DEA is at around 13.5 eV, which is well supported by the resonance detected at 13.58 eV. The cross sections reported here find a variety of applications in the plasma technology.

Heterogeneous catalysis with lasers

NASA Astrophysics Data System (ADS)

George, T. F.

1986-06-01

Theoretical techniques have been developed to describe a variety of laser-induced molecular rate processes occurring at solid surfaces which are involved in heterogeneous catalysis. Such processes include adsorption, migration, chemical reactions and desorption. The role of surface phonons in laser-selective processes and laser heating has been analyzed. The importance of electronic degrees of freedom has been considered for semiconductor and metal substrates, with special emphasis on the laser excitation of surface states. Surface-modified photochemistry has also been investigated, where the effect of a metal surface on the resonance fluorescence spectrum of a laser-driven atom/molecule has been assessed by means of surface-dressed optical Bloch equations. It is seen that the spectrum can be significantly different from the gas-phase case. Two related gas-surface collision processes have also been studied. First, the feasibility of the formation of the electron-hole pairs in a semiconductor by vibrationally excited molecules has been explored. Second, charge transfer in ion-surface collisions has been examined for both one-electron and two-electron transfer processes. Work has been initiated on microstructures and rough structures, including clusters and surface gratings.

Specific cationic emission of cisplatin following ionization by swift protons

NASA Astrophysics Data System (ADS)

Moretto-Capelle, Patrick; Champeaux, Jean-Philippe; Deville, Charlotte; Sence, Martine; Cafarelli, Pierre

2016-05-01

We have investigated collision-induced ionization and fragmentation by 100 keV protons of the radio sensitizing molecule cisplatin, which is used in cancer treatments. A large emission of HCl+ and NH2+ is observed, but surprisingly, no cationic fragments containing platinum are detected, in contrast to ionization-dissociation induced by electronic collision. Theoretical investigations show that the ionization processes take place on platinum and on chlorine atoms. We propose new ionization potentials for cisplatin. Dissociation limits corresponding to the measured fragmentation mass spectrum have been evaluated and the theoretical results show that the non-observed cationic fragments containing platinum are mostly associated with low dissociation energies. We have also investigated the reaction path for the hydrogen transfer from the NH3 group to the Cl atom, as well as the corresponding dissociation limits from this tautomeric form. Here again the cations containing platinum correspond to lower dissociation limits. Thus, the experimental results suggest that excited states, probably formed via inner-shell ionization of the platinum atom of the molecule, correlated to higher dissociation limits are favored.

Collision-induced evaporation of water clusters and contribution of momentum transfer

NASA Astrophysics Data System (ADS)

Calvo, Florent; Berthias, Francis; Feketeová, Linda; Abdoul-Carime, Hassan; Farizon, Bernadette; Farizon, Michel

2017-05-01

The evaporation of water molecules from high-velocity argon atoms impinging on protonated water clusters has been computationally investigated using molecular dynamics simulations with the reactive OSS2 potential to model water clusters and the ZBL pair potential to represent their interaction with the projectile. Swarms of trajectories and an event-by-event analysis reveal the conditions under which a specific number of molecular evaporation events is found one nanosecond after impact, thereby excluding direct knockout events from the analysis. These simulations provide velocity distributions that exhibit two main features, with a major statistical component arising from a global redistribution of the collision energy into intermolecular degrees of freedom, and another minor but non-ergodic feature at high velocities. The latter feature is produced by direct impacts on the peripheral water molecules and reflects a more complete momentum transfer. These two components are consistent with recent experimental measurements and confirm that electronic processes are not explicitly needed to explain the observed non-ergodic behavior. Contribution to the Topical Issue "Dynamics of Systems at the Nanoscale", edited by Andrey Solov'yov and Andrei Korol.

High-Sensitivity, Broad-Range Vacuum Gauge Using Nanotubes for Micromachined Cavities

NASA Technical Reports Server (NTRS)

Manohara, Harish; Kaul, Anupama B.

2011-01-01

A broad-range vacuum gauge has been created by suspending a single-walled carbon nanotube (SWNT) (metallic or semiconducting) in a Schottky diode format or in a bridge conductor format, between two electrically charged mesas. SWNTs are highly sensitive to molecular collisions because of their extremely small diameters in the range of 1 to 3 nanometers. The measurement parameter will be the change in conductivity of SWNT due to decreasing rate of molecular collisions as the pressure inside a chamber decreases. The rate of heat removal approaches a saturation limit as the mean free path (m.f.p.) lengths of molecules increase due to decreasing pressure. Only those sensing elements that have a long relaxation time can produce a measureable response when m.f.p. of molecules increases (or time between two consecutive collisions increases). A suspended SWNT offers such a capability because of its one-dimensional nature and ultrasmall diameter. In the initial approach, similar architecture was used as that of a SWNT-Schottky diode that has been developed at JPL, and has its changing conductivity measured as the test chamber is pumped down from atmospheric pressure to high vacuum (10(exp -7) Torr). Continuous response of decreasing conductivity has been measured as a function of decreasing pressure (SWNT is a negative thermal coefficient material) from atmosphere to less than 10(exp -6) Torr. A measureable current change in the hundreds of nA range has been recorded in the 10(exp -6) Torr regime.

Influence of instrumental parameters on the kinetic energy of ions and plasma temperature for a hexapole collision/reaction-cell-based inductively coupled plasma quadrupole mass spectrometer.

PubMed

Favre, Georges; Brennetot, René; Chartier, Frédéric; Tortajada, Jeanine

2009-02-01

Inductively coupled plasma mass spectrometry (ICP-MS) is widely used in inorganic analytical chemistry for element and/or isotope ratio measurements. The presence of interferences, which is one of the main limitations of this method, has been addressed in recent years with the introduction of collision/reaction cell devices on ICP-MS apparatus. The study of ion-molecule reactions in the gas phase then became of great importance for the development of new analytical strategies. Knowing the kinetic energy and the electronic states of the ions prior to their entrance into the cell, i.e., just before they react, thereby constitutes crucial information for the interpretation of the observed reactivities. Such studies on an ICP-MS commonly used for routine analyses require the determination of the influence of different instrumental parameters on the energy of the ions and on the plasma temperature from where ions are sampled. The kinetic energy of ions prior to their entrance into the cell has been connected to the voltage applied to the hexapole according to a linear relationship determined from measurements of ion energy losses due to collisions with neutral gas molecules. The effects of the plasma forward power, sampling depth, and the addition of a torch shield to the ICP source were then examined. A decrease of the plasma potential due to the torch shielding, already mentioned in the literature, has been quantified in this study at about 3 V.

Production of cold beams of ND{sub 3} with variable rotational state distributions by electrostatic extraction of He and Ne buffer-gas-cooled beams

DOE Office of Scientific and Technical Information (OSTI.GOV)

Twyman, Kathryn S.; Bell, Martin T.; Heazlewood, Brianna R.

2014-07-14

The measurement of the rotational state distribution of a velocity-selected, buffer-gas-cooled beam of ND{sub 3} is described. In an apparatus recently constructed to study cold ion-molecule collisions, the ND{sub 3} beam is extracted from a cryogenically cooled buffer-gas cell using a 2.15 m long electrostatic quadrupole guide with three 90° bends. (2+1) resonance enhanced multiphoton ionization spectra of molecules exiting the guide show that beams of ND{sub 3} can be produced with rotational state populations corresponding to approximately T{sub rot} = 9–18 K, achieved through manipulation of the temperature of the buffer-gas cell (operated at 6 K or 17 K),more » the identity of the buffer gas (He or Ne), or the relative densities of the buffer gas and ND{sub 3}. The translational temperature of the guided ND{sub 3} is found to be similar in a 6 K helium and 17 K neon buffer-gas cell (peak kinetic energies of 6.92(0.13) K and 5.90(0.01) K, respectively). The characterization of this cold-molecule source provides an opportunity for the first experimental investigations into the rotational dependence of reaction cross sections in low temperature collisions.« less

Theoretical study of the vibrational relaxation of the methyl radical in collisions with helium

NASA Astrophysics Data System (ADS)

Ma, Qianli; Dagdigian, Paul J.; Alexander, Millard H.

2013-03-01

We report a theoretical investigation of the relaxation of the umbrella vibrational mode (the ν2 mode) of the CH3 molecule in its ground tilde{X}^2A_2^' ' } electronic state in collisions with helium. We have calculated a four-dimensional potential energy surface (PES) for the interaction between CH3 with different umbrella displacements and a helium atom, using a restricted open-shell coupled-cluster method with inclusion of all single, double, and (perturbatively) triple excitations [RCCSD(T)]. With this PES we carried out full close-coupling scattering calculations including all CH3 umbrella-rotational levels with v2 ⩽ 3. To our knowledge, this work represents the first fully quantum calculations of ro-vibrational relaxation of a polyatomic. In more detail, we investigate propensities in the calculated ro-vibrational cross sections and the dependence on initial rotational excitation, as well as determining thermal rate constants. Overall, ro-vibrational relaxation is nearly two orders of magnitude less efficient than pure-rotational relaxation, with a noticeable dependence on the initial rotational level. We predict the room temperature v2 = 1 vibrational relaxation rate constant to be 5.4 × 10-12 cm3 molecule-1 s-1, compared to the rate constants for pure-rotational relaxation of the lower rotational levels (˜2.0 × 10-10 cm3 molecule-1 s-1).

Absolute cross section measurements for the scattering of low- and intermediate-energy electrons from PF3. I. Elastic scattering

NASA Astrophysics Data System (ADS)

Hishiyama, N.; Hoshino, M.; Blanco, F.; García, G.; Tanaka, H.

2017-12-01

We report absolute elastic differential cross sections (DCSs) for electron collisions with phosphorus trifluoride, PF3, molecules (e- + PF3) in the impact energy range of 2.0-200 eV and over a scattering angle range of 10°-150°. Measured angular distributions of scattered electron intensities were normalized by reference to the elastic DCSs of He. Corresponding integral and momentum-transfer cross sections were derived by extrapolating the angular range from 0° to 180° with the help of a modified phase-shift analysis. In addition, due to the large dipole moment of the considered molecule, the dipole-Born correction for the forward scattering angles has also been applied. As a part of this study, independent atom model calculations in combination with screening corrected additivity rule were also performed for elastic and inelastic (electronic excitation plus ionization) scattering using a complex optical potential method. Rotational excitation cross sections have been estimated with a dipole-Born approximation procedure. Vibrational excitations are not considered in this calculation. Theoretical data, at the differential and integral levels, were found to reasonably agree with the present experimental results. Furthermore, we explore the systematics of the elastic DCSs for the four-atomic trifluoride molecules of XF3 (X = B, N, and P) and central P-atom in PF3, showing that, owing to the comparatively small effect of the F-atoms, the present angular distributions of elastic DCSs are essentially dominated by the characteristic of the central P-atom at lower impact energies. Finally, these quantitative results for e- - PF3 collisions were compiled together with the previous data available in the literature in order to obtain a cross section dataset for modeling purposes. To comprehensively describe such a considerable amount of data, we proceed by first discussing, in this paper, the vibrationally elastic scattering processes whereas vibrational and electronic excitation shall be the subject of our following paper devoted to inelastic collisions.

Determination of the structure of the X(3872) in p¯A collisions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Larionov, A. B.; Strikman, M.; Bleicher, M.

2015-07-22

The structure of the X(3872) meson is unknown. Different competing models of the cc¯ exotic state X(3872) exist, including the possibilities that this state is either a mesonic molecule with dominating D 0D¯* 0 + c.c. composition, a cc¯qq¯ tetraquark, or a cc¯-gluon hybrid state. It is expected that the X(3872) state is rather strongly coupled to the pp¯ channel and, therefore, can be produced in pp¯ and p¯A collisions at PANDA. We propose to test the hypothetical molecular structure of X(3872) by studying the D or D¯* source stripping reactions on a nuclear residue.

Accuracy of Hartree-Fock wave functions for electron-H/sub 2/ scattering calculations

DOE Office of Scientific and Technical Information (OSTI.GOV)

Feldt, A.N.

1988-05-01

Recent papers on electron-N/sub 2/ scattering by Rumble, Stevens, and Truhlar (J. Phys. B 17, 3151 (1984)) and Weatherford, Brown, and Temkin (Phys. Rev. A 35, 4561 (1987)) have suggested that Hartree-Fock (HF) wave functions may not be accurate for calculating potentials for use in studying electron-molecule collisions. A comparison of results for electron-H/sub 2/ scattering using both correlated and HF wave functions is presented. It is found that for both elastic and inelastic collisions and for all energies considered (up to 10 eV) the HF wave functions yield results in excellent agreement with those obtained from the more accuratemore » wave functions.« less

Infrared line parameters at low temperatures relevant to planetary atmospheres

NASA Technical Reports Server (NTRS)

Varanasi, Prasad

1990-01-01

Employing the techniques that were described in several publications for measuring infrared lineshifts, linewidths and line intensities with a tunable diode laser, these parameters were measures for lines in the important infrared bands of several molecules of interest to the planetary astronomer at low temperatures that are relevant to planetary atmospheres using He, Ne, Ar, H2, N2, O2, and air as the perturbers. In addition to obtaining the many original data on the temperature dependence of the intensities and linewidths, it was also the first measurement of the same for the collision-induced lineshift of an infrared line and it showed that it was markedly different from that of the corresponding collision-broadened linewidth.

Effect of multiple plasmon excitation on single, double and multiple ionizations of C60 in collisions with fast highly charged Si ions

NASA Astrophysics Data System (ADS)

Kelkar, A. H.; Kadhane, U.; Misra, D.; Kumar, A.; Tribedi, L. C.

2007-06-01

We have investigated the single and multiple ionizations of the C60 molecule in collisions with fast Siq+ projectiles for various projectile charge states (q) between q = 6 and 14. The q-dependence of the ionization cross sections and their ratios is compared with the giant dipole plasmon resonance (GDPR) model. The excellent qualitative agreement with the model in case of single and double ionizations and also a reasonable agreement with the triple (and to some extent with quadruple) ionization (without evaporation) yields signify dominant contributions of the single-, double- and triple-plasmon excitations on the single- and multiple-ionization process.

Measurement of partial pressures in vacuum technology and vacuum physics

NASA Technical Reports Server (NTRS)

Huber, W. K.

1986-01-01

It is pointed out that the measurement of gaseous pressures of less than 0.0001 torr is based on the ionization of gas atoms and molecules due to collisions with electrons. The particle density is determined in place of the pressure. The ionization cross sections for molecules of various gases are discussed. It is found that the true pressure in a vacuum system cannot be determined with certainty if it is unknown which gas is present. Effects of partial pressure determination on the condition of the vacuum system are discussed together with ion sources, systems of separation, and ion detection.

Laser cooling of BaF

NASA Astrophysics Data System (ADS)

Bo, Yan; Bu, Wenhao; Chen, Tao; Lv, Guitao

2017-04-01

In this poster, we report our recently experimental progresses in laser cooling of BaF molecule. Our theoretic calculation shows BaF is a good candidate for laser cooling: quasi-cycling transitions, good wavelengths (around 900nm) for the main transitions. We have built a 4K cryogenic machine, laser ablate the target to make BaF molecules. The precise spectroscopy of BaF is measured and the laser cooling related transitions are identified. The collision between BaF and 4K He is carefully characterized. The quasi-cycling transition is demonstrated. And laser cooling experiment is going on.

Continuous-Time Random Walk Models of DNA Electrophoresis in a Post Array: II. Mobility and Sources of Band Broadening

PubMed Central

Olson, Daniel W.; Dutta, Sarit; Laachi, Nabil; Tian, Mingwei; Dorfman, Kevin D.

2011-01-01

Using the two-state, continuous-time random walk model, we develop expressions for the mobility and the plate height during DNA electrophoresis in an ordered post array that delineate the contributions due to (i) the random distance between collisions and (ii) the random duration of a collision. These contributions are expressed in terms of the means and variances of the underlying stochastic processes, which we evaluate from a large ensemble of Brownian dynamics simulations performed using different electric fields and molecular weights in a hexagonal array of 1 μm posts with a 3 μm center-to-center distance. If we fix the molecular weight, we find that the collision frequency governs the mobility. In contrast, the average collision duration is the most important factor for predicting the mobility as a function of DNA size at constant Péclet number. The plate height is reasonably well-described by a single post rope-over-pulley model, provided that the extension of the molecule is small. Our results only account for dispersion inside the post array and thus represent a theoretical lower bound on the plate height in an actual device. PMID:21290387

State selected ion--molecule reactions by a TESICO technique. V. N/sub 2//sup +/(v)+Ar. -->. N/sub 2/+Ar/sup +/

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kato, T.; Tanaka, K.; Koyano, I.

1982-07-15

Charge transfer reactions N/sub 2//sup +/(v)+Ar..-->..Ar/sup +/+N/sub 2/ (1) have been studied by selecting the vibrational states of N/sub 2//sup +/ using the threshold electron--secondary ion coincidence (TESICO) technique. Relative cross sections sigma(v) for the individual vibrational states v = 0--3 have been determined at three collision energies, 0.3, 1.5, and 11.8 eV. Results show that Reaction (1), which is endoergic for v = 0, is considerably enhanced by the vibrational excitation of N/sub 2//sup +/ at all collision energies. While excitation of one vibrational quantum enhances the cross section substantially, excitation of additional quanta further increases the cross sectionmore » up to v = 3. The ratios sigma(2)/sigma(1) and sigma(3)/sigma(2) are, however, much smaller than sigma(1)/sigma(0) and are significantly larger at the highest collision energy than at the other two collision energies. These results are discussed in conjunction with the calculated results based on the simple two-state theory of Rapp and Francis and the Franck--Condon factors.« less

Building one molecule from a reservoir of two atoms.

PubMed

Liu, L R; Hood, J D; Yu, Y; Zhang, J T; Hutzler, N R; Rosenband, T; Ni, K-K

2018-05-25

Chemical reactions typically proceed via stochastic encounters between reactants. Going beyond this paradigm, we combined exactly two atoms in a single, controlled reaction. The experimental apparatus traps two individual laser-cooled atoms [one sodium (Na) and one cesium (Cs)] in separate optical tweezers and then merges them into one optical dipole trap. Subsequently, photoassociation forms an excited-state NaCs molecule. The discovery of previously unseen resonances near the molecular dissociation threshold and measurement of collision rates are enabled by the tightly trapped ultracold sample of atoms. As laser-cooling and trapping capabilities are extended to more elements, the technique will enable the study of more diverse, and eventually more complex, molecules in an isolated environment, as well as synthesis of designer molecules for qubits. Copyright © 2018 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.

An advanced molecule-surface scattering instrument for study of vibrational energy transfer in gas-solid collisions.

PubMed

Ran, Qin; Matsiev, Daniel; Wodtke, Alec M; Auerbach, Daniel J

2007-10-01

We describe an advanced and highly sensitive instrument for quantum state-resolved molecule-surface energy transfer studies under ultrahigh vacuum (UHV) conditions. The apparatus includes a beam source chamber, two differential pumping chambers, and a UHV chamber for surface preparation, surface characterization, and molecular beam scattering. Pulsed and collimated supersonic molecular beams are generated by expanding target molecule mixtures through a home-built pulsed nozzle, and excited quantum state-selected molecules were prepared via tunable, narrow-band laser overtone pumping. Detection systems have been designed to measure specific vibrational-rotational state, time-of-flight, angular and velocity distributions of molecular beams coming to and scattered off the surface. Facilities are provided to clean and characterize the surface under UHV conditions. Initial experiments on the scattering of HCl(v = 0) from Au(111) show many advantages of this new instrument for fundamental studies of the energy transfer at the gas-surface interface.

Dissipation dynamics of field-free molecular alignment for symmetric-top molecules: Ethane (C2H6)

NASA Astrophysics Data System (ADS)

Zhang, H.; Billard, F.; Yu, X.; Faucher, O.; Lavorel, B.

2018-03-01

The field-free molecular alignment of symmetric-top molecules, ethane, induced by intense non-resonant linearly polarized femtosecond laser pulses is investigated experimentally in the presence of collisional relaxation. The dissipation dynamics of field-free molecular alignment are measured by the balanced detection of ultrafast molecular birefringence of ethane gas samples at high pressures. By separating the molecular alignment into the permanent alignment and the transient alignment, the decay time-constants of both components are quantified at the same pressure. It is observed that the permanent alignment always decays slower compared to the transient alignment within the measured pressure range. This demonstrates that the propensity of molecules to conserve the orientation of angular momentum during collisions, previously observed for linear species, is also applicable to symmetric-top molecules. The results of this work provide valuable information for further theoretical understanding of collisional relaxation within nonlinear polyatomic molecules, which are expected to present interesting and nontrivial features due to an extra rotational degree of freedom.

Roto-translational Raman spectra of pairs of hydrogen molecules from first principles.

PubMed

Gustafsson, Magnus; Frommhold, Lothar; Li, Xiaoping; Hunt, K L C

2009-04-28

We calculate the collision-induced, roto-translational, polarized, and depolarized Raman spectra of pairs of H(2) molecules. The Schrodinger equation of H(2)-H(2) scattering in the presence of a weak radiation field is integrated in the close-coupled scheme. This permits the accounting for the anisotropy of the intermolecular potential energy surface and thereby it includes mixing of polarizability components. The static polarizability invariants, trace and anisotropy, of two interacting H(2) molecules were obtained elsewhere [Li et al., J. Chem. Phys. 126, 214302 (2007)] from first principles. Here we report the associated spherical tensor components which, along with the potential surface, are input in the calculation of the supramolecular Raman spectra. Special attention is paid to the interferences in the wings of the rotational S(0)(0) and S(0)(1) lines of the H(2) molecule. The calculated Raman pair spectra show reasonable consistency with existing measurements of the polarized and depolarized Raman spectra of pairs of H(2) molecules.

Gas-phase hydrogen atom abstraction reactions of S- with H2, CH4, and C2H6

NASA Astrophysics Data System (ADS)

Angel, Laurence A.; Dogbevia, Moses K.; Rempala, Katarzyna M.; Ervin, Kent M.

2003-11-01

Reaction cross sections, product axial velocity distributions, and potential energy surfaces are presented for the hydrogen atom abstraction reactions S-+RH→R+HS- (R=H, CH3, C2H5) as a function of collision energy. The observed threshold energy, E0, for S-+H2→H+HS- agrees with the reaction endothermicity, ΔrH0. At low collision energies, the H+HS- products exhibit symmetric, low-recoil-velocity scattering, consistent with statistical reaction behavior. The S-+CH4→CH3+HS- and S-+C2H6→C2H5+HS reactions, in contrast, show large excess threshold energies when compared to ΔrH0. The excess energies are partly explained by a potential energy barrier separating products from reactants. However, additional dynamical constraints must account for more than half of the excess threshold energy. The observed behavior seems to be general for collisional activation of anion-molecule reactions that proceed through a tight, late transition state. For RH=CH4 and C2H6, the HS- velocity distributions show anisotropic backward scattering at low collision energies indicating small impact parameters and a direct rebound reaction mechanism. At higher collision energies, there is a transition to HS- forward scattering and high velocities consistent with grazing collisions and a stripping mechanism.

Solution of the Wang Chang-Uhlenbeck equation for molecular hydrogen

NASA Astrophysics Data System (ADS)

Anikin, Yu. A.

2017-06-01

Molecular hydrogen is modeled by numerically solving the Wang Chang-Uhlenbeck equation. The differential scattering cross sections of molecules are calculated using the quantum mechanical scattering theory of rigid rotors. The collision integral is computed by applying a fully conservative projection method. Numerical results for relaxation, heat conduction, and a one-dimensional shock wave are presented.

Crossed Molecular Beam Studies and Dynamics of Decomposition of Chemically Activated Radicals

DOE R&D Accomplishments Database

Lee, Y. T.

1973-09-01

The power of the crossed molecular beams method in the investigation of the dynamics of chemical reactions lies mainly in the direct observation of the consequences of single collisions of well controlled reactant molecules. The primary experimental observations which provide information on reaction dynamics are the measurements of angular and velocity distributions of reaction products.

Extracting conformational structure information of benzene molecules via laser-induced electron diffraction

DOE PAGES

Ito, Yuta; Wang, Chuncheng; Le, Anh-Thu; ...

2016-05-01

Here, we have measured the angular distributions of high energy photoelectrons of benzene molecules generated by intense infrared femtosecond laser pulses. These electrons arise from the elastic collisions between the benzene ions with the previously tunnel-ionized electrons that have been driven back by the laser field. Theory shows that laser-free elastic differential cross sections (DCSs) can be extracted from these photoelectrons, and the DCS can be used to retrieve the bond lengths of gas-phase molecules similar to the conventional electron diffraction method. From our experimental results, we have obtained the C-C and C-H bond lengths of benzene with a spatialmore » resolution of about 10 pm. Our results demonstrate that laser induced electron diffraction (LIED) experiments can be carried out with the present-day ultrafast intense lasers already. Looking ahead, with aligned or oriented molecules, more complete spatial information of the molecule can be obtained from LIED, and applying LIED to probe photo-excited molecules, a “molecular movie” of the dynamic system may be created with sub-A°ngstrom spatial and few-ten femtosecond temporal resolutions.« less

The bound states of ultracold KRb molecules

NASA Astrophysics Data System (ADS)

Julienne, Paul; Hanna, Thomas

2009-03-01

Recently ultracold vibrational ground state ^40K^87Rb polar molecules have been made using magnetoassociation of two cold atoms to a weakly bound Feshbach molecule, followed by a two-color optical STIRAP process to transfer molecules to the molecular ground state [1]. We have used accurate potential energy curves for the singlet and triplet states of the KRb molecule [2] with coupled channels calculations to calculate all of the bound states of the ^40K^87Rb molecule as a function of magnetic field from the cold atom collision threshold to the v=0 ground state. We have also developed approximate models for understanding the changing properties of the molecular bound states as binding energy increases. Some overall conclusions from these calculations will be presented. [1] K.-K. Ni, S. Ospelkaus, M. H. G. de Miranda, A. Peer, B. Neyenhuis, J. J. Zirbel, S. Kotochigova, P. S. Julienne, D. S. Jin, and J. Ye, Science, 2008, 322, 231--235. [2] A. Pashov, O. Docenko, M. Tamanis, R. Ferber, H. Kn"ockel, and E. Tiemann, Phys. Rev. A, 2007, 76, 022511.

Optoelectrical Cooling of Formaldehyde to Sub-Millikelvin Temperatures

NASA Astrophysics Data System (ADS)

Zeppenfeld, Martin

2016-05-01

Due to their strong long-range dipole-dipole interactions and large number of internal states, polar molecules cooled to ultracold temperatures enable fascinating applications ranging from ultracold chemistry to investigation of dipolar quantum gases. However, realizing a simple and general technique to cool molecules to ultracold temperatures, akin to laser cooling of atoms, has been a formidable challenge. We present results for opto-electrical Sisyphus cooling applied to formaldehyde (H2 CO). In this generally applicable cooling scheme, molecules repeatedly move up and down electric field gradients of a trapping potential in different rotational states to efficiently extract kinetic energy. A total of about 300,000 molecules are thereby cooled by a factor of 1000 to 400uK, resulting in a record-large ensemble of ultracold molecules. In addition to cooling of the motional degrees of freedom, optical pumping via a vibrational transition allows us to control the internal rotational state. We thereby achieve a purity of over 80% of formaldehyde molecules in a single rotational M-sublevel. Our experiment provides an excellent starting point for precision spectroscopy and investigation of ultracold collisions.

Collision cross sections of N2 by H+ impact at keV energies within time-dependent density-functional theory

NASA Astrophysics Data System (ADS)

Yu, W.; Gao, C.-Z.; Zhang, Y.; Zhang, F. S.; Hutton, R.; Zou, Y.; Wei, B.

2018-03-01

We calculate electron capture and ionization cross sections of N2 impacted by the H+ projectile at keV energies. To this end, we employ the time-dependent density-functional theory coupled nonadiabatically to molecular dynamics. To avoid the explicit treatment of the complex density matrix in the calculation of cross sections, we propose an approximate method based on the assumption of constant ionization rate over the period of the projectile passing the absorbing boundary. Our results agree reasonably well with experimental data and semi-empirical results within the measurement uncertainties in the considered energy range. The discrepancies are mainly attributed to the inadequate description of exchange-correlation functional and the crude approximation for constant ionization rate. Although the present approach does not predict the experiments quantitatively for collision energies below 10 keV, it is still helpful to calculate total cross sections of ion-molecule collisions within a certain energy range.

Fine-structure resolved rotational transitions and database for CN+H2 collisions

NASA Astrophysics Data System (ADS)

Burton, Hannah; Mysliwiec, Ryan; Forrey, Robert C.; Yang, B. H.; Stancil, P. C.; Balakrishnan, N.

2018-06-01

Cross sections and rate coefficients for CN+H2 collisions are calculated using the coupled states (CS) approximation. The calculations are benchmarked against more accurate close-coupling (CC) calculations for transitions between low-lying rotational states. Comparisons are made between the two formulations for collision energies greater than 10 cm-1. The CS approximation is used to construct a database which includes highly excited rotational states that are beyond the practical limitations of the CC method. The database includes fine-structure resolved rotational quenching transitions for v = 0 and j ≤ 40, where v and j are the vibrational and rotational quantum numbers of the initial state of the CN molecule. Rate coefficients are computed for both para-H2 and ortho-H2 colliders. The results are shown to be in good agreement with previous calculations, however, the rates are substantially different from mass-scaled CN+He rates that are often used in astrophysical models.

Quenching of internally 'hot' H2 and N2 gases by collisions with ultracold electrons: a computational 'experiment'

NASA Astrophysics Data System (ADS)

Gianturco, F. A.

2008-11-01

Quantum mechanical methods are employed to obtain superelastic cross sections involving H2 and N2 molecules, in excited rotational states, colliding with electrons at the very low collision energies which are encountered in cold trap experiments. This computational analysis intends to explore the feasibility of cold electrons for the collisional quenching of molecular gases down to the nanokelvin regimes. The results are obtained using rigorous coupled-channel (CC) calculations in the laboratory frame of reference which allows one to correctly describe the cross section behaviour at ultralow energies. The results are analysed down to the ultracold region of validity of Wigner's law, where it is found that electron-driven collisions exhibit substantial efficiency for the quenching of rotational populations in molecular gases involving the title systems. This work is affectionately dedicated to Anna Giardini, a creative experimentalist and a long-time friend, on the occasion of her 'official' retirement.

The thermochromic behavior of aromatic amine-SO2 charge transfer complexes

NASA Astrophysics Data System (ADS)

Monezi, Natália M.; Borin, Antonio C.; Santos, Paulo S.; Ando, Rômulo A.

2017-02-01

The distinct thermochromism observed in solutions containing N,N-dimethylaniline (DMA) and N,N-diethylaniline (DEA) and SO2 was investigated by resonance Raman spectroscopy in a wide range of temperatures. The results indicate in addition to the charge transfer (CT) complexes DMA-SO2 and DEA-SO2, the presence of collision complexes involving the CT complexes and excess DMA and DEA molecules. The latter in fact is the chromophore responsible for the long wavelength absorption originating the color. The Raman signature of the collision complex was attributed to the distinct enhancement of a band at 1140 cm- 1 assigned to νs(SO2), in contrast to the same mode in the 1:1 complex at 1115 cm- 1. The intensity of such band, assigned to the collision complex is favored at high temperatures and depends on the steric hindrance associated to amines, as well as the SO2 molar fraction. Quantum chemical calculations based on time-dependent density functional theory (TDDFT) support the proposed interpretation.

Charge Transfer Dissociation of Complex Oligosaccharides: Comparison with Collision-Induced Dissociation and Extreme Ultraviolet Dissociative Photoionization

NASA Astrophysics Data System (ADS)

Ropartz, David; Li, Pengfei; Fanuel, Mathieu; Giuliani, Alexandre; Rogniaux, Hélène; Jackson, Glen P.

2016-10-01

The structural characterization of oligosaccharides still challenges the field of analytical chemistry. Tandem mass spectrometry offers many advantages toward this aim, although the generic fragmentation method (low-energy collision-induced dissociation) shows clear limitations and is often insufficient to retrieve some essential structural information on these molecules. In this work, we present the first application of helium charge transfer dissociation (He-CTD) to characterize the structure of complex oligosaccharides. We compare this method with low-energy collision-induced dissociation and extreme-ultraviolet dissociative photoionization (XUV-DPI), which was shown previously to ensure the successful characterization of complex glycans. Similarly to what could be obtained by XUV-DPI, He-CTD provides a complete description of the investigated structures by producing many informative cross-ring fragments and no ambiguous fragmentation. Unlike XUV-DPI, which is performed at a synchrotron source, He-CTD has the undeniable advantage of being implementable in a conventional benchtop ion trap in a conventional laboratory setting.

Theory of low-energy electron-molecule collision physics in the coupled-channel method and application to e-CO/sub 2/ scattering. [0. 01 to 10 eV, potentials, partial waves

DOE Office of Scientific and Technical Information (OSTI.GOV)

Morrison, M.A.

1976-08-01

A theory of electron-molecule scattering based on the fixed-nuclei approximation in a body-fixed reference frame is formulated and applied to e-CO/sub 2/ collisions in the energy range from 0.07 to 10.0 eV. The procedure used is a single-center coupled-channel method which incorporates a highly accurate static interaction potential, an approximate local exchange potential, and an induced polarization potential. Coupled equations are solved by a modification of the integral equations algorithm; several partial waves are required in the region of space near the nuclei, and a transformation procedure is developed to handle the consequent numerical problems. The potential energy is convergedmore » by separating electronic and nuclear contributions in a Legendre-polynomial expansion and including a large number of the latter. Formulas are derived for total elastic, differential, momentum transfer, and rotational excitation cross sections. The Born and asymptotic decoupling approximations are derived and discussed in the context of comparison with the coupled-channel cross sections. Both are found to be unsatisfactory in the energy range under consideration. An extensive discussion of the technical aspects of calculations for electron collisions with highly nonspherical targets is presented, including detailed convergence studies and a discussion of various numerical difficulties. The application to e-CO/sub 2/ scattering produces converged results in good agreement with observed cross sections. Various aspects of the physics of this collision are discussed, including the 3.8 eV shape resonance, which is found to possess both p and f character, and the anomalously large low-energy momentum transfer cross sections, which are found to be due to ..sigma../sub g/ symmetry. Comparison with static and static-exchange approximations are made.« less

Linewidth and lineshift parameters of rotation-vibration transitions of linear molecule perturbed by inert gas

NASA Astrophysics Data System (ADS)

Johri, Manoj; Johri, Gajendra K.; Rishishwar, Rajendra P.

1990-12-01

The study of spectral lineshape is important to understand intermolecular forces1-5. We have calculated the linewidth and the lineshift for different rotation-vibration transitions of linear molecules (CO and HCl) perturbed by argon using generalized interaction potential4. The Murphy Boggs6 (MB), Mehrotra Boggs7 and perturbation theories have been used for the linewidth calculation. The lineshift parameters have been calculated using the MEB theory7 including the phase shift effect and ignoring Ji=Ji and Jf=Jf transitions. In these calculation the variation of the rotational constant with the vibrational quantum number has been taken into account. The calculated lineshift parameters decrease with an increase in the initial rotation quamtum numbers (Ji). It remains positive for the lower values of Ji and becomes negative for the higher values of Ji where as the measured8 values are negative for all the transitions. The calculated linewidth parameters using the MEB theory7 are lower by about 15% than the measured values for CO-A collisions. The vibrational dependence in CO-A collisions show significant change in the lineshift. For H Cl-A collisions the discrepancy between the calculated lienwidth parameters using the Mehrotra Boggs theory and the measured9 values is about 46% for J=0-1 transitions and decreases to 22% for J=8-9 transition. The results of the perturbation theory do not show regular variation of the linewidth parameters with the rotational state. The linewidth parameters using the Murphy Boggs theory are lower than the measured9 values by about 50% for all the transitions considered. It is found that the contribution of the diabetic collisions is important as included in the perturbtive and the Mehrotra Boggs approaches. Further, if the pressure broadening method is used to probe anisotropy of the intermolecular forces, there is need of modifying the existing theoretical models and the experimental techniques.

The quantum dynamics of electronically nonadiabatic chemical reactions

NASA Technical Reports Server (NTRS)

Truhlar, Donald G.

1993-01-01

Considerable progress was achieved on the quantum mechanical treatment of electronically nonadiabatic collisions involving energy transfer and chemical reaction in the collision of an electronically excited atom with a molecule. In the first step, a new diabatic representation for the coupled potential energy surfaces was created. A two-state diabatic representation was developed which was designed to realistically reproduce the two lowest adiabatic states of the valence bond model and also to have the following three desirable features: (1) it is more economical to evaluate; (2) it is more portable; and (3) all spline fits are replaced by analytic functions. The new representation consists of a set of two coupled diabatic potential energy surfaces plus a coupling surface. It is suitable for dynamics calculations on both the electronic quenching and reaction processes in collisions of Na(3p2p) with H2. The new two-state representation was obtained by a three-step process from a modified eight-state diatomics-in-molecules (DIM) representation of Blais. The second step required the development of new dynamical methods. A formalism was developed for treating reactions with very general basis functions including electronically excited states. Our formalism is based on the generalized Newton, scattered wave, and outgoing wave variational principles that were used previously for reactive collisions on a single potential energy surface, and it incorporates three new features: (1) the basis functions include electronic degrees of freedom, as required to treat reactions involving electronic excitation and two or more coupled potential energy surfaces; (2) the primitive electronic basis is assumed to be diabatic, and it is not assumed that it diagonalizes the electronic Hamiltonian even asymptotically; and (3) contracted basis functions for vibrational-rotational-orbital degrees of freedom are included in a very general way, similar to previous prescriptions for locally adiabatic functions in various quantum scattering algorithms.

Quantum Theory of (H,H{Sub 2}) Scattering: Approximate Treatments of Reactive Scattering

DOE R&D Accomplishments Database

Tang, K. T.; Karplus, M.

1970-10-01

A quantum mechanical study is made of reactive scattering in the (H, H{sub 2}) system. The problem is formulated in terms of a form of the distorted-wave Born approximation (DWBA) suitable for collisions in which all particles have finite mass. For certain incident energies, differential and total cross sections, as well as other attributes of the reactive collisions, (e.g. reaction configuration), are determined. Two limiting models in the DWBA formulation are compared; in one, the molecule is unperturbed by the incoming atom and in the other, the molecule adiabatically follows the incoming atom. For thermal incident energies and semi-empirical interaction potential employed, the adiabatic model seems to be more appropriate. Since the DWBA method is too complicated for a general study of the (H, H{sub 2}) reaction, a much simpler approximation method, the ?linear model? is developed. This model is very different in concept from treatments in which the three atoms are constrained to move on a line throughout the collision. The present model includes the full three-dimensional aspect of the collision and it is only the evaluation of the transition matrix element itself that is simplified. It is found that the linear model, when appropriately normalized, gives results in good agreement with that of the DWBA method. By application of this model, the energy dependence, rotational state of dependence and other properties of the total and differential reactions cross sections are determined. These results of the quantum mechanical treatment are compared with the classical calculation for the same potential surface. The most important result is that, in agreement with the classical treatment, the differential cross sections are strongly backward peaked at low energies and shifts in the forward direction as the energy increases. Finally, the implications of the present calculations for a theory of chemical kinetics are discussed.

Implementation of dipolar direct current (DDC) collision-induced dissociation in storage and transmission modes on a quadrupole/time-of-flight tandem mass spectrometer.

PubMed

Webb, Ian K; Londry, Frank A; McLuckey, Scott A

2011-09-15

Means for effecting dipolar direct current collision-induced dissociation (DDC CID) on a quadrupole/time-of-flight in a mass spectrometer have been implemented for the broadband dissociation of a wide range of analyte ions. The DDC fragmentation method in electrodynamic storage and transmission devices provides a means for inducing fragmentation of ions over a large mass-to-charge range simultaneously. It can be effected within an ion storage step in a quadrupole collision cell that is operated as a linear ion trap or as ions are continuously transmitted through the collision cell. A DDC potential is applied across one pair of rods in the quadrupole collision cell of a QqTOF hybrid mass spectrometer to effect fragmentation. In this study, ions derived from a small drug molecule, a model peptide, a small protein, and an oligonucleotide were subjected to the DDC CID method in either an ion trapping or an ion transmission mode (or both). Several key experimental parameters that affect DDC CID results, such as time, voltage, low mass cutoff, and bath gas pressure, are illustrated with protonated leucine enkephalin. The DDC CID dissociation method gives a readily tunable, broadband tool for probing the primary structures of a wide range of analyte ions. The method provides an alternative to the narrow resonance conditions of conventional ion trap CID and it can access more extensive sequential fragmentation, depending upon conditions. The DDC CID approach constitutes a collision analog to infrared multiphoton dissociation (IRMPD). Copyright © 2011 John Wiley & Sons, Ltd.

Internal state control of a dense sample of ultracold 23Na87Rb molecules

NASA Astrophysics Data System (ADS)

Ye, Xin; Guo, Mingyang; He, Junyu; Wang, Dajun; Quemener, Goulven; Gonzalez-Martinez, Maykel; Dulieu, Oliver

2017-04-01

We report the optimized production of ultracold 23Na87Rb molecules with completely controlled population distribution among internal states. Starting from a sample of 104 weakly bound Feshbach molecules, we achieved a hyperfine-structure-resolved STIRAP transfer to the ground state with an efficiency up to 95%. By tuning the frequency difference between the Raman lasers and applying an additional microwave signal, we realized the preparation of NaRb samples in different vibrational, rotational, and hyperfine levels. Based on this achievement, some results on molecular collisions with a range of possible loss channels will also be reported. This work was supported by the French ANR/Hong Kong RGC COPOMOL project (Grant No. A-CUHK403/13), the RGC General Research Fund (Grant No. CUHK14301815).

Gas-phase binding energies for non-covalent Aβ-40 peptide/small molecule complexes from CID mass spectrometry and RRKM theory.

PubMed

Mayer, Paul M; Martineau, Eric

2011-03-21

The gas-phase binding of small molecules to the Amyloid β-40 peptide generated by electrospray ionization has been explored with collision-induced dissociation mass spectrometry and kinetic rate theory. This study discusses a simple procedure used to theoretically model the experimental breakdown diagrams for the Aβ-40 peptide complexed with a series of aminosulfonate small molecules, namely homotaurine, 3-cyclohexylamino-2-hydroxy-1-propanesulfonic acid (CAPSO), 3-(1,3,4,9-tetrahydro-2H-β-carbolin-2-yl)propane-1-sulfonic acid, 3-(1,3,4,9-tetrahydro-2H-β-carbolin-2-yl)butane-1-sulfonic acid, and 3-(cyclohexylamino)propane-1-sulfonic acid. An alternative procedure employing an extrapolation procedure for k(E) is also discussed.

Efficient rotational cooling of Coulomb-crystallized molecular ions by a helium buffer gas.

PubMed

Hansen, A K; Versolato, O O; Kłosowski, L; Kristensen, S B; Gingell, A; Schwarz, M; Windberger, A; Ullrich, J; López-Urrutia, J R Crespo; Drewsen, M

2014-04-03

The preparation of cold molecules is of great importance in many contexts, such as fundamental physics investigations, high-resolution spectroscopy of complex molecules, cold chemistry and astrochemistry. One versatile and widely applied method to cool molecules is helium buffer-gas cooling in either a supersonic beam expansion or a cryogenic trap environment. Another more recent method applicable to trapped molecular ions relies on sympathetic translational cooling, through collisional interactions with co-trapped, laser-cooled atomic ions, into spatially ordered structures called Coulomb crystals, combined with laser-controlled internal-state preparation. Here we present experimental results on helium buffer-gas cooling of the rotational degrees of freedom of MgH(+) molecular ions, which have been trapped and sympathetically cooled in a cryogenic linear radio-frequency quadrupole trap. With helium collision rates of only about ten per second--that is, four to five orders of magnitude lower than in typical buffer-gas cooling settings--we have cooled a single molecular ion to a rotational temperature of 7.5(+0.9)(-0.7) kelvin, the lowest such temperature so far measured. In addition, by varying the shape of, or the number of atomic and molecular ions in, larger Coulomb crystals, or both, we have tuned the effective rotational temperature from about 7 kelvin to about 60 kelvin by changing the translational micromotion energy of the ions. The extremely low helium collision rate may allow for sympathetic sideband cooling of single molecular ions, and eventually make quantum-logic spectroscopy of buffer-gas-cooled molecular ions feasible. Furthermore, application of the present cooling scheme to complex molecular ions should enable single- or few-state manipulations of individual molecules of biological interest.

Ion mobility spectrometry-mass spectrometry examination of the structures, stabilities, and extents of hydration of dimethylamine-sulfuric acid clusters.

PubMed

Thomas, Jikku M; He, Siqin; Larriba-Andaluz, Carlos; DePalma, Joseph W; Johnston, Murray V; Hogan, Christopher J

2016-08-17

We applied an atmospheric pressure differential mobility analyzer (DMA) coupled to a time-of-flight mass spectrometer to examine the stability, mass-mobility relationship, and extent of hydration of dimethylamine-sulfuric acid cluster ions, which are of relevance to nucleation in ambient air. Cluster ions were generated by electrospray ionization and were of the form: [H((CH3)2NH)x(H2SO4)y](+) and [(HSO4)((CH3)2NH)x(H2SO4)y](-), where 4 ≤ x ≤ 8, and 5 ≤ y ≤ 12. Under dry conditions, we find that positively charged cluster ions dissociated via loss of both multiple dimethylamine and sulfuric acid molecules after mobility analysis but prior to mass analysis, and few parent ions were detected in the mass spectrometer. Dissociation also occurred for negative ions, but to a lesser extent than for positive ions for the same mass spectrometer inlet conditions. Under humidified conditions (relative humidities up to 30% in the DMA), positively charged cluster ion dissociation in the mass spectrometer inlet was mitigated and occurred primarily by H2SO4 loss from ions containing excess acid molecules. DMA measurements were used to infer collision cross sections (CCSs) for all identifiable cluster ions. Stokes-Millikan equation and diffuse/inelastic gas molecule scattering predicted CCSs overestimate measured CCSs by more than 15%, while elastic-specular collision model predictions are in good agreement with measurements. Finally, cluster ion hydration was examined by monitoring changes in CCSs with increasing relative humidity. All examined cluster ions showed a modest amount of water molecule adsorption, with percentage increases in CCS smaller than 10%. The extent of hydration correlates directly with cluster ion acidity for positive ions.

Measurements of trap dynamics of cold OH molecules using resonance-enhanced multiphoton ionization

NASA Astrophysics Data System (ADS)

Gray, John M.; Bossert, Jason A.; Shyur, Yomay; Lewandowski, H. J.

2017-08-01

Trapping cold, chemically important molecules with electromagnetic fields is a useful technique to study small molecules and their interactions. Traps provide long interaction times, which are needed to precisely examine these low-density molecular samples. However, the trapping fields lead to nonuniform molecular density distributions in these systems. Therefore, it is important to be able to experimentally characterize the spatial density distribution in the trap. Ionizing molecules at different locations in the trap using resonance-enhanced multiphoton ionization (REMPI) and detecting the resulting ions can be used to probe the density distribution even at the low density present in these experiments because of the extremely high efficiency of detection. Until recently, one of the most chemically important molecules, OH, did not have a convenient REMPI scheme identified. Here, we use a newly developed 1 +1' REMPI scheme to detect trapped cold OH molecules. We use this capability to measure the trap dynamics of the central density of the cloud and the density distribution. These types of measurements can be used to optimize loading of molecules into traps, as well as to help characterize the energy distribution, which is critical knowledge for interpreting molecular collision experiments.

What is measured by hyper-Rayleigh scattering from a liquid?

NASA Astrophysics Data System (ADS)

Rodriquez, Micheal B.; Shelton, David P.

2018-04-01

Polarization and angle dependence of hyper-Rayleigh scattering (HRS) measured for liquid acetonitrile and dimethyl sulfoxide (DMSO) is analyzed in terms of contributions from randomly oriented molecules and additional contributions produced during intermolecular collisions and induced by the electric field of dissolved ions. All three contributions show the effect of long-range correlation, and the correlation functions are determined using the HRS observations combined with the results of molecular dynamics simulations. HRS from acetonitrile is polarized transverse to the scattering vector. This is due to long-range molecular orientation correlation produced by the dipole-dipole interaction, and correlation at distances r > 100 nm must be included to account for the HRS observations. Analysis of the HRS measurements for acetonitrile determines the length scale a = 0.185 nm for the long-range longitudinal and transverse orientation correlation functions BL=-2 BT=a3/r3. Transverse polarized collision-induced HRS is also observed for acetonitrile, indicating long-range correlation of intermolecular modes. Strong longitudinal HRS is induced by the radial electric field of dissolved ions in acetonitrile. For DMSO, the angle between the molecular dipole and the vector part of the first hyperpolarizability tensor is about 100°. As a result, HRS from the randomly oriented molecules in DMSO is nearly unaffected by dipole correlation, and ion-induced HRS is weak. The strong longitudinal polarized HRS observed for DMSO is due to the collision-induced contribution, indicating long-range correlation of intermolecular modes. The HRS observations require correlation that has r-3 long-range asymptotic form, for molecular orientation and for intermolecular vibration and libration, for both acetonitrile and DMSO.

Cluster-collision frequency. I. The long-range intercluster potential

DOE Office of Scientific and Technical Information (OSTI.GOV)

Amadon, A.S.; Marlow, W.H.

1991-05-15

In recent years, gas-borne atomic and molecular clusters have emerged as subjects of basic physical and chemical interest and are gaining recognition for their importance in numerous applications. To calculate the evolution of the mass distribution of these clusters, their thermal collision rates are required. For computing these collision rates, the long-range interaction energy between clusters is required and is the subject of this paper. Utilizing a formulation of the iterated van der Waals interaction over discrete molecules that can be shown to converge with increasing numbers of atoms to the Lifshitz--van der Waals interaction for condensed matter, we calculatemore » the interaction energy as a function of center-of-mass separation for identical pairs of clusters of 13, 33, and 55 molecules of carbon tetrachloride in icosahedral and dodecahedral configurations. Two different relative orientations are chosen for each pair of clusters, and the energies are compared with energies calculated from the standard formula for continuum matter derived by summing over pair interactions with the Hamaker constant calculated according to Lifshitz theory. The results of these calculations give long-range interaction energies that assume typical adhesion-type values at cluster contact, unlike the unbounded results for the Lifshitz-Hamaker model. The relative difference between the discrete molecular energies and the continuum energies vanishes for {ital r}{sup *}{approx}2, where {ital r}{sup *} is the center-of-mass separation distance in units of cluster diameter. For larger separations, the relative difference changes sign, showing a value of approximately 15%, with the difference diminishing for increasing-sized clusters.« less

New rate coefficients of CS in collision with para- and ortho-H2 and astrophysical implications

NASA Astrophysics Data System (ADS)

Denis-Alpizar, Otoniel; Stoecklin, Thierry; Guilloteau, Stéphane; Dutrey, Anne

2018-05-01

Astronomers use the CS molecule as a gas mass tracer in dense regions of the interstellar medium, either to measure the gas density through multi-line observations or the level of turbulence. This necessarily requires the knowledge of the rates coefficients with the most common colliders in the interstellar medium, He and H2. In the present work, the close coupling collisional rates are computed for the first thirty rotational states of CS in collision with para- and ortho-H2 using a recent rigid rotor potential energy surface. Some radiative transfer calculations, using typical astrophysical conditions, are also performed to test this new set of data and to compare with the existing ones.

Determination of molecular spectroscopic parameters and energy-transfer rates by double-resonance spectroscopy

NASA Technical Reports Server (NTRS)

Steinfeld, J. I.; Foy, B.; Hetzler, J.; Flannery, C.; Klaassen, J.; Mizugai, Y.; Coy, S.

1990-01-01

The spectroscopy of small to medium-size polyatomic molecules can be extremely complex, especially in higher-lying overtone and combination vibrational levels. The high density of levels also complicates the understanding of inelastic collision processes, which is required to model energy transfer and collision broadening of spectral lines. Both of these problems can be addressed by double-resonance spectroscopy, i.e., time-resolved pump-probe measurements using microwave, infrared, near-infrared, and visible-wavelength sources. Information on excited-state spectroscopy, transition moments, inelastic energy transfer rates and propensity rules, and pressure-broadening parameters may be obtained from such experiments. Examples are given for several species of importance in planetary atmospheres, including ozone, silane, ethane, and ammonia.

A kinetic theory description of the viscosity of dense fluids consisting of chain molecules.

PubMed

de Wijn, Astrid S; Vesovic, Velisa; Jackson, George; Trusler, J P Martin

2008-05-28

An expression for the viscosity of a dense fluid is presented that includes the effect of molecular shape. The molecules of the fluid are approximated by chains of equal-sized, tangentially jointed, rigid spheres. It is assumed that the collision dynamics in such a fluid can be approximated by instantaneous collisions between two rigid spheres belonging to different chains. The approach is thus analogous to that of Enskog for a fluid consisting of rigid spheres. The description is developed in terms of two molecular parameters, the diameter sigma of the spherical segment and the chain length (number of segments) m. It is demonstrated that an analysis of viscosity data of a particular pure fluid alone cannot be used to obtain independently effective values of both sigma and m. Nevertheless, the chain lengths of n-alkanes are determined by assuming that the diameter of each rigid sphere making up the chain can be represented by the diameter of a methane molecule. The effective chain lengths of n-alkanes are found to increase linearly with the number C of carbon atoms present. The dependence can be approximated by a simple relationship m=1+(C-1)3. The same relationship was reported within the context of a statistical associating fluid theory equation of state treatment of the fluid, indicating that both the equilibrium thermodynamic properties and viscosity yield the same value for the chain lengths of n-alkanes.

Relaxation of heavy species and gas temperature in the afterglow of a N2 microwave discharge

NASA Astrophysics Data System (ADS)

Pintassilgo, Carlos D.; Guerra, Vasco

2017-10-01

In this paper we present a self-consistent kinetic model to study the temporal variation of the gas temperature in the afterglow of a 440 Pa microwave nitrogen discharge operating at 433 MHz in a 3.8 cm diameter tube. The initial conditions in the afterglow are determined by a kinetic model that solves the electron Boltzmann equation coupled to the gas thermal balance equation and a system of rate-balance equations for N2(X 1∑g+, v) molecules, electronically excited states of N2, ground and excited states of atomic nitrogen and the main positive ions. Once the initial concentrations of the heavy species and gas temperature are known, their relaxation in the afterglow is obtained from the solutions to the corresponding time-dependent equations. Modelling predictions are found to be in good agreement with previously measured values for the concentrations of N(4S) atoms and N2(A 3∑u+) molecules, and the radially averaged gas temperature Tg along the afterglow of a microwave discharge in N2 under the same working conditions. It is shown that gas heating in the afterglow comes essentially from the energy transfer involving non-resonant vibration-vibration (V-V) collisions between vibrationally excited nitrogen molecules, as well as from energy exchanges in vibration-translation (V-T) on N2-N collisions. Contribution to the topical issue "Plasma Sources and Plasma Processes (PSPP)", edited by Luis Lemos Alves, Thierry Belmonte and Tiberiu Minea

Comment on ''Theory of collisions between an atom and a diatomic molecule in the body-fixed coordinate system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schatz, G.C.; Kuppermann, A.

1979-03-15

It is shown that the phase factor i/sup J+j+l/ omitted in a theory of atom-diatom monreactive scattering formulated by Schatz and Kupperman but included in the Choi, Poe, and Tang theory does not lead to errors in the analysis of te (H,H/sub 2/) system.

Electron collisions with F2CO molecules

NASA Astrophysics Data System (ADS)

Freitas, Thiago Corrêa; Barbosa, Alessandra Souza; Bettega, Márcio Henrique Franco

2017-07-01

In this paper we present elastic differential, integral, and momentum-transfer cross sections for electron collisions with carbonyl fluoride (F2CO ) molecules for the incident electron's energy from 0.5 eV to 20 eV. The Schwinger multichannel method with pseudopotentials was employed to obtain the cross sections in the static-exchange and static-exchange plus polarization approximations. The present results were compared with the available data in the literature, in particular, with the results of Kaur, Mason, and Antony [Phys. Rev. A 92, 052702 (2015), 10.1103/PhysRevA.92.052702] for the differential, total, and momentum-transfer cross sections. We have found a π* shape resonance centered at 2.6 eV in the B1 symmetry and other resonance, in the B2 symmetry, located at around 9.7 eV. A systematic study of the inclusion of polarization effects was performed in order to have a well balanced description of this negative-ion transient state. The effects of the long-range electric dipole potential were included by the Born closure scheme. Electronic structure calculations were also performed to help in the interpretation of the scattering results, and associate the transient states to the unoccupied orbitals.

Effect of laser fluence and ambient gas pressure on surface morphology and chemical composition of hydroxyapatite thin films deposited using pulsed laser deposition

NASA Astrophysics Data System (ADS)

Nishikawa, Hiroaki; Hasegawa, Tsukasa; Miyake, Akiko; Tashiro, Yuichiro; Komasa, Satoshi; Hashimoto, Yoshiya

2018-01-01

The dependence of the surface morphology and chemical composition of hydroxyapatite (HA) thin films on the laser fluence and ambient gas pressure during their formation by pulsed laser deposition was studied as the first step to investigate the effect of physical and chemical interactions between the ablated chemical species and ambient gas molecules on HA film formation. It was found that a higher fluence could decrease the number of large protrusions on the surface of HA thin films. However, too high a fluence caused a phosphorus deficiency from the stoichiometric value, particularly in the case of lower ambient gas pressure. It was also found that for lower fluences, the atomic species among the ablated chemical species were easily scattered by collision processes with ambient gas molecules. This was caused by the lower velocity of the ablated chemical species and higher ambient gas pressure, which induced a shorter mean free path. In addition, these collision processes played an important role in the adsorption, migration, and re-evaporation of the ablated chemical species on the substrate via chemical reactions.

The rotational excitation of HF by H

NASA Astrophysics Data System (ADS)

Desrousseaux, Benjamin; Lique, François

2018-06-01

The HF molecule is a key tracer of molecular hydrogen in diffuse interstellar medium (ISM). Accurate modelling of the HF abundance in such media requires one to model its excitation by both radiation and collisions. In diffuse ISM, the dominant collisional partners are atomic and molecular hydrogen. We report quantum time-independent calculations of collisional cross-sections and rate coefficients for the rotational excitation of HF by H. The reactive hydrogen exchange channels are taken into account in the scattering calculations. For the first time, HF-H rate coefficients are provided for temperature ranging from 10 to 500 K. The strongest collision-induced rotational HF transitions are those with Δj = 1, and the order of magnitude of the new HF-H rate coefficients is similar to that of the HF-H2 ones previously computed. As a first application, we simulate the excitation of HF by both H and H2 in typical diffuse ISM. We show that, depending on the rotational transition, hydrogen atoms increase or decrease the simulated excitation temperatures compared to collisional excitation only due to H2 molecules. Such results suggest that the new HF-H collisional data have to be used for properly modelling the abundance of HF in diffuse ISM.

Reduction of polyatomic interferences in ICP-MS by collision/reaction cell (CRC-ICP-MS) techniques

DOE Office of Scientific and Technical Information (OSTI.GOV)

Eiden, Greg C; Barinaga, Charles J; Koppenaal, David W

2012-05-01

Polyatomic and other spectral interferences in plasma source mass spectrometry (PSMS) can be dramatically reduced using collision and reaction cells (CRC). These devices have been used for decades in fundamental studies of ion-molecule chemistry, but have only recently been applied to PSMS. Benefits of this approach as applied in inductively coupled plasma MS (ICP-MS) include interference reduction, isobar separation, and thermalization/focusing of ions. Novel ion-molecule chemistry schemes are now routinely designed and empirically evaluated with relative ease. These “chemical resolution” techniques can avert interferences requiring mass spectral resolutions of >600,000 (m/m). Purely physical ion beam processes, including collisional dampening andmore » collisional dissociation, are also employed to provide improved sensitivity, resolution, and spectral simplicity. CRC techniques are now firmly entrenched in current-day ICP-MS technology, enabling unprecedented flexibility and freedom from many spectral interferences. A significant body of applications has now been reported in the literature. CRC techniques are found to be most useful for specialized or difficult analytical needs and situations, and are employed in both single- and multi-element determination modes.« less

Pressure broadening of the ((dt. mu. )dee)* formation resonances

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cohen, J.S.; Leon, M.; Padial, N.T.

1988-12-27

The treatment of ((dt..mu..)dee)* formation at high densities as a pressure broadening process is discussed. Cross sections for collisions of the complex (dt..mu..)dee, and of the D/sub 2/ molecule from which it is formed, with the bath molecules have been accurately calculated. These cross sections are used to calculate the collisional width in three variations of the impact approximation that have been proposed for this problem. In general, the quasistatic approximation is shown to satisfy the usual conditions of muon-catalyzed fusion better than does the impact approximation. A preliminary rough treatment is presented to illustrate the quasistatic approximation.

Methyl group transfer upon gas phase decomposition of protonated methyl benzoate and similar compounds.

PubMed

Frański, Rafał; Gierczyk, Błażej; Zalas, Maciej; Jankowski, Wojciech; Hoffmann, Marcin

2018-05-01

Gas phase decompositions of protonated methyl benzoate and its conjugates have been studied by using electrospray ionization-collision induced dissociation-tandem mass spectrometry. Loss of CO 2 molecule, thus transfer of methyl group, has been observed. In order to better understand this process, the theoretical calculations have been performed. For methyl benzoate conjugates, it has been found that position of substituent affects the loss of CO 2 molecule, not the electron donor/withdrawing properties of the substituent. Therefore, electrospray ionization-mass spectrometry in positive ion mode may be useful for differentiation of isomers of methyl benzoate conjugates. Copyright © 2018 John Wiley & Sons, Ltd.

Vibrational energy distribution in aniline scattered from surfaces covered with organized organic monolayers

NASA Astrophysics Data System (ADS)

Paz, Y.; Naaman, R.

1990-08-01

Energy distribution in aniline molecules scattered from organized organic monolayers was investigated using a resonance-enhanced two-photon ionization technique. Two type of monolayers were used, one exposing a floppy unsubstituted aliphatic chain (OTS, n-octadecyltrichlorosilane), and the second having a perfluorinated tail (PFDA, perfluorodecanoic acid). The dependence of the internal and translational energy of the scattered aniline is monitored as a function of collision energy and surface properties. The data reveal an unusually high propensity for excitation of the NH 2 inversion mode in aniline. Vibrationally excited molecules are scattered with a narrower time-of-flight (TOF) distribution than those in the ground vibrational state.

Rotational quenching of H2O by He: mixed quantum/classical theory and comparison with quantum results.

PubMed

Ivanov, Mikhail; Dubernet, Marie-Lise; Babikov, Dmitri

2014-04-07

The mixed quantum/classical theory (MQCT) formulated in the space-fixed reference frame is used to compute quenching cross sections of several rotationally excited states of water molecule by impact of He atom in a broad range of collision energies, and is tested against the full-quantum calculations on the same potential energy surface. In current implementation of MQCT method, there are two major sources of errors: one affects results at energies below 10 cm(-1), while the other shows up at energies above 500 cm(-1). Namely, when the collision energy E is below the state-to-state transition energy ΔE the MQCT method becomes less accurate due to its intrinsic classical approximation, although employment of the average-velocity principle (scaling of collision energy in order to satisfy microscopic reversibility) helps dramatically. At higher energies, MQCT is expected to be accurate but in current implementation, in order to make calculations computationally affordable, we had to cut off the basis set size. This can be avoided by using a more efficient body-fixed formulation of MQCT. Overall, the errors of MQCT method are within 20% of the full-quantum results almost everywhere through four-orders-of-magnitude range of collision energies, except near resonances, where the errors are somewhat larger.

Collisional charging of individual submillimeter particles: Using ultrasonic levitation to initiate and track charge transfer

NASA Astrophysics Data System (ADS)

Lee, Victor; James, Nicole M.; Waitukaitis, Scott R.; Jaeger, Heinrich M.

2018-03-01

Electrostatic charging of insulating fine particles can be responsible for numerous phenomena ranging from lightning in volcanic plumes to dust explosions. However, even basic aspects of how fine particles become charged are still unclear. Studying particle charging is challenging because it usually involves the complexities associated with many-particle collisions. To address these issues, we introduce a method based on acoustic levitation, which makes it possible to initiate sequences of repeated collisions of a single submillimeter particle with a flat plate, and to precisely measure the particle charge in situ after each collision. We show that collisional charge transfer between insulators is dependent on the hydrophobicity of the contacting surfaces. We use glass, which we modify by attaching nonpolar molecules to the particle, the plate, or both. We find that hydrophilic surfaces develop significant positive charges after contacting hydrophobic surfaces. Moreover, we demonstrate that charging between a hydrophilic and a hydrophobic surface is suppressed in an acidic environment and enhanced in a basic one. Application of an electric field during each collision is found to modify the charge transfer, again depending on surface hydrophobicity. We discuss these results within the context of contact charging due to ion transfer, and we show that they lend strong support to O H- ions as the charge carriers.

Rotationally inelastic collisions of He and Ar with NaK: Theory and Experiment

NASA Astrophysics Data System (ADS)

Richter, K.; Price, T.; Jones, J.; Faust, C.; Hickman, A. P.; Huennekens, J.; Malenda, R. F.; Ross, A. J.; Crozet, P.

2014-05-01

Rotationally inelastic collisions of NaK (A1Σ+) molecules with He and Ar have been studied. At Lehigh, we use a pump-probe scheme (the probe is scanned over transitions to the 31 Π state) with either polarization labeling (PL) or laser-induced fluorescence (LIF) spectroscopy. At Lyon, one-laser excitation is used with Fourier Transform (FT) fluorescence spectroscopy. In both cases, the pump laser excites a particular ro-vibrational level A1Σ+ (v , J). We observe strong direct lines corresponding to transitions from the (v , J) level pumped, and weak satellite lines corresponding to transitions from collisionally-populated levels (v ,J' = J + ΔJ). The ratios of satellite to direct line intensities in LIF and PL yield information about population and orientation transfer. A strong propensity for ΔJ = even transitions is observed for both He and Ar perturbers. In the FT fluorescence experiment we also observe v changing collisions. Theoretical calculations are also underway for collisions in both the A1Σ+ and X1Σ+ states. For He-NaK we have calculated potential surfaces using GAMESS and carried out coupled channel scattering calculations of transfer of population, orientation, and alignment. Work supported by NSF, XSEDE and CNRS (PICS).

Comparison of DNA decatenation by Escherichia coli topoisomerase IV and topoisomerase III: implications for non-equilibrium topology simplification

PubMed Central

Seol, Yeonee; Hardin, Ashley H.; Strub, Marie-Paule; Charvin, Gilles; Neuman, Keir C.

2013-01-01

Type II topoisomerases are essential enzymes that regulate DNA topology through a strand-passage mechanism. Some type II topoisomerases relax supercoils, unknot and decatenate DNA to below thermodynamic equilibrium. Several models of this non-equilibrium topology simplification phenomenon have been proposed. The kinetic proofreading (KPR) model postulates that strand passage requires a DNA-bound topoisomerase to collide twice in rapid succession with a second DNA segment, implying a quadratic relationship between DNA collision frequency and relaxation rate. To test this model, we used a single-molecule assay to measure the unlinking rate as a function of DNA collision frequency for Escherichia coli topoisomerase IV (topo IV) that displays efficient non-equilibrium topology simplification activity, and for E. coli topoisomerase III (topo III), a type IA topoisomerase that unlinks and unknots DNA to equilibrium levels. Contrary to the predictions of the KPR model, topo IV and topo III unlinking rates were linearly related to the DNA collision frequency. Furthermore, topo III exhibited decatenation activity comparable with that of topo IV, supporting proposed roles for topo III in DNA segregation. This study enables us to rule out the KPR model for non-equilibrium topology simplification. More generally, we establish an experimental approach to systematically control DNA collision frequency. PMID:23460205

Born Hartree Bethe approximation in the theory of inelastic electron molecule scattering

NASA Astrophysics Data System (ADS)

Kretinin, I. Yu; Krisilov, A. V.; Zon, B. A.

2008-11-01

We propose a new approximation in the theory of inelastic electron atom and electron molecule scattering. Taking into account the completeness property of atomic and molecular wavefunctions, considered in the Hartree approximation, and using Bethe's parametrization for electronic excitations during inelastic collisions via the mean excitation energy, we show that the calculation of the inelastic total integral cross-sections (TICS), in the framework of the first Born approximation, involves only the ground-state wavefunction. The final analytical formula obtained for the TICS, i.e. for the sum of elastic and inelastic ones, contains no adjusting parameters. Calculated TICS for electron scattering by light atoms and molecules (He, Ne, and H2) are in good agreement within the experimental data; results show asymptotic coincidence for heavier ones (Ar, Kr, Xe and N2).

Slowing and cooling of heavy or light (even with a tiny electric dipole moment) polar molecules using a novel, versatile electrostatic Stark decelerator.

PubMed

Wang, Qin; Hou, Shunyong; Xu, Liang; Yin, Jianping

2016-02-21

To meet some demands for realizing precise measurements of an electric dipole moment of electron (eEDM) and examining cold collisions or cold chemical physics, we have proposed a novel, versatile electrostatic Stark decelerator with an array of true 3D electric potential wells, which are created by a series of horizontally-oriented, U-shaped electrodes with time-sequence controlling high voltages (± HV) and two guiding electrodes with a constant voltage. We have calculated the 2D electric field distribution, the Stark shifts of the four lowest rotational sub-levels of PbF molecules in the X1(2)Π1/2(v = 0) electronic and vibrational ground states as well as the population in the different rotational levels. We have discussed the 2D longitudinal and transverse phase-space acceptances of PbF molecules in our decelerator. Subsequently, we have simulated the dynamic processes of the decelerated PbF molecules using the 3D Monte-Carlo method, and have found that a supersonic PbF beam with a velocity of 300 m s(-1) can be efficiently slowed to about 5 m s(-1), which will greatly enhance the sensitivities to research a parity violation and measure an eEDM. In addition, we have investigated the dependences of the longitudinal velocity spread, longitudinal temperature and bunching efficiency on both the number of guiding stages and high voltages, and found that after bunching, a cold packet of PbF molecules in the J = 7/2, MΩ = -7/4 state with a longitudinal velocity spread of 0.69 m s(-1) (corresponding to a longitudinal temperature of 2.35 mK) will be produced by our high-efficient decelerator, which will generate a high energy-resolution molecular beam for studying cold collision physics. Finally, our novel decelerator can also be used to efficiently slow NO molecules with a tiny electric dipole moment (EDM) of 0.16 D from 315 m s(-1) to 28 m s(-1). It is clear that our proposed new decelerator has a good slowing performance and experimental feasibility as well as wide applications in the field of precise measurements and cold molecule physics.

Vector correlations study of the reaction N(2D)+H2(X1Σg+)→NH(a1Δ)+H(2S) with different collision energies and reagent vibration excitations

NASA Astrophysics Data System (ADS)

Li, Yong-Qing; Zhang, Yong-Jia; Zhao, Jin-Feng; Zhao, Mei-Yu; Ding, Yong

2015-11-01

Vector correlations of the reaction are studied based on a recent DMBE-SEC PES for the first excited state of NH2 [J. Phys. Chem. A 114 9644 (2010)] by using a quasi-classical trajectory method. The effects of collision energy and the reagent initial vibrational excitation on cross section and product polarization are investigated for v = 0-5 and j = 0 states in a wide collision energy range (10-50 kcal/mol). The integral cross section could be increased by H2 vibration excitation remarkably based on the DMBE-SEC PES. The different phenomena of differential cross sections with different collision energies and reagent vibration excitations are explained. Particularly, the NH molecules are scattered mainly in the backward hemisphere at low vibration quantum number and evolve from backward to forward direction with increasing vibration quantum number, which could be explained by the fact that the vibrational excitation enlarges the H-H distance in the entrance channel, thus enhancing the probability of collision between N atom and H atom. A further study on product polarization demonstrates that the collision energy and vibrational excitation of the reagent remarkably influence the distributions of P(θr), P(ϕr), and P(θr, ϕr). Project supported by the National Natural Science Foundation of China (Grant Nos. 11474141 and 11404080), the Special Fund Based Research New Technology of Methanol conversion and Coal Instead of Oil, the China Postdoctoral Science Foundation (Grant No. 2014M550158) , the Scientific Research Foundation for the Returned Overseas Chinese Scholars, State Education Ministry of China (Grant No. 2014-1685), and the Program for Liaoning Excellent Talents in University, China (Grant Nos. LJQ2015040 and LJQ2014001).

Steric effects in state-to-state scattering of OH ({sup 2}{pi}{sub 3/2},J=3/2,f) by HCl

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cireasa, R.; Moise, A.; Meulen, J.J. ter

2005-08-08

In this paper we address stereodynamical issues in the inelastic encounters between OH ({chi}{sup 2}{pi}) radicals and HCl ({chi}{sup 1}{sigma}{sup +}). The experiments were performed in a crossed molecular-beam machine at the nominal collision energy of 920 cm{sup -1}. Prior to the collisions, the OH molecules were selected using a hexapole in a well-defined rotational state v=0, {omega}=3/2, J=3/2, M{sub J}=3/2, f, and subsequently oriented in a homogeneous electrical field. We have measured rotationally resolved relative cross sections for collisions in which OH is oriented with either the O side or the H side towards HCl, from which we havemore » calculated the corresponding steric asymmetry factors S. The results are presented in comparison with data previously obtained by our group for the inelastic scattering of OH by CO (E{sub coll}=985 cm{sup -1}) and N{sub 2} (E{sub coll}=985 cm{sup -1}) studied under similar experimental conditions. The dissimilarity in the behavior of the OH+HCl system revealed by this comparison is explained on the basis of the difference in the anisotropy of the interaction potential governing the collisions. The interpretation of the data takes into account the specific features of both nonreactive and reactive parts of the potential-energy surface. The results indicate that the scattering dynamics at this collision energy may be influenced by the HO-HCl van der Waals well and by reorientation effects determined by the long-range electrostatic forces and, furthermore, may involve reactive collisions.« less

Calculating constants of the rates of the reactions of excitation, ionization, and atomic exchange: A model of a shock oscillator with a change of the Hamiltonian of the system

NASA Astrophysics Data System (ADS)

Tsyganov, D. L.

2017-11-01

A new model for calculating the rates of reactions of excitation, ionization, and atomic exchange is proposed. Diatomic molecule AB is an unstructured particle M upon the exchange of elastic-vibrational (VT) energy, i.e., a model of a shock forceful oscillator with a change in Hamiltonian (SFOH). The SFOH model is based on the quantum theory of strong perturbations. The SFOH model allows generalization in simulating the rates of the reactions of excitation, ionization, and atomic exchange in the vibrational-vibrational (VV) energy exchange of diatomic molecules, and the exchange of VV- and VT-energy of polyatomic molecules. The rate constants of the excitation of metastables A 3Σ u +, B 3Π g , W 3Δ u , B'3Σ u -, a'3Σ u -, and the ionization of a nitrogen molecules from ground state X2Σ g + upon a collision with a heavy structureless particle (a nitrogen molecule), are found as examples.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ito, Yuta; Wang, Chuncheng; Le, Anh-Thu

Here, we have measured the angular distributions of high energy photoelectrons of benzene molecules generated by intense infrared femtosecond laser pulses. These electrons arise from the elastic collisions between the benzene ions with the previously tunnel-ionized electrons that have been driven back by the laser field. Theory shows that laser-free elastic differential cross sections (DCSs) can be extracted from these photoelectrons, and the DCS can be used to retrieve the bond lengths of gas-phase molecules similar to the conventional electron diffraction method. From our experimental results, we have obtained the C-C and C-H bond lengths of benzene with a spatialmore » resolution of about 10 pm. Our results demonstrate that laser induced electron diffraction (LIED) experiments can be carried out with the present-day ultrafast intense lasers already. Looking ahead, with aligned or oriented molecules, more complete spatial information of the molecule can be obtained from LIED, and applying LIED to probe photo-excited molecules, a “molecular movie” of the dynamic system may be created with sub-A°ngstrom spatial and few-ten femtosecond temporal resolutions.« less

The molecular composition of dense interstellar clouds

NASA Technical Reports Server (NTRS)

Allen, M.; Robinson, G. W.

1977-01-01

Presented in this paper is an ab initio chemical model for dense interstellar clouds that incorporates 598 grain surface reactions, with small grains providing the reaction area. Gas-phase molecules are depleted through collisions with grains. The abundances of 372 chemical species are calculated as a function of time and are found to be of sufficient magnitude to explain most observations. Peak abundances are achieved on time scales of the order of 100,000 to 1 million years, depending on cloud density and kinetic temperature. The reaction rates for ion-molecule chemistry are approximately the same, indicating that surface and gas-phase chemistry may be coupled in certain regions. The composition of grain mantles is shown to be a function of grain radius. In certain grain-size ranges, large molecules containing two or more heavy atoms are more predominant than lighter 'ices' - H2O, NH3, and CH4. It is possible that absorption due to these large molecules in the mantle may contribute to the observed 3-micron band in astronomical spectra.

Study of ground state optical transfer for ultracold alkali dimers

NASA Astrophysics Data System (ADS)

Bouloufa-Maafa, Nadia; Londono, Beatriz; Borsalino, Dimitri; Vexiau, Romain; Mahecha, Jorge; Dulieu, Olivier; Luc-Koenig, Eliane

2013-05-01

Control of molecular states by laser pulses offer promising potential applications. The manipulation of molecules by external fields requires precise knowledge of the molecular structure. Our motivation is to perform a detailed analysis of the spectroscopic properties of alkali dimers, with the aim to determine efficient optical paths to form molecules in the absolute ground state and to determine the optimal parameters of the optical lattices where those molecules are manipulated to avoid losses by collisions. To this end, we use state of the art molecular potentials, R-dependent spin-orbit coupling and transition dipole moment to perform our calculations. R-dependent SO coupling are of crucial importance because the transitions occur at internuclear distances where they are affected by this R-dependence. Efficient schemes to transfer RbCs, KRb and KCs to the absolute ground state as well as the optimal parameters of the optical lattices will be presented. This work was supported in part by ``Triangle de la Physique'' under contract 2008-007T-QCCM (Quantum Control of Cold Molecules).

Steric Effects of Solvent Molecules on SN2 Substitution Dynamics.

PubMed

Liu, Xu; Xie, Jing; Zhang, Jiaxu; Yang, Li; Hase, William L

2017-04-20

Influences of solvent molecules on S N 2 reaction dynamics of microsolvated F - (H 2 O) n with CH 3 I, for n = 0-3, are uncovered by direct chemical dynamics simulations. The direct substitution mechanism, which is important without microsolvation, is quenched dramatically upon increasing hydration. The water molecules tend to force reactive encounters to proceed through the prereaction collision complex leading to indirect reaction. In contrast to F - (H 2 O), reaction with higher hydrated ions shows a strong propensity for ion desolvation in the entrance channel, diminishing steric hindrance for nucleophilic attack. Thus, nucleophilic substitution avoids the potential energy barrier with all of the solvent molecules intact and instead occurs through the less solvated barrier, which is energetically unexpected because the former barrier has a lower energy. The work presented here reveals a trade-off between reaction energetics and steric effects, with the latter found to be crucial in understanding how hydration influences microsolvated S N 2 dynamics.

Plasma/Neutral-Beam Etching Apparatus

NASA Technical Reports Server (NTRS)

Langer, William; Cohen, Samuel; Cuthbertson, John; Manos, Dennis; Motley, Robert

1989-01-01

Energies of neutral particles controllable. Apparatus developed to produce intense beams of reactant atoms for simulating low-Earth-orbit oxygen erosion, for studying beam-gas collisions, and for etching semiconductor substrates. Neutral beam formed by neutralization and reflection of accelerated plasma on metal plate. Plasma ejected from coaxial plasma gun toward neutralizing plate, where turned into beam of atoms or molecules and aimed at substrate to be etched.

H- and He-like Charge-Exchange Induced X-ray Emission due to Ion Collisions with H, He, and H2

NASA Astrophysics Data System (ADS)

Cumbee, Renata; Mullen, Patrick; Miller, Ansley; Lyons, David; Shelton, Robin L.; Schultz, David R.; Stancil, Phillip C.; Leutenegger, Maurice A.

2017-08-01

When a hot plasma collides with a cold neutral gas interactions occur between the microscopic constituents including charge exchange (CX). CX is a process in which an electron can be transferred from a neutral atom or molecule into an excited energy level of an ion. Following this transfer, the excited electron relaxes to lower energy levels, emitting X-rays. This process has been established as a primary source of X-ray emission within our solar system, such as when the solar wind interacts with cometary and planetary atmospheres, and outside of our solar system, such as in the hot outflows of starburst galaxies.Since the CX X-ray emission spectrum varies greatly with collision velocity, it is critical that realistic CX data are included in X-ray spectral models of astrophysical environments in which CX might be significant in order to correctly estimate the ion abundance and plasma velocities. Here, line ratios and spectra are computed using theoretical CX cross sections obtained with the multi-channel Landau-Zener, atomic-orbital close-coupling, and classical-trajectory Monte Carlo methods for a variety of collision energies relevant to various astrophysical environments. Collisions of bare and H-like C, N, O, Ne, Mg, Al, Si, P, S, and Cl ions are shown with H, He, and H2 as the neutral collision targets. An X-ray model using line ratios for C-Si ions is then performed within XSPEC for a region of the Cygnus Loop supernova remnant for 8 collision energies in order to highlight the variation in CX spectral models with collision energy.R. Cumbee’s research was partially supported by an appointment to the NASA Postdoctoral Program at NASA GSFC, administered by Universities Space Research Association under contract with NASA. Work at UGA was partially supported by NASA grants NNX09AC46G and NNG09WF24I.

Zeeman relaxation of MnH (X7Σ+) in collisions with He3: Mechanism and comparison with experiment

NASA Astrophysics Data System (ADS)

Turpin, F.; Stoecklin, T.; Halvick, Ph.

2011-03-01

We present a theoretical study of the Zeeman relaxation of the magnetically trappable lowest field seeking state of MnH (7Σ) in collisions with He3. We analyze the collisional Zeeman transition mechanism as a function of the final diatomic state and its variation as a function of an applied magnetic field. We show that as a result of this mechanism the levels with ΔMj>2 give negligible contributions to the Zeemam relaxation cross section. We also compare our results to the experimental cross sections obtained from the buffer-gas cooling and magnetic trapping of this molecule and investigate the dependence of the Zeeman relaxation cross section on the accuracy of the three-body interaction at ultralow energies.

Absorption effects in electron-sulfur-dioxide collisions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Machado, L. E.; Sugohara, R. T.; Santos, A. S. dos

2011-09-15

A joint experimental-theoretical study on electron-SO{sub 2} collisions in the low and intermediate energy range is reported. More specifically, experimental elastic differential, integral, and momentum transfer cross sections in absolute scale are measured in the 100-1000 eV energy range using the relative-flow technique. Calculated elastic differential, integral, and momentum transfer cross sections as well as grand-total and total absorption cross sections are also presented in the 1-1000 eV energy range. A complex optical potential is used to represent the electron-molecule interaction dynamics, whereas the Schwinger variational iterative method combined with the distorted-wave approximation is used to solve the scattering equations.more » Comparison of the present results is made with the theoretical and experimental results available in the literature.« less

Chemical Recycling of Molecules in Cometary Comae

NASA Astrophysics Data System (ADS)

Boice, Daniel C.; Kawakita, Hideyo; Shinnaka, Yoshiharu; Kobayashi, Hitomi

2015-08-01

Modeling is essential to understand the important physical and chemical processes that occur in cometary comae, especially the relationship between native and sibling molecules, such as, HCN and CN. Photochemistry is a major source of ions and electrons that further initiate key gas-phase reactions, leading to the plethora of molecules and atoms observed in comets. The effects of photoelectrons that react via impacts are important to the overall ionization in the inner coma. We have found that many molecules undergo protonation reactions with primarily water, followed by electron recombination resulting in the original molecules in a vibrationally excited state. These excited molecules spontaneously emit photons back to the ground state. We identify this series of reactions as chemical “recycling.” We discuss the importance of this mechanism for HCN, NH3, and water in comets. We also identify other relevant processes in the collision-dominated, inner coma of a comet within a global modeling framework to better understand observations and in situ measurements of cometary species, especially relationships between native and sibling molecules for the Rosetta Mission to Comet 67P/Churyumov-Gerasimenko.Acknowledgements: We appreciate support from the NSF Planetary Astronomy Program under Grant No. 0908529. This program is partially supported by the MEXT Supported Program for the Strategic Research Foundation at Private Universities, 2014-2018.

Experimental study of the reactive processes in the gas phase K{sup +}+i-C{sub 3}H{sub 7}Cl collisions: A comparison with Li and Na ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aguilar, J.; Lucas, J. M.; Andres, J. de

2013-05-14

Reactive collisions between alkali ions (Li{sup +}, Na{sup +}, and K{sup +}) and halogenated hydrocarbon molecules have been studied recently in our research group. In this paper, we have reported on the K{sup +}+i-C{sub 3}H{sub 7}Cl system in the 0.20-14.00 eV center-of-mass energy range using a radio frequency guided-ion beam apparatus developed in our laboratory. Aiming at increasing our knowledge about this kind of reactions, we compare our latest results for K{sup +} with those obtained previously for Li{sup +} and Na{sup +}. While the reaction channels are the same in all three cases, their energy profiles, reactivity, measured reactivemore » cross-section energy dependences, and even their reaction mechanisms, differ widely. By comparing experimentally measured reactive cross-sections as a function of the collision energy with the ab initio calculations for the different potential energy surfaces, a qualitative interpretation of the dynamics of the three reactive systems is presented in the present work.« less

The Effect of the Spin-Forbidden Co((sup 1) Sigma plus) plus O((sup 3) P) Yields CO2 (1 Sigma (sub G) plus) Recombination Reaction on Afterbody Heating of Mars Entry Vehicles

NASA Technical Reports Server (NTRS)

Xu, Lu T.; Jaffe, Richard L.; Schwenke, David W.; Panesi, Marco

2017-01-01

Vibrationally excited CO2, formed by two-body recombination from CO((sup 1) sigma plus) and O((sup 3) P) in the wake behind spacecraft entering the Martian atmosphere reaction, is potentially responsible for the higher than anticipated radiative heating of the backshell, compared to pre-flight predictions. This process involves a spin-forbidden transition of the transient triplet CO2 molecule to the longer-lived singlet. To accurately predict the singlet-triplet transition probability and estimate the thermal rate coefficient of the recombination reaction, ab initio methods were used to compute the first singlet and three lowest triplet CO2 potential energy surfaces and the spin-orbit coupling matrix elements between these states. Analytical fits to these four potential energy surfaces were generated for surface hopping trajectory calculations, using Tully's fewest switches surface hopping algorithm. Preliminary results for the trajectory calculations are presented. The calculated probability of a CO((sup 1) sigma plus) and O((sup 3) P) collision leading to singlet CO2 formation is on the order of 10 (sup -4). The predicted flowfield conditions for various Mars entry scenarios predict temperatures in the range of 1000 degrees Kelvin - 4000 degrees Kelvin and pressures in the range of 300-2500 pascals at the shoulder and in the wake, which is consistent with a heavy-particle collision frequency of 10 (sup 6) to 10 (sup 7) per second. Owing to this low collision frequency, it is likely that CO((sup 1) sigma plus) molecules formed by this mechanism will mostly be frozen in a highly nonequilibrium rovibrational energy state until they relax by photoemission.

Quantum chaos in ultracold collisions of gas-phase erbium atoms.

PubMed

Frisch, Albert; Mark, Michael; Aikawa, Kiyotaka; Ferlaino, Francesca; Bohn, John L; Makrides, Constantinos; Petrov, Alexander; Kotochigova, Svetlana

2014-03-27

Atomic and molecular samples reduced to temperatures below one microkelvin, yet still in the gas phase, afford unprecedented energy resolution in probing and manipulating the interactions between their constituent particles. As a result of this resolution, atoms can be made to scatter resonantly on demand, through the precise control of a magnetic field. For simple atoms, such as alkalis, scattering resonances are extremely well characterized. However, ultracold physics is now poised to enter a new regime, where much more complex species can be cooled and studied, including magnetic lanthanide atoms and even molecules. For molecules, it has been speculated that a dense set of resonances in ultracold collision cross-sections will probably exhibit essentially random fluctuations, much as the observed energy spectra of nuclear scattering do. According to the Bohigas-Giannoni-Schmit conjecture, such fluctuations would imply chaotic dynamics of the underlying classical motion driving the collision. This would necessitate new ways of looking at the fundamental interactions in ultracold atomic and molecular systems, as well as perhaps new chaos-driven states of ultracold matter. Here we describe the experimental demonstration that random spectra are indeed found at ultralow temperatures. In the experiment, an ultracold gas of erbium atoms is shown to exhibit many Fano-Feshbach resonances, of the order of three per gauss for bosons. Analysis of their statistics verifies that their distribution of nearest-neighbour spacings is what one would expect from random matrix theory. The density and statistics of these resonances are explained by fully quantum mechanical scattering calculations that locate their origin in the anisotropy of the atoms' potential energy surface. Our results therefore reveal chaotic behaviour in the native interaction between ultracold atoms.

Computational Investigations of Rovibrational Quenching of HD due to Collisions in the Interstellar Medium

NASA Astrophysics Data System (ADS)

Goodman Veazey, Clark; Wan, Yier; Yang, Benhui H.; Stancil, P.

2017-06-01

When conducting an examination of distant astronomical objects, scientists rely on measurements derived from astronomical observations of these objects, which are primarily collected using spectroscopy. In order to interpret spectroscopic data collected on astronomical objects, it is necessary to have a background of accurate dynamical information on interstellar molecules at one’s disposal. Seeing as most of the observable infrared radiation in the universe is emitted by molecules excited by collisional processes in the interstellar gas, generating accurate data on the rate of molecular collisions is of salient interest to astronomical endeavors.The collisional system we will be focusing on here is He-HD, an atom-diatom system in which He collides with HD. We are primarily interested in the cooling capabilities of this system, as these species are predicted to have played an important role in the formation of primordial stars, which emerged from a background composed solely of Hydrogen, Helium, and their compounds. HD is being investigated because it has a finite dipole moment and is hence a powerful radiator, and He due to its relative abundance in the early universe. Using a hybrid OpenMP/MPI adaption (vrrm) of a public-domain scattering package, cross sections for He-HD collisions are computed for a swathe of both rotational and vibrational states across a range of relevant kinetic energies, then integrated to produce rate coefficients. Due to the vast computational requirements for performing these operations, the use of high-powered computational resources is necessary.The work of CV was funded by a UGA Center for Undergraduate Research Opportunities award. We thank the University of Georgia GACRC and NERSC at Lawrence-Berkeley for computational resources and Brendan McLaughlin for assistance.

Rotationally specific rates of vibration-vibration energy exchange in collisions of NO(X 2Π1/2,v=3) with NO(X 2Π,v=0)

NASA Astrophysics Data System (ADS)

Islam, Meezanul; Smith, Ian W. M.

1999-11-01

Infrared ultraviolet double resonance (IRUVDR) experiments have been performed to investigate the rotational specificity of the vibrational-vibrational (V-V) exchange process, NO(X 2Π1/2,v=3,Ji)+NO(v=0)→NO(X2Π1/2,v=2,Jf)+NO(v=1), for which the vibrational energy discrepancy corresponds to 55.9 cm-1. Radiation from an optical parametric oscillator was used to excite NO molecules into a specific rotational level (Ji) in the X 2Π, Ω=1/2, v=3 state. Laser-induced fluorescence (LIF) spectra of the (0,2) band of the A 2Σ+-X 2Π1/2 system were then recorded at delays corresponding to a fraction of a collision. From the relative line intensities, rate coefficients were determined for transfer of the excited NO molecule from the level X 2Π1/2, v=3, Ji to different final rotational levels (Jf) in the X 2Π1/2, v=2 state. Results are reported for Ji=3.5, 4.5, 7.5, 10.5, and 15.5. The data show a significant, though not strong, propensity for J to decrease by one; i.e., for ΔJ=Jf-Ji=-1, especially for the higher Ji levels. This result is interpreted as arising from a combination of (a) the tendency to minimize the energy that has to be accommodated in the relative translation of the collision partners, and (b) the favoring of ΔJ=±1 changes when V-V intermolecular exchange occurs under the influence of dipole-dipole interactions.

Fast method for reactor and feature scale coupling in ALD and CVD

DOEpatents

Yanguas-Gil, Angel; Elam, Jeffrey W.

2017-08-08

Transport and surface chemistry of certain deposition techniques is modeled. Methods provide a model of the transport inside nanostructures as a single-particle discrete Markov chain process. This approach decouples the complexity of the surface chemistry from the transport model, thus allowing its application under general surface chemistry conditions, including atomic layer deposition (ALD) and chemical vapor deposition (CVD). Methods provide for determination of determine statistical information of the trajectory of individual molecules, such as the average interaction time or the number of wall collisions for molecules entering the nanostructures as well as to track the relative contributions to thin-film growth of different independent reaction pathways at each point of the feature.

Failure of hydrogenation in protecting polycyclic aromatic hydrocarbons from fragmentation

NASA Astrophysics Data System (ADS)

Gatchell, M.; Stockett, M. H.; de Ruette, N.; Chen, T.; Giacomozzi, L.; Nascimento, R. F.; Wolf, M.; Anderson, E. K.; Delaunay, R.; Vizcaino, V.; Rousseau, P.; Adoui, L.; Huber, B. A.; Schmidt, H. T.; Zettergren, H.; Cederquist, H.

2015-11-01

A recent study of soft x-ray absorption in native and hydrogenated coronene cations, C24H12+m +m =0 -7 , led to the conclusion that additional hydrogen atoms protect (interstellar) polycyclic aromatic hydrocarbon (PAH) molecules from fragmentation [Reitsma et al., Phys. Rev. Lett. 113, 053002 (2014), 10.1103/PhysRevLett.113.053002]. The present experiment with collisions between fast (30-200 eV) He atoms and pyrene (C16H10+m + , m =0 , 6, and 16) and simulations without reference to the excitation method suggests the opposite. We find that the absolute carbon-backbone fragmentation cross section does not decrease but increases with the degree of hydrogenation for pyrene molecules.

A Fokker-Planck based kinetic model for diatomic rarefied gas flows

NASA Astrophysics Data System (ADS)

Gorji, M. Hossein; Jenny, Patrick

2013-06-01

A Fokker-Planck based kinetic model is presented here, which also accounts for internal energy modes characteristic for diatomic gas molecules. The model is based on a Fokker-Planck approximation of the Boltzmann equation for monatomic molecules, whereas phenomenological principles were employed for the derivation. It is shown that the model honors the equipartition theorem in equilibrium and fulfills the Landau-Teller relaxation equations for internal degrees of freedom. The objective behind this approximate kinetic model is accuracy at reasonably low computational cost. This can be achieved due to the fact that the resulting stochastic differential equations are continuous in time; therefore, no collisions between the simulated particles have to be calculated. Besides, because of the devised energy conserving time integration scheme, it is not required to resolve the collisional scales, i.e., the mean collision time and the mean free path of molecules. This, of course, gives rise to much more efficient simulations with respect to other particle methods, especially the conventional direct simulation Monte Carlo (DSMC), for small and moderate Knudsen numbers. To examine the new approach, first the computational cost of the model was compared with respect to DSMC, where significant speed up could be obtained for small Knudsen numbers. Second, the structure of a high Mach shock (in nitrogen) was studied, and the good performance of the model for such out of equilibrium conditions could be demonstrated. At last, a hypersonic flow of nitrogen over a wedge was studied, where good agreement with respect to DSMC (with level to level transition model) for vibrational and translational temperatures is shown.

The G value in plasma and radiation chemistry

NASA Technical Reports Server (NTRS)

Baird, James K.; Miller, George P.; Li, Ning

1990-01-01

The application of the G-value concept to plasma chemistry is considered. A general formula which expresses the G value for a general reaction in terms of experimentally controllable parameters is derived by applying simple gas-dynamic theory to a plasma reactor with straight walls. The formula expresses the G value as a function of the electrical power absorbed, the fraction of molecules transformed, and the flow rate of the gas entering the reactor. The formula was applied to the ammonia plasma radio-frequency discharge data of d'Agostino et al. (1981); the results showed that the G(-NH3) value lies in the range of 6.0-20 molecules/100 eV, depending on the conditions. This similarity of the G(-NH3) value with Peterson's (1974) range 2.7-10 found for the gas-phase radiolysis of ammonia, suggests that there might be a common reaction mechanism initiated by inelastic electron-molecule collisions.

The HITRAN2016 molecular spectroscopic database

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gordon, I. E.; Rothman, L. S.; Hill, C.

This paper describes the contents of the 2016 edition of the HITRAN molecular spectroscopic compilation. The new edition replaces the previous HITRAN edition of 2012 and its updates during the intervening years. The HITRAN molecular absorption compilation is comprised of five major components: the traditional line-by-line spectroscopic parameters required for high-resolution radiative-transfer codes, infrared absorption cross-sections for molecules not yet amenable to representation in a line-by-line form, collision-induced absorption data, aerosol indices of refraction, and general tables such as partition sums that apply globally to the data. The new HITRAN is greatly extended in terms of accuracy, spectral coverage, additionalmore » absorption phenomena, added line-shape formalisms, and validity. Moreover, molecules, isotopologues, and perturbing gases have been added that address the issues of atmospheres beyond the Earth. Of considerable note, experimental IR cross-sections for almost 200 additional significant molecules have been added to the database.« less

Ultracold Nonreactive Molecules in an Optical Lattice: Connecting Chemistry to Many-Body Physics.

PubMed

Doçaj, Andris; Wall, Michael L; Mukherjee, Rick; Hazzard, Kaden R A

2016-04-01

We derive effective lattice models for ultracold bosonic or fermionic nonreactive molecules (NRMs) in an optical lattice, analogous to the Hubbard model that describes ultracold atoms in a lattice. In stark contrast to the Hubbard model, which is commonly assumed to accurately describe NRMs, we find that the single on-site interaction parameter U is replaced by a multichannel interaction, whose properties we elucidate. Because this arises from complex short-range collisional physics, it requires no dipolar interactions and thus occurs even in the absence of an electric field or for homonuclear molecules. We find a crossover between coherent few-channel models and fully incoherent single-channel models as the lattice depth is increased. We show that the effective model parameters can be determined in lattice modulation experiments, which, consequently, measure molecular collision dynamics with a vastly sharper energy resolution than experiments in a free-space ultracold gas.

Visualizing Energy on Target: Molecular Dynamics Simulations

DTIC Science & Technology

2017-12-01

to be construed as an official Department of the Army position unless so designated by other authorized documents. Citation of manufacturer’s or...tend to be small, whereas corresponding coefficients for molecules with low-frequency vibrations close to the impact surface are comparatively much...This is due to the reduced number of N2 collisions with the target resulting from this comparatively weak value of vimp. Figures 10–12 are

Recombination reactions of 5-eV O(3P) atoms on a MgF2 surface

NASA Technical Reports Server (NTRS)

Orient, O. J.; Chutjian, A.; Murad, E.

1990-01-01

A source of hyperthermal, ground-state, impurity-free, atomic oxygen of an energy variable in the range 2-100 eV has been developed. Experimental results are presented of emission spectra in the wavelength range 250-850 nm produced by collisions of 5-eV O(3P) atoms with adsorbed NO and CO molecules on a MgF2 surface.

New cross sections for H on H2 collisional transitions

NASA Astrophysics Data System (ADS)

Zou, Qianxia

2011-12-01

The cross section for H on H2 collisions is important for astrophysics as well as our understanding of the simple chemical systems. This is the simplest atom-molecule cross section. With a new H3 potential surface by Mielke et al., we have modified the ABC code by Skouteris, Castillo and Manolopoulos to calculate new cross sections. These cross sections are compared to previous cross section calculations.

l- and n-changing collisions during interaction of a pulsed beam of Li Rydberg atoms with CO2

NASA Astrophysics Data System (ADS)

Dubreuil, B.; Harnafi, M.

1989-07-01

The pulsed Li atomic beam produced in our experiment is based on controlled transversely-excited-atmospheric CO2 laser-induced ablation of a Li metal target. The atomic beam is propagated in vacuum or in CO2 gas at low pressure. Atoms in the beam are probed by laser-induced fluorescence spectroscopy. This allows the determination of time-of-flight and velocity distributions. Li Rydberg states (n=5-13) are populated in the beam by two-step pulsed-laser excitation. The excited atoms interact with CO2 molecules. l- and n-changing cross sections are deduced from the time evolution of the resonant or collision-induced fluorescence following this selective excitation. l-changing cross sections of the order of 104 AṦ are measured; they increase with n as opposed to the plateau observed for Li* colliding with a diatomic molecule. This behavior is qualitatively well explained in the framework of the free-electron model. n-->n' changing processes with large cross sections (10-100 AṦ) are also observed even in the case of large electronic energy change (ΔEnn'>103 cm-1). These results can be interpreted in terms of resonant-electronic to vibrational energy transfers between Li Rydberg states and CO2 vibrational modes.

Use of dc Ar microdischarge with nonlocal plasma for identification of metal samples

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kudryavtsev, A. A., E-mail: akud@ak2138.spb.edu; Stefanova, M. S.; Pramatarov, P. M.

2015-04-07

The possibility of using the collisional electron spectroscopy (CES) method for the detection of atoms from metal samples is experimentally verified. The detection and identification of metal atoms from a Pt sample in the nonlocal plasma of short (without positive column) dc Ar microdischarge at intermediate pressures (5–30 Torr) is realized in this work. Cathode sputtering is used for atomization of the metal under analysis. The identification of the analyzed metal is made from the energy spectra of groups of fast nonlocal electrons—characteristic electrons released in the Penning ionization of the Pt atoms by Ar metastable atoms and molecules. The acquisitionmore » of the electron energy spectra is performed using an additional electrode—a sensor located at the boundary of the discharge volume. The Pt characteristic Penning electrons form the maxima in the electron energy spectra at the energies of their appearance, which are 2.6 eV and 1.4 eV. From the measured energy of the maxima, identification of the metal atoms is accomplished. The characteristic Ar maxima due to pair collisions between Ar metastable atoms and molecules and super-elastic collisions are also recorded. This study demonstrates the possibility of creating a novel microplasma analyzer for atoms from metal samples.« less

Collisional Transfer of Population and Orientation in NaK

NASA Astrophysics Data System (ADS)

Wolfe, C. M.; Ashman, S.; Huennekens, J.; Beser, B.; Bai, J.; Lyyra, A. M.

2010-03-01

We report current work to study transfer of population and orientation in collisions of NaK molecules with argon and potassium atoms using polarization labeling (PL) and laser- induced fluorescence (LIF) spectroscopy. In the PL experiment, a circularly polarized pump laser excites a specific NaK A^1&+circ;(v'=16, J') <- X^1&+circ;(v''=0, J'±1) transition, creating an orientation (non-uniform MJ' level distribution) in both levels. The linearly polarized probe laser is scanned over various 3^1π(v, J'±1) <- A^1&+circ;(v'=16, J') transitions. The probe laser passes through a crossed linear polarizer before detection, and signal is recorded if the probe laser polarization has been modified by the vapor (which occurs when it comes into resonance with an oriented level). Using both spectroscopic methods, analysis of weak collisional satellite lines adjacent to these directly populated lines, as a function of argon buffer gas pressure and cell temperature, allows us to discern separately the effects collisions with argon atoms and potassium atoms have on the population and orientation of the molecule. In addition, code has been written which provides a theoretical analysis of the process, through a solution of the density matrix equations of motion for the system.

Modeling the Flow of Rarefied Gases at NASA

NASA Technical Reports Server (NTRS)

Forrest E. Lumpkin, III

2012-01-01

At modest temperatures, the thermal energy of atmospheric diatomic gases such as nitrogen is primarily distributed between only translational and rotational energy modes. Furthermore, these energy modes are fully excited such that the specific heat at constant volume is well approximated by the simple expression C(sub v) = 5/2 R. As a result, classical mechanics provides a suitable approximation at such temperatures of the true quantum mechanical behavior of the inter-molecular collisions of such molecules. Using classical mechanics, the transfer of energy between rotational and translation energy modes is studied. The approach of Lordi and Mates is adopted to compute the trajectories and time dependent rotational orientations and energies during the collision of two non-polar diatomic molecules. A Monte-Carlo analysis is performed collecting data from the results of many such simulations in order to estimate the rotational relaxation time. A Graphical Processing Unit (GPU) is employed to improve the performance of the Monte-Carlo analysis. A comparison of the performance of the GPU implementation to an implementation on traditional computer architecture is made. Effects of the assumed inter-molecular potential on the relaxation time are studied. The seminar will also present highlights of computational analyses performed at NASA Johnson Space Center of heat transfer in rarefied gases.

Evaluation of evaporation coefficient for micro-droplets exposed to low pressure: A semi-analytical approach

NASA Astrophysics Data System (ADS)

Chakraborty, Prodyut R.; Hiremath, Kirankumar R.; Sharma, Manvendra

2017-02-01

Evaporation rate of water is strongly influenced by energy barrier due to molecular collision and heat transfer limitations. The evaporation coefficient, defined as the ratio of experimentally measured evaporation rate to that maximum possible theoretical limit, varies over a conflicting three orders of magnitude. In the present work, a semi-analytical transient heat diffusion model of droplet evaporation is developed considering the effect of change in droplet size due to evaporation from its surface, when the droplet is injected into vacuum. Negligible effect of droplet size reduction due to evaporation on cooling rate is found to be true. However, the evaporation coefficient is found to approach theoretical limit of unity, when the droplet radius is less than that of mean free path of vapor molecules on droplet surface contrary to the reported theoretical predictions. Evaporation coefficient was found to reduce rapidly when the droplet under consideration has a radius larger than the mean free path of evaporating molecules, confirming the molecular collision barrier to evaporation rate. The trend of change in evaporation coefficient with increasing droplet size predicted by the proposed model will facilitate obtaining functional relation of evaporation coefficient with droplet size, and can be used for benchmarking the interaction between multiple droplets during evaporation in vacuum.

Non-adiabatic couplings and dynamics in proton transfer reactions of Hn+ systems: application to H2+H2+→H+H3+ collisions

PubMed Central

Sanz-Sanz, Cristina; Aguado, Alfredo; Roncero, Octavio; Naumkin, Fedor

2016-01-01

Analytical derivatives and non-adiabatic coupling matrix elements are derived for Hn+ systems (n=3, 4 and 5). The method uses a generalized Hellmann-Feynman theorem applied to a multi-state description based on diatomics-in-molecules (for H3+) or triatomics-in-molecules (for H4+ and H5+) formalisms, corrected with a permutationally invariant many-body term to get high accuracy. The analytical non-adiabatic coupling matrix elements are compared with ab initio calculations performed at multi-reference configuration interaction level. These magnitudes are used to calculate H2(v′=0,j′=0)+H2+(v,j=0) collisions, to determine the effect of electronic transitions using a molecular dynamics method with electronic transitions. Cross sections for several initial vibrational states of H2+ are calculated and compared with the available experimental data, yielding an excellent agreement. The effect of vibrational excitation of H2+ reactant, and its relation with non-adiabatic processes are discussed. Also, the behavior at low collisional energies, in the 1 meV-0.1 eV interval, of interest in astrophysical environments, are discussed in terms of the long range behaviour of the interaction potential which is properly described within the TRIM formalism. PMID:26696058

Rotational Quenching Study in Isovalent H+ + CO and H+ + CS Systems

NASA Astrophysics Data System (ADS)

Kaur, Rajwant; Dhilip Kumar, T. J.

2016-06-01

Cooling and trapping of polar molecules has attracted attention at cold and ultracold temperatures. Extended study of molecular inelastic collision processes of polar interstellar species with proton finds an important astrophysical application to model interstellar medium. Present study includes computation of rate coefficient for molecular rotational quenching process in proton collision with isovalent CO and CS molecules using quantum dynamical close-coupling calculations. Full dimensional ab initio potential energy surfaces have been computed for the ground state for both the systems using internally contracted multireference configuration interaction method and basis sets. Quantum scattering calculations for rotational quenching of isovalent species are studied in the rigid-rotor approximation with CX (X=O, S) bond length fixed at an experimental equilibrium value of 2.138 and 2.900 a.u., respectively. Asymptotic potentials are computed using the dipole and quadrupole moments, and the dipole polarizability components. The resulting long-range potentials with the short-range ab initio interaction potentials have been fitted to study the anisotropy of the rigid-rotor surface using the multipolar expansion coefficients. Rotational quenching cross-section and corresponding rates from j=4 level of CX to lower j' levels have been obtained and found to obey Wigner's threshold law at ultra cold temperatures.

Collision Processes in Methyl Chloride

NASA Astrophysics Data System (ADS)

Pape, Travis W.

Time-resolved, double resonance spectroscopy using infrared pump radiation and millimeter-wave and submillimeter -wave probe radiation (IRMMDR) has been used to study rotational and vibrational collision processes in CH_3 ^{35}Cl and CH_3 ^{37}Cl. A collisional energy transfer model using only five parameters for rotational processes plus those needed for vibrational processes accurately models over 500 IRMMDR time responses for 105 pump-probe combinations, using three pump coincidences and a wide range of probed rotational states. Previous studies in this laboratory revealed that J- and K-changing rotational energy transfer (RET) have vastly different characteristics in CH_3 F. As was found for CH_3F, J-changing rotational collision rates in CH_3 Cl are modeled accurately by both the Statistical Power Gap law and the Infinite Order Sudden approximation using a power law expression for the basis rates. However, in contrast to CH_3F, where all IRMMDR time responses for K-changing collisions have the same shape, many time responses of CH_3 Cl states populated by K-changing collisions contain an additional early-time feature (ETF) that varies with pump and probe state. Nonetheless, a simple generalization of the previously reported model for K-changing collisions is shown to account for all of the additional features observed in CH_3Cl. Rather than observing a fixed temperature for K-changing collisions as was the case for CH_3F, the temperature is found to be a function of time for CH_3 Cl. Moreover, the two new parameters this adds to the RET model are related to known physical quantities. A qualitative argument of K-changing collisions based on a classical picture is offered to explain the difference between the measured J- and K-changing state-to-state rates in CH_3Cl. As was observed in CH_3F, the principal vibrational collision processes are the near -resonant V-swap process, in which two colliding molecules exchange a quantum of vibrational energy, and a nonresonant process that directly moves population from the pumped {bf v}_6 = 1 vibrational state to the {bf v}_3 = 1 vibrational state. A V to T/R process was also measured. Finally, a V-swap process was measured that populates vibrational states of the other isotopic species.

Quantitatively probing water and its isotopomers: from theory to experiments; the contribution of a chemical and astrophysical European network 'Our Astrochemical History'

NASA Astrophysics Data System (ADS)

Wiesenfeld, Laurent

2015-08-01

In order to retrieve actual molecular abundances from astrophysical observations of molecular spectral lines, knowledge of the rotational levels excitation schemes is essential to go beyond Local Thermodynamical Equilibrium. These rates are almost always obtained from theoretical investigations, by computing classical or quantum dynamics of the interaction of molecules with these colliders (roueff2013).Our laboratories have recently calculated a set of collision coefficients characterizing the efficiency of energy transfer between molecular hydrogen of helium and a large variety of interstellar molecules. One of the main goal has been water and its isotopomers, computingrates for H2O, HDO and D2O in collision with H2 (valiron2008,faure2012,daniel2011).We felt it necessary to have a multidisciplinary approach: theoretical on the one hand, experimental on the second. Indeed, excitation coefficient computation is a process involving many codes and approximations. Hence we compared our theoretical results to several experiments: spectroscopy of the H2O-H2 van der Waals complex (vanderavoird 2012), differential cross sections (yang 2010, 2011), pressure broadening (drouin 2012).Thanks to these precise determinations, many water abundances could be quantitatively measured, like the HDO/H2O ratio (coutens 2012).While the excitation of water is by now well understood, much remains to be done for heavier molecules, paving the way to quantitative measures of complex organic molecules . A multi disciplinary approach is necessary, that keeps in mind the necessities of actual astrophysical observations. To do so, we describe the European COST network ‘Our Astrochemical History’ (http://prague2015astrohistory.vscht.cz/) , which brings together specialists of many areas of chemistry together with astronomy, in order to address this kind of problem. It focussses on the molecular evolution towards higher complexity and aim sat delivering new schemes for physical chemistry at large, like chemistry of transient species and photochemistry, in gas or on surfaces.

The dissociative chemisorption of water on Ni(111): Mode- and bond-selective chemistry on metal surfaces

DOE Office of Scientific and Technical Information (OSTI.GOV)

Farjamnia, Azar; Jackson, Bret, E-mail: jackson@chem.umass.edu

A fully quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore the dissociative chemisorption of H{sub 2}O, HOD, and D{sub 2}O on Ni(111). For this late barrier system, excitation of both the bending and stretching modes significantly enhances dissociative sticking. The vibrational efficacies vary somewhat from mode-to-mode but are all relatively close to one, in contrast to methane dissociation, where the behavior is less statistical. Similar to methane dissociation, the motion of lattice atoms near the dissociating molecule can significantly modify the height of the barrier to dissociation, leading to a strong variation in dissociativemore » sticking with substrate temperature. Given a rescaling of the barrier height, our results are in reasonable agreement with measurements of the dissociative sticking of D{sub 2}O on Ni(111), for both laser-excited molecules with one or two quanta of excitation in the antisymmetric stretch and in the absence of laser excitation. Even without laser excitation, the beam contains vibrationally excited molecules populated at the experimental source temperature, and these make significant contributions to the sticking probability. At high collision energies, above the adiabatic barrier heights, our results correlate with these barrier heights and mode softening effects. At lower energies, dissociative sticking occurs primarily via vibrationally nonadiabatic pathways. We find a preference for O–H over O–D bond cleavage for ground state HOD molecules at all but the highest collision energies, and excitation of the O–H stretch gives close to 100% O–H selectivity at lower energies. Excitation of the O–D stretch gives a lower O–D cleavage selectivity, as the interaction with the surface leads to energy transfer from the O–D stretch into the O–H bond, when mode softening makes these vibrations nearly degenerate.« less

Predicting the stochastic guiding of kinesin-driven microtubules in microfabricated tracks: a statistical-mechanics-based modeling approach.

PubMed

Lin, Chih-Tin; Meyhofer, Edgar; Kurabayashi, Katsuo

2010-01-01

Directional control of microtubule shuttles via microfabricated tracks is key to the development of controlled nanoscale mass transport by kinesin motor molecules. Here we develop and test a model to quantitatively predict the stochastic behavior of microtubule guiding when they mechanically collide with the sidewalls of lithographically patterned tracks. By taking into account appropriate probability distributions of microscopic states of the microtubule system, the model allows us to theoretically analyze the roles of collision conditions and kinesin surface densities in determining how the motion of microtubule shuttles is controlled. In addition, we experimentally observe the statistics of microtubule collision events and compare our theoretical prediction with experimental data to validate our model. The model will direct the design of future hybrid nanotechnology devices that integrate nanoscale transport systems powered by kinesin-driven molecular shuttles.

Recent advances in collisional effects on spectra of molecular gases and their practical consequences

NASA Astrophysics Data System (ADS)

Hartmann, Jean-Michel; Tran, Ha; Armante, Raymond; Boulet, Christian; Campargue, Alain; Forget, François; Gianfrani, Livio; Gordon, Iouli; Guerlet, Sandrine; Gustafsson, Magnus; Hodges, Joseph T.; Kassi, Samir; Lisak, Daniel; Thibault, Franck; Toon, Geoffrey C.

2018-07-01

We review progress, since publication of the book ``Collisional effects on molecular spectra: Laboratory experiments and models, consequences for applications" (Elsevier, Amsterdam, 2008), on measuring, modeling and predicting the influence of pressure (ie of intermolecular collisions) on the spectra of gas molecules. We first introduce recently developed experimental techniques of high accuracy and sensitivity. We then complement the aforementioned book by presenting the theoretical approaches, results and data proposed (mostly) in the last decade on the topics of isolated line shapes, line-broadening and -shifting, line-mixing, the far wings and associated continua, and collision-induced absorption. Examples of recently demonstrated consequences of the progress in the description of spectral shapes for some practical applications (metrology, probing of gas media, climate predictions) are then given. Remaining issues and directions for future research are finally discussed.

Energy Scaling of Cold Atom-Atom-Ion Three-Body Recombination

NASA Astrophysics Data System (ADS)

Krükow, Artjom; Mohammadi, Amir; Härter, Arne; Denschlag, Johannes Hecker; Pérez-Ríos, Jesús; Greene, Chris H.

2016-05-01

We study three-body recombination of Ba++Rb +Rb in the mK regime where a single 138Ba+ ion in a Paul trap is immersed into a cloud of ultracold 87Rb atoms. We measure the energy dependence of the three-body rate coefficient k3 and compare the results to the theoretical prediction, k3∝Ecol-3 /4, where Ecol is the collision energy. We find agreement if we assume that the nonthermal ion energy distribution is determined by at least two different micromotion induced energy scales. Furthermore, using classical trajectory calculations we predict how the median binding energy of the formed molecules scales with the collision energy. Our studies give new insights into the kinetics of an ion immersed in an ultracold atom cloud and yield important prospects for atom-ion experiments targeting the s -wave regime.

Vibration-translation energy transfer in anharmonic diatomic molecules. 2: The vibrational quantum number dependence

NASA Technical Reports Server (NTRS)

Mckenzie, R. L.

1975-01-01

A semiclassical model of the inelastic collision between a vibrationally excited anharmonic oscillator and a structureless atom was used to predict the variation of thermally averaged vibration-translation rate coefficients with temperature and initial-state quantum number. Multiple oscillator states were included in a numerical solution for collinear encounters. The results are compared with CO-He experimental values for both ground and excited initial states using several simplified forms of the interaction potential. The numerical model was also used as a basis for evaluating several less complete but analytic models. Two computationally simple analytic approximations were found that successfully reproduced the numerical rate coefficients for a wide range of molecular properties and collision partners. Their limitations were also identified. The relative rates of multiple-quantum transitions from excited states were evaluated for several molecular types.

State-to-State integral cross section for the H+H2O-->H2+OH abstraction reaction.

PubMed

Zhang, Dong H; Xie, Daiqian; Yang, Minghui; Lee, Soo-Y

2002-12-31

The initial state selected time-dependent wave-packet method was extended to calculate the state-to-state integral cross section for the title reaction with H2O in the ground rovibrational state on the potential energy surface of Yang, Zhang, Collins, and Lee. One OH bond length was fixed in the study, which is justifiable for the abstraction reaction, but the remaining 5 degrees of freedom were treated exactly. It was found that the H2 molecule is produced vibrationally cold for collision energy up to 1.6 eV. The OH rotation takes away about 4% of total available energy in the products, while the fraction of energy going to H2 rotation increases with collision energy to about 20% at 1.6 eV.

A novel coarsening mechanism of droplets in immiscible fluid mixtures

NASA Astrophysics Data System (ADS)

Shimizu, Ryotaro; Tanaka, Hajime

2015-06-01

In our daily lives, after shaking a salad dressing, we see the coarsening of oil droplets suspended in vinegar. Such a demixing process is observed everywhere in nature and also of technological importance. For a case of high droplet density, domain coarsening proceeds with inter-droplet collisions and the resulting coalescence. This phenomenon has been explained primarily by the so-called Brownian-coagulation mechanism: stochastic thermal forces exerted by molecules induce random motion of individual droplets, causing accidental collisions and subsequent interface-tension-driven coalescence. Contrary to this, here we demonstrate that the droplet motion is not random, but hydrodynamically driven by the composition Marangoni force due to an interfacial tension gradient produced in each droplet as a consequence of composition correlation among droplets. This alters our physical understanding of droplet coarsening in immiscible liquid mixtures on a fundamental level.

Atomic and molecular data for spacecraft re-entry plasmas

NASA Astrophysics Data System (ADS)

Celiberto, R.; Armenise, I.; Cacciatore, M.; Capitelli, M.; Esposito, F.; Gamallo, P.; Janev, R. K.; Laganà, A.; Laporta, V.; Laricchiuta, A.; Lombardi, A.; Rutigliano, M.; Sayós, R.; Tennyson, J.; Wadehra, J. M.

2016-06-01

The modeling of atmospheric gas, interacting with the space vehicles in re-entry conditions in planetary exploration missions, requires a large set of scattering data for all those elementary processes occurring in the system. A fundamental aspect of re-entry problems is represented by the strong non-equilibrium conditions met in the atmospheric plasma close to the surface of the thermal shield, where numerous interconnected relaxation processes determine the evolution of the gaseous system towards equilibrium conditions. A central role is played by the vibrational exchanges of energy, so that collisional processes involving vibrationally excited molecules assume a particular importance. In the present paper, theoretical calculations of complete sets of vibrationally state-resolved cross sections and rate coefficients are reviewed, focusing on the relevant classes of collisional processes: resonant and non-resonant electron-impact excitation of molecules, atom-diatom and molecule-molecule collisions as well as gas-surface interaction. In particular, collisional processes involving atomic and molecular species, relevant to Earth (N2, O2, NO), Mars (CO2, CO, N2) and Jupiter (H2, He) atmospheres are considered.

Rydberg Molecules for Ion-Atom Scattering in the Ultracold Regime

NASA Astrophysics Data System (ADS)

Schmid, T.; Veit, C.; Zuber, N.; Löw, R.; Pfau, T.; Tarana, M.; Tomza, M.

2018-04-01

We propose a novel experimental method to extend the investigation of ion-atom collisions from the so far studied cold, essentially classical regime to the ultracold, quantum regime. The key aspect of this method is the use of Rydberg molecules to initialize the ultracold ion-atom scattering event. We exemplify the proposed method with the lithium ion-atom system, for which we present simulations of how the initial Rydberg molecule wave function, freed by photoionization, evolves in the presence of the ion-atom scattering potential. We predict bounds for the ion-atom scattering length from ab initio calculations of the interaction potential. We demonstrate that, in the predicted bounds, the scattering length can be experimentally determined from the velocity of the scattered wave packet in the case of 6Li+ = 6Li and from the molecular ion fraction in the case of 7Li+ - 7Li. The proposed method to utilize Rydberg molecules for ultracold ion-atom scattering, here particularized for the lithium ion-atom system, is readily applicable to other ion-atom systems as well.

Rydberg Molecules for Ion-Atom Scattering in the Ultracold Regime.

PubMed

Schmid, T; Veit, C; Zuber, N; Löw, R; Pfau, T; Tarana, M; Tomza, M

2018-04-13

We propose a novel experimental method to extend the investigation of ion-atom collisions from the so far studied cold, essentially classical regime to the ultracold, quantum regime. The key aspect of this method is the use of Rydberg molecules to initialize the ultracold ion-atom scattering event. We exemplify the proposed method with the lithium ion-atom system, for which we present simulations of how the initial Rydberg molecule wave function, freed by photoionization, evolves in the presence of the ion-atom scattering potential. We predict bounds for the ion-atom scattering length from ab initio calculations of the interaction potential. We demonstrate that, in the predicted bounds, the scattering length can be experimentally determined from the velocity of the scattered wave packet in the case of ^{6}Li^{+}-^{6}Li and from the molecular ion fraction in the case of ^{7}Li^{+}-^{7}Li. The proposed method to utilize Rydberg molecules for ultracold ion-atom scattering, here particularized for the lithium ion-atom system, is readily applicable to other ion-atom systems as well.

Hyperthermal Carbon Dioxide Interactions with Self-Assembled Monolayer Surfaces

DTIC Science & Technology

2013-09-08

comparison of the scattering behavior from the liquid and semi-solid surfaces to allow new insight into the pivotal initial step in gas -surface reaction...scattering dynamics of atoms and molecules on liquid and SAM surfaces, in order to deepen the understanding of gas -surface interactions at liquid and... gas - liquid and gas -SAM interface have developed a basic picture of the gas -surface collision dynamics. The previous experiments showed a bimodal

Observation of Single-Protein and DNA Macromolecule Collisions on Ultramicroelectrodes.

PubMed

Dick, Jeffrey E; Renault, Christophe; Bard, Allen J

2015-07-08

Single-molecule detection is the ultimate sensitivity in analytical chemistry and has been largely unavailable in electrochemical analysis. Here, we demonstrate the feasibility of detecting electrochemically inactive single biomacromolecules, such as enzymes, antibodies, and DNA, by blocking a solution redox reaction when molecules adsorb and block electrode sites. By oxidizing a large concentration of potassium ferrocyanide on an ultramicroelectrode (UME, radius ≤150 nm), time-resolved, discrete adsorption events of antibodies, enzymes, DNA, and polystyrene nanospheres can be differentiated from the background by their "footprint". Further, by assuming that the mass transport of proteins to the electrode surface is controlled mainly by diffusion, a size estimate using the Stokes-Einstein relationship shows good agreement of electrochemical data with known protein sizes.

Highly vibrationally excited CO generated in a low-temperature chemical reaction between carbon vapor and molecular oxygen

NASA Astrophysics Data System (ADS)

Jans, E.; Frederickson, K.; Yurkovich, M.; Musci, B.; Rich, J. W.; Adamovich, I. V.

2016-08-01

A chemical flow reactor is used to study the vibrational population distribution of CO produced by a reaction between carbon vapor generated in an arc discharge and molecular oxygen. The results demonstrate formation of highly vibrationally excited CO, up to vibrational level v = 14, at low temperatures, T = 400-450 K, with population inversion at v = 4-7, in a collision-dominated environment, 15-20 Torr. The average vibrational energy per CO molecule formed by the reaction is 0.6-1.2 eV/molecule, which corresponds to 10-20% of reaction enthalpy. The results show feasibility of development of a new CO chemical laser using carbon vapor and oxygen as reactants.

New approximate orientation averaging of the water molecule interacting with the thermal neutron

DOE Office of Scientific and Technical Information (OSTI.GOV)

Markovic, M.I.; Minic, D.M.; Rakic, A.D.

1992-02-01

This paper reports that exactly describing the time of thermal neutron collisions with water molecules, orientation averaging is performed by an exact method (EOA{sub k}) and four approximate methods (two well known and two less known). Expressions for the microscopic scattering kernel are developed. The two well-known approximate orientation averaging methods are Krieger-Nelkin (K-N) and Koppel-Young (K-Y). The results obtained by one of the two proposed approximate orientation averaging methods agree best with the corresponding results obtained by EOA{sub k}. The largest discrepancies between the EOA{sub k} results and the results of the approximate methods are obtained using the well-knowmore » K-N approximate orientation averaging method.« less

Investigation of drift gas selectivity in high resolution ion mobility spectrometry with mass spectrometry detection.

PubMed

Matz, Laura M; Hill, Herbert H; Beegle, Luther W; Kanik, Isik

2002-04-01

Recent studies in electrospray ionization (ESI)/ion mobility spectrometry (IMS) have focussed on employing different drift gases to alter separation efficiency for some molecules. This study investigates four structurally similar classes of molecules (cocaine and metabolites, amphetamines, benzodiazepines, and small peptides) to determine the effect of structure on relative mobility changes in four drift gases (helium, nitrogen, argon, carbon dioxide). Collision cross sections were plotted against drift gas polarizability and a linear relationship was found for the nineteen compounds evaluated in the study. Based on the reduced mobility database, all nineteen compounds could be separated in one of the four drift gases, however, the drift gas that provided optimal separation was specific for the two compounds.

Two-potential approach for electron-molecular collisions at intermediate and high energies - Application to e-N2 scatterings

NASA Technical Reports Server (NTRS)

Choi, B. H.; Poe, R. T.; Sun, J. C.; Shan, Y.

1979-01-01

A general theoretical approach is proposed for the calculation of elastic, vibrational, and rotational transitions for electron-molecule scattering at intermediate and high-electron-impact energies. In this formulation, contributions to the scattering process come from the incoherent sum of two dominant potentials: a short-range shielded nuclear Coulomb potential from individual atomic centers, and a permanent/induced long-range potential. Application to e-N2 scattering from 50-500 eV incident electron energies has yielded good agreement with absolutely calibrated experiments. Comparisons with other theoretical approaches are made. The physical picture as well as the general features of electron-molecule scattering process are discussed within the framework of the two-potential approach.

Dynamics of alkali ions-neutral molecules reactions: Radio frequency-guided beam experimental cross-sections and direct quasiclassical trajectory studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Aguilar, J.; Andres, J. de; Lucas, J. M.

2012-11-27

Different reactive processes taking place in collisions between alkali ions and neutral i-C{sub 3}H{sub 7}Cl molecules in the low (center of mass frame) energy range have been studied using an octopole radiofrequency guided-ion-beam apparatus developed in our laboratory. Cross-section energy dependences for all these reactions have been obtained in absolute units. Ab initio electronic structure calculations for those colliding systems evolving on the ground single potential surface have given relevant information on the main topological features of the surfaces. For some of the reactions a dynamic study by 'on the fly' trajectories has complemented the available experimental and electronic structuremore » information.« less

Thermophoretic force on nonspherical particles in the free-molecule regime

NASA Astrophysics Data System (ADS)

Yu, Song; Wang, Jun; Xia, Guodong; Zong, Luxiang

2018-05-01

The present paper is devoted to studying the thermophoresis of a nonspherical convex particle suspended in a gas with nonuniform temperature distribution in the free-molecule regime. Based on the gas kinetic theory and the assumption of a rigid-body collision for the gas-particle interaction, analytical expressions for the thermophoretic forces are obtained for several typical nonspherical bodies, including cylinders, spheroids, needles, disks, and cuboids. The orientation dependences of the thermophoretic forces and thermophoretic velocities are evaluated based on these expressions. It is found that the influence of the pitching effect of the nonspheres can be significant. The expressions for the orientation-averaged thermophoretic forces are also obtained under the assumption of a uniform particle orientation distribution.

Angular motion of a PAH molecule in interstellar environment

NASA Technical Reports Server (NTRS)

Rouan, D.; Leger, Alain; Omont, A.; Giard, Martin

1989-01-01

Polycyclic aromatic hydrocarbon (PAH) molecules have recently been proposed as an important and hitherto undetected component of the Interstellar Medium (ISM). The theory was based on an explanation of the Unidentified IR Emission Bands by Leger et al. It has already led to a verified prediction on extended galactic and extragalactic emissions measured by IRAS, or by a recent balloon borne experiment. The physics that rules the motion of such molecules in the ISM was studied, taking into account their coupling with the ambient gas, the radiation field (absorption and emission) and the static magnetic field. This is important for many implications of the PAH theory such as the radio emission by these molecules or the expected polarization of their IR emission. A reflection nebulae is considered where the situation is rather well known. Every day life of a mean PAH molecule in such a region is as follows: every 3 hrs a UV photon is absorbed heating the molecule to a thousand degs; the temperature decay due to cooling by IR emission follows then within a few seconds. A collision with a molecule of gas occurs typically once a week, while an H atom is ejected or captured at the same rate. A typical cooling cycle after a heat impulse is given. The PAH molecules studied as representative of the family has typically 50 atoms, a radius of 4.5 A, is circular and has a molecular mass of M = 300; its permanent dipole moment is 3 Debye.

Collisional transfer of population and orientation in sodium potassium

NASA Astrophysics Data System (ADS)

Wolfe, Christopher Matthew

Collisional spectral satellite lines have been identified in recent optical-optical double resonance (OODR) excitation spectra of the NaK molecule. These satellite lines represent both a transfer of population, and a partial preservation of angular momentum orientation, to a rotational level adjacent to the one directly excited by the pump laser beam. A rate equation model was used to study the intensities of these satellite lines as a function of argon pressure and heat pipe oven temperature, in order to separate the collisional effects of argon and potassium atoms (being the most populous species in the vapor by an order of magnitude over the third most populous). Using a fit of this rate equation model to the data, it was found that collisions between NaK and potassium are more likely to transfer population and destroy orientation than argon collisions, and also more likely to transfer population to rotational levels higher in energy than the one being pumped (i.e. a propensity for positive Delta J collisions). Also, collisions between NaK and argon atoms show a propensity toward even-numbered changes in J. In addition to the above study, an analysis of collisional line broadening and velocity-changes in J-changing collisions was performed, showing potassium has a higher line broadening rate coefficient, as well as a smaller velocity change in J-changing collisions, than argon. A program was also written in Fortran 90/95 which solves the density matrix equations of motion in steady state for a coupled system of 3 (or 4) energy levels with their constituent degenerate magnetic sublevels. The solution to these equations yields the populations of each sublevel in steady state, as well as the laser-induced coherences between each sublevel (which are needed to model the polarization spectroscopy lineshape precisely). Development of an appropriate theoretical model for collisional transfer will yield a more rigorous study of the problem than the empirical rate equation model used in the analysis of our experiment.

Rotationally inelastic collisions of He and Ar with NaK: Theory and Experiment

NASA Astrophysics Data System (ADS)

Price, T. J.; Towne, A. C.; Richter, K.; Jones, J.; Hickman, A. P.; Huennekens, J.; Faust, C.; Malenda, R. F.; Ross, A. J.; Crozet, P.; Talbi, D.; Forrey, R. C.

2016-05-01

Rotationally inelastic thermal collisions of NaK A1Σ+ molecules with He and Ar have been studied at Lehigh and Lyon. In both laboratories, a pump laser excites a particular ro-vibrational level A1Σ+ (v , J). Strong transitions from the pumped (v , J) level and weaker transitions from collisionally-populated levels (v ,J' = J + ΔJ) occur. Ratios of line intensities yield information about population and orientation transfer. At Lyon, we also identify v changing collisions. A strong propensity for ΔJ = even transitions is observed for He and Ar. Theoretical calculations are underway; we've calculated He-NaK and Ar-NaK potential surfaces using GAMESS and performed coupled channel scattering calculations for JM -->J'M' transitions. Semiclassical formulas for the cross sections have been obtained and agree well with our quantum mechanical calculations. Using the vector model, where J precesses with polar angle θ about the z-axis, we derived the distribution of final polar angles θ' and final M' states. We identify a special case where the θ' distribution is a Lorentzian centered at θ. Work supported by NSF, XSEDE and CNRS (PICS).

Angular distributions for the inelastic scattering of NO(X2Π ) with O2(X3Σg-)

NASA Astrophysics Data System (ADS)

Brouard, M.; Gordon, S. D. S.; Nichols, B.; Squires, E.; Walpole, V.; Aoiz, F. J.; Stolte, S.

2017-05-01

The inelastic scattering of NO(X2Π ) by O2(X3Σg-) was studied at a mean collision energy of 550 cm-1 using velocity-map ion imaging. The initial quantum state of the NO(X2Π , v = 0, j = 0.5, Ω =0.5 , 𝜖 = -1 , f) molecule was selected using a hexapole electric field, and specific Λ-doublet levels of scattered NO were probed using (1 +1' ) resonantly enhanced multiphoton ionization. A modified "onion-peeling" algorithm was employed to extract angular scattering information from the series of "pancaked," nested Newton spheres arising as a consequence of the rotational excitation of the molecular oxygen collision partner. The extracted differential cross sections for NO(X) f →f and f →e Λ-doublet resolved, spin-orbit conserving transitions, partially resolved in the oxygen co-product rotational quantum state, are reported, along with O2 fragment pair-correlated rotational state population. The inelastic scattering of NO with O2 is shown to share many similarities with the scattering of NO(X) with the rare gases. However, subtle differences in the angular distributions between the two collision partners are observed.

Collision-Induced Infrared Absorption by Hydrogen-Helium gas mixtures at Thousands of Kelvin

NASA Astrophysics Data System (ADS)

Abel, Martin; Frommhold, Lothar; Li, Xiaoping; Hunt, Katharine L. C.

2010-10-01

The interaction-induced absorption by collisional pairs of H2 molecules is an important opacity source in the atmospheres of the outer planets and cool stars ^[1]. The emission spectra of cool white dwarf stars differ significantly in the infrared from the expected blackbody spectra of their cores, which is largely due to absorption by collisional H2--H2, H2--He, and H2--H complexes in the stellar atmospheres. Using quantum-chemical methods we compute the atmospheric absorption from hundreds to thousands of kelvin ^[2]. Laboratory measurements of interaction-induced absorption spectra by H2 pairs exist only at room temperature and below. We show that our results reproduce these measurements closely ^[2], so that our computational data permit reliable modeling of stellar atmosphere opacities even for the higher temperatures ^[2]. [1] L. Frommhold, Collision-Induced Absorption in Gases, Cambridge University Press, Cambridge, New York, 1993 and 2006 [2] Xiaoping Li, Katharine L. C. Hunt, Fei Wang, Martin Abel, and Lothar Frommhold, ``Collision-Induced Infrared Absorption by Molecular Hydrogen Pairs at Thousands of Kelvin'', International Journal of Spectroscopy, vol. 2010, Article ID 371201, 11 pages, 2010. doi: 10.1155/2010/371201

Rotationally inelastic scattering of ND3 with H2 as a probe of the intermolecular potential energy surface

NASA Astrophysics Data System (ADS)

Tkáč, Ondřej; Saha, Ashim K.; Loreau, Jérôme; Ma, Qianli; Dagdigian, Paul J.; Parker, David H.; van der Avoird, Ad; Orr-Ewing, Andrew J.

2015-12-01

Differential cross sections (DCSs) are reported for rotationally inelastic scattering of ND3 with H2, measured using a crossed molecular beam apparatus with velocity map imaging (VMI). ND3 molecules were quantum-state selected in the ground electronic and vibrational levels and, optionally, in the j±k = 11- rotation-inversion level prior to collisions. Inelastic scattering of state-selected ND3 with H2 was measured at the mean collision energy of 580 cm-1 by resonance-enhanced multiphoton ionisation spectroscopy and VMI of ND3 in selected single final j'±k' levels. Comparison of experimental DCSs with close-coupling quantum-mechanical scattering calculations serves as a test of a recently reported ab initio potential energy surface. Calculated integral cross sections reveal the propensities for scattering into various final j'±k' levels of ND3 and differences between scattering by ortho and para H2. Integral and differential cross sections are also computed at a mean collision energy of 430 cm-1 and compared to our recent results for inelastic scattering of state-selected ND3 with He.

The Rate of Intramolecular Loop Formation in DNA and Polypeptides: The Absence of the Diffusion-Controlled Limit and Fractional Power-Law Viscosity Dependence

PubMed Central

Cheng, Ryan R.; Uzawa, Takanori; Plaxco, Kevin W.; Makarov, Dmitrii E.

2010-01-01

The problem of determining the rate of end-to-end collisions for polymer chains has attracted the attention of theorists and experimentalists for more than three decades. The typical theoretical approach to this problem has focused on the case where a collision is defined as any instantaneous fluctuation that brings the chain ends to within a specific capture distance. In this paper, we study the more experimentally relevant case, where the end-to-end collision dynamics are probed by measuring the excited state lifetime of a fluorophore (or other lumiphore) attached to one chain end and quenched by a quencher group attached to the other end. Under this regime, a “contact” is defined not by the chain ends approach to within some sharp cutoff but, instead, typically by an exponentially distance-dependent process. Previous theoretical models predict that, if quenching is sufficiently rapid, a diffusion-controlled limit is attained, where such measurements report on the probe-independent, intrinsic end-to-end collision rate. In contrast, our theoretical considerations, simulations, and an analysis of experimental measurements of loop closure rates in single-stranded DNA molecules all indicate that no such limit exists, and that the measured effective collision rate has a nontrivial, fractional power-law dependence on both the intrinsic quenching rate of the fluorophore and the solvent viscosity. We propose a simple scaling formula describing the effective loop closure rate and its dependence on the viscosity, chain length, and properties of the probes. Previous theoretical results are limiting cases of this more general formula. PMID:19780594

Experimental and ab initio studies of the reactive processes in gas phase i-C{sub 3}H{sub 7}Br and i-C{sub 3}H{sub 7}OH collisions with potassium ions

DOE Office of Scientific and Technical Information (OSTI.GOV)

López, E.; Lucas, J. M.; Andrés, J. de

2014-10-28

Collisions between potassium ions and neutral i-C{sub 3}H{sub 7}Br and i-C{sub 3}H{sub 7}OH, all in their electronic ground state, have been studied in the 0.10–10.00 eV center of mass (CM) collision energy range, using the radiofrequency-guided ion beam technique. In K{sup +} + i-C{sub 3}H{sub 7}Br collisions KHBr{sup +} formation was observed and quantified, while the analogous KH{sub 2}O{sup +} formation in K{sup +} + i-C{sub 3}H{sub 7}OH was hardly detected. Moreover, formation of the ion-molecule adducts and their decomposition leading to C{sub 3}H{sub 7}{sup +} and either KBr or KOH, respectively, have been observed. For all these processes, absolutemore » cross-sections were measured as a function of the CM collision energy. Ab initio structure calculations at the MP2 level have given information about the potential energy surfaces (PESs) involved. In these, different stationary points have been characterized using the reaction coordinate method, their connectivity being ensured by using the intrinsic-reaction-coordinate method. From the measured excitation function for KHBr{sup +} formation the corresponding thermal rate constant at 303 K has been calculated. The topology of the calculated PESs allows an interpretation of the main features of the reaction dynamics of both systems, and in particular evidence the important role played by the potential energy wells in controlling the reactivity for the different reaction channels.« less

Sequential evaporation of water molecules from protonated water clusters: measurement of the velocity distributions of the evaporated molecules and statistical analysis.

PubMed

Berthias, F; Feketeová, L; Abdoul-Carime, H; Calvo, F; Farizon, B; Farizon, M; Märk, T D

2018-06-22

Velocity distributions of neutral water molecules evaporated after collision induced dissociation of protonated water clusters H+(H2O)n≤10 were measured using the combined correlated ion and neutral fragment time-of-flight (COINTOF) and velocity map imaging (VMI) techniques. As observed previously, all measured velocity distributions exhibit two contributions, with a low velocity part identified by statistical molecular dynamics (SMD) simulations as events obeying the Maxwell-Boltzmann statistics and a high velocity contribution corresponding to non-ergodic events in which energy redistribution is incomplete. In contrast to earlier studies, where the evaporation of a single molecule was probed, the present study is concerned with events involving the evaporation of up to five water molecules. In particular, we discuss here in detail the cases of two and three evaporated molecules. Evaporation of several water molecules after CID can be interpreted in general as a sequential evaporation process. In addition to the SMD calculations, a Monte Carlo (MC) based simulation was developed allowing the reconstruction of the velocity distribution produced by the evaporation of m molecules from H+(H2O)n≤10 cluster ions using the measured velocity distributions for singly evaporated molecules as the input. The observed broadening of the low-velocity part of the distributions for the evaporation of two and three molecules as compared to the width for the evaporation of a single molecule results from the cumulative recoil velocity of the successive ion residues as well as the intrinsically broader distributions for decreasingly smaller parent clusters. Further MC simulations were carried out assuming that a certain proportion of non-ergodic events is responsible for the first evaporation in such a sequential evaporation series, thereby allowing to model the entire velocity distribution.

[Excitation transfer between high-lying states in K2 in collisions with ground state K and H2 molecules].

PubMed

Shen, Xiao-Yan; Liu, Jing; Dai, Kang; Shen, Yi-Fan

2010-02-01

Pure potassium vapor or K-H2 mixture was irradiated in a glass fluorescence cell with pulses of 710 nm radiation from an OPO laser, populating K2 (1lambda(g)) state by two-photon absorption. Cross sections for 1lambda(g)-3lambda(g) transfer in K2 were determined using methods of molecular fluorescence. During the experiments with pure K vapor, the cell temperature was varied between 553 and 603 K. The K number density was determined spectroscopically by the white-light absorption measurement in the blue wing of the self-broadened resonance D2 line. The resulting fluorescence included a direct component emitted in the decay of the optically excitation and a sensitized component arising from the collisionally populated state. The decay signal of time-resolved fluorescence from1lambda(g) -->1 1sigma(u)+ transition was monitored. It was seen that just after the laser pulse the fluorescence of the photoexcited level decreased exponentially. The effective lifetimes of the 1lambda(g) state can be resolved. The plot of reciprocal of effective lifetimes of the 1lambda(g) state against K densities yielded the slope that indicated the total cross section for deactivation and the intercept that provided the radiative lifetime of the state. The radiative lifetime (20 +/- 2) ns was obtained. The cross section for deactivation of the K2(1lambda(g)) molecules by collisions with K is (2.5 +/- 0.3) x 10(-14) cm2. The time-resolved intensities of the K23lambda(g) --> 1 3sigma(u)+ (484 nm) line were measured. The radiative lifetime (16.0 +/- 3.2) ns and the total cross section (2.5 +/- 0.6) x 10(-14) cm2 for deactivation of the K2 (3lambda(g)) state can also be determined through the analogous procedure. The time-integrated intensities of 1lambda(g) --> 1 1sigma(u)+ and 3lambda(g) --> 1 3sigma(u)+ transitions were measured. The cross section (1.1 +/- 0.3) x10(-14) cm2 was obtained for K2 (1lambda(g))+ K --> K2 (3lambda(g)) + K collisions. During the experiments with K-H2 mixture, the cell temperature was kept constant at 553 K. The H2 pressure was varied between 40 and 400 Pa. The effects of K2-K collisions could not be neglected. These effects were subtracted out using the results of the pure K experiments. The cross section (2.7 +/- 1.1) x 10(-15) cm2 was obtained for K2 (1lambda(g)) + H2 --> K2 (3lambda(g))+H2 collisions. The cross section is (6.8 +/- 2.7) x 10(-15) cm2 for K2 (3lambda(g)) + H2 --> states out of K2 (3lambda(g)) + H2 collisions.

Studies of electron-molecule collisions - Applications to e-H2O

NASA Technical Reports Server (NTRS)

Brescansin, L. M.; Lima, M. A. P.; Gibson, T. L.; Mckoy, V.; Huo, W. M.

1986-01-01

Elastic differential and momentum transfer cross sections for the elastic scattering of electrons by H2O are reported for collision energies from 2 to 20 eV. These fixed-nuclei static-exchange cross sections were obtained using the Schwinger variational approach. In these studies the exchange potential is directly evaluated and not approximated by local models. The calculated differential cross sections, obtained with a basis set expansion of the scattering wave function, agree well with available experimental data at intermediate and larger angles. As used here, the results cannot adequately describe the divergent cross sections at small angles. An interesting feature of the calculated cross sections, particularly at 15 and 20 eV, is their significant backward peaking. This peaking occurs in the experimentally inaccessible region beyond a scattering angle of 120 deg. The implication of this feature for the determination of momentum transfer cross sections is described.

The atmosphere of a dirty-clathrate cometary nucleus - A two-phase, multifluid model

NASA Astrophysics Data System (ADS)

Marconi, M. L.; Mendis, D. A.

1983-10-01

The dynamical and thermal structure of a dirty-clathrate cometary nucleus' gas atmosphere is presently given a self-consistent, transonic multifluid solution in which, although the heavy neutron and ion species are treated as a single fluid in the collision-dominated region, the photoproduced H is treated separately. The thermal profile of the atmosphere thus obtained is entirely different from those predicted by the earlier, single-fluid models as well as the multifluid models which assumed equipartition of energy between electrons and ions. While the electron gas, like the neutrals and the ions, cools due to expansion, its main mode of energy loss in the inner coma is by way of inelastic collisions with the predominant H2O molecule. The high electron temperature in the outer coma also decreases the efficiency of electron removal by dissociative recombination, thereby increasing electron density throughout the coma.

Charge exchange between two nearest neighbour ions immersed in a dense plasma

NASA Astrophysics Data System (ADS)

Sauvan, P.; Angelo, P.; Derfoul, H.; Leboucher-Dalimier, E.; Devdariani, A.; Calisti, A.; Talin, B.

1999-04-01

In dense plasmas the quasimolecular model is relevant to describe the radiative properties: two nearest neighbor ions remain close to each other during a time scale of the order of the emission time. Within the frame of a quasistatic approach it has been shown that hydrogen-like spectral line shapes can exhibit satellite-like features. In this work we present the effect on the line shapes of the dynamical collision between the two ions exchanging transiently their bound electron. This model is suitable for the description of the core, the wings and the red satellite-like features. It is post-processed to the self consistent code (IDEFIX) giving the adiabatic transition energies and the oscillator strengths for the transient molecule immersed in a dense free electron bath. It is shown that the positions of the satellites are insensitive to the dynamics of the ion-ion collision. Results for fluorine Lyβ are presented.

Dissociative electron attachment to C{sub 2}F{sub 5} radicals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Haughey, Sean A.; Field, Thomas A.; Langer, Judith

Dissociative electron attachment to the reactive C{sub 2}F{sub 5} molecular radical has been investigated with two complimentary experimental methods; a single collision beam experiment and a new flowing afterglow Langmuir probe technique. The beam results show that F{sup -} is formed close to zero electron energy in dissociative electron attachment to C{sub 2}F{sub 5}. The afterglow measurements also show that F{sup -} is formed in collisions between electrons and C{sub 2}F{sub 5} molecules with rate constants of 3.7 Multiplication-Sign 10{sup -9} cm{sup 3} s{sup -1} to 4.7 Multiplication-Sign 10{sup -9} cm{sup 3} s{sup -1} at temperatures of 300-600 K. Themore » rate constant increases slowly with increasing temperature, but the rise observed is smaller than the experimental uncertainty of 35%.« less

Ionization, evaporation and fragmentation of C60 in collisions with highly charged C, O and F ions—effect of projectile charge state.

NASA Astrophysics Data System (ADS)

Kelkar, A. H.; Misra, D.; Tribedi, L. C.

2007-09-01

We study the various inelastic processes such ionization, fragmentation and evaporation of C60 molecule in collisions with fast heavy ions. We have used 2.33 MeV/u C, O and F projectile ion beams. Various ionization and fragmentation products were detected using time-of-flight mass spectrometer. The multiply charged C60r+ ions were detected for maximum r = 4. The projectile charge state (qp) dependence of the single and double ionization cross sections is well reproduced by a model based on the giant dipole plasmon resonance (GDPR). The qp-dependence of the fragmentation yields, was found to be linear. Variation of relative yields of the evaporation products of C602+ (i.e. C582+, C562+ etc) and C603+ (i.e. C583+, C563+ etc) with qp has also been investigated for various projectiles.

Collisional Removal of O2 (c(sup 1) Sigma(sup-)(sub u), nu=9) by O2, N2, and He

NASA Technical Reports Server (NTRS)

Copeland, Richard A.; Knutsen, Karen; Onishi, Marc E.; Yalcin, Talat

1996-01-01

The collisional removal Of 02 molecules in selected vibrational levels of the c state is studied using a two-laser double-resonance technique. The output of the first laser excites the 02 to nu = 9 or 10 of the c Sigma - state, and the ultraviolet output of the second laser monitors specific rovibrational levels via resonance-enhanced ionization. The temporal evolution of the c Sigma u state vibrational level is observed by scanning the time delay between the two pulsed lasers. As the rate constants for 02 and N2 are similar in magnitude, N2 collisions dominate the removal rate in the earth's atmosphere. For v= 10 colliding with 02, we find a removal rate constant that is 2-5 times that for v=9 and that single quantum collision cascade is an important pathway for removal.

Kinetic-energy release distributions of fragment anions from collisions of potassium atoms with D-Ribose and tetrahydrofuran*

NASA Astrophysics Data System (ADS)

Rebelo, André; Cunha, Tiago; Mendes, Mónica; da Silva, Filipe Ferreira; García, Gustavo; Limão-Vieira, Paulo

2016-06-01

Kinetic-energy release distributions have been obtained from the width and shapes of the time-of-flight (TOF) negative ion mass peaks formed in collisions of fast potassium atoms with D-Ribose (DR) and tetrahydrofuran (THF) molecules. Recent dissociative ion-pair formation experiments yielding anion formation have shown that the dominant fragment from D-Ribose is OH- [D. Almeida, F. Ferreira da Silva, G. García, P. Limão-Vieira, J. Chem. Phys. 139, 114304 (2013)] whereas in the case of THF is O- [D. Almeida, F. Ferreira da Silva, S. Eden, G. García, P. Limão-Vieira, J. Phys. Chem. A 118, 690 (2014)]. The results for DR and THF show an energy distribution profile reminiscent of statistical degradation via vibrational excitation and partly due to direct transformation of the excess energy in translational energy.

Recognizing Single Collisions of PtCl6(2-) at Femtomolar Concentrations on Ultramicroelectrodes by Nucleating Electrocatalytic Clusters.

PubMed

Dick, Jeffrey E; Bard, Allen J

2015-11-04

We report the electrodeposition of electrocatalytic clusters of platinum from femtomolar platinate solutions. An inert carbon fiber ultramicroelectrode (UME) was held at a potential where proton reduction was unfavorable on carbon but favorable on platinum in a 1 M sulfuric acid solution. Upon addition of femtomolar amounts of hexachloroplatinic acid, which will also reduce to Pt(0) at the applied potential on the carbon fiber UME, cathodic blips were observed in the amperometric i-t response. These blips correspond to the reduction of protons to molecular hydrogen at the small platinum clusters followed by a rapid deactivation likely due to hydrogen bubble formation. On average, these current spikes occur when five platinum atoms have been formed on the electrode, as determined by a comparative analysis of experimental cathodic blips and calculated hexachloroplatinate molecule collision frequencies.

Stereodynamics in NO(X) + Ar inelastic collisions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brouard, M., E-mail: mark.brouard@chem.ox.ac.uk; Chadwick, H.; Gordon, S. D. S.

2016-06-14

The effect of orientation of the NO(X) bond axis prior to rotationally inelastic collisions with Ar has been investigated experimentally and theoretically. A modification to conventional velocity-map imaging ion optics is described, which allows the orientation of hexapole state-selected NO(X) using a static electric field, followed by velocity map imaging of the resonantly ionized scattered products. Bond orientation resolved differential cross sections are measured experimentally for a series of spin-orbit conserving transitions and compared with quantum mechanical calculations. The agreement between experimental results and those from quantum mechanical calculations is generally good. Parity pairs, which have previously been observed inmore » collisions of unpolarized NO with various rare gases, are not observed due to the coherent superposition of the two j = 1/2, Ω = 1/2 Λ-doublet levels in the orienting field. The normalized difference differential cross sections are found to depend predominantly on the final rotational state, and are not very sensitive to the final Λ-doublet level. The differential steric effect has also been investigated theoretically, by means of quantum mechanical and classical calculations. Classically, the differential steric effect can be understood by considering the steric requirement for different types of trajectories that contribute to different regions of the differential cross section. However, classical effects cannot account quantitatively for the differential steric asymmetry observed in NO(X) + Ar collisions, which reflects quantum interference from scattering at either end of the molecule. This quantum interference effect is dominated by the repulsive region of the potential.« less

Electron Collisions in our Atmosphere — How the Microscopic Drives the Macroscopic

NASA Astrophysics Data System (ADS)

Buckman, S. J.; Brunger, M. J.; Campbell, L.; Jelisavcic, M.; Petrovic, Z. Lj.

2005-05-01

Recent measurements of low energy, absolute electron scattering cross sections for vibrational excitation of NO have been used to update the cross set used for modeling atmospheric auroral processes. These new cross sections, which highlight the role that intermediate negative ions (resonances) play at energies below 5 eV in mediating vibrational excitation, also indicate that electron-driven processes play an important role in the infrared (˜5 um) auroral emissions from the NO molecule.

From Nanoscale Systems to Ultracold Atoms and Molecules, and Back

DTIC Science & Technology

2016-08-05

H. Jing, C. Raman, P. Meystre. Optical control of a quantum rotor , Physical Review A, (03 2013): 0. doi: 10.1103/PhysRevA.87.031601 Huatang Tan...study of proposed interferometric gravitational wave detectors in the 1970s and 1980s (and which resulted to the first direct detection of...gravitational waves originating from the collision of massive blackholes by the LIGO gravitational wave antennas in 2015.) In parallel to these kilometer-size

Molecular spectroscopy and collisional excitation. [in astrophysics

NASA Technical Reports Server (NTRS)

Green, S.

1975-01-01

The paper examines the basic principles underlying the molecular transitions responsible for interstellar molecular spectra. The energy levels of molecules are discussed in detail with special attention given to the Born-Oppenheimer approximation, the electronic Hamiltonian, and the parameters of vibrational and rotational energy. The probabilities for radiative and collisional transitions are calculated. A brief review of techniques for molecular spectroscopy is presented along with methods used to determine collision cross sections on both an experimental and a theoretical basis.

Valence ionized states of iron pentacarbonyl and eta5-cyclopentadienyl cobalt dicarbonyl studied by symmetry-adapted cluster-configuration interaction calculation and collision-energy resolved Penning ionization electron spectroscopy.

PubMed

Fukuda, Ryoichi; Ehara, Masahiro; Nakatsuji, Hiroshi; Kishimoto, Naoki; Ohno, Koichi

2010-02-28

Valence ionized states of iron pentacarbonyl Fe(CO)(5) and eta(5)-cyclopentadienyl cobalt dicarbonyl Co(eta(5)-C(5)H(5))(CO)(2) have been studied by ultraviolet photoelectron spectroscopy, two-dimensional Penning ionization electron spectroscopy (2D-PIES), and symmetry-adapted cluster-configuration interaction calculations. Theory provided reliable assignments for the complex ionization spectra of these molecules, which have metal-carbonyl bonds. Theoretical ionization energies agreed well with experimental observations and the calculated wave functions could explain the relative intensities of PIES spectra. The collision-energy dependence of partial ionization cross sections (CEDPICS) was obtained by 2D-PIES. To interpret these CEDPICS, the interaction potentials between the molecules and a Li atom were examined in several coordinates by calculations. The relation between the slope of the CEDPICS and the electronic structure of the ionized states, such as molecular symmetry and the spatial distribution of ionizing orbitals, was analyzed. In Fe(CO)(5), an attractive interaction was obtained for the equatorial CO, while the interaction for the axial CO direction was repulsive. For Co(eta(5)-C(5)H(5))(CO)(2), the interaction potential in the direction of both Co-C-O and Co-Cp ring was attractive. These anisotropic interactions and ionizing orbital distributions consistently explain the relative slopes of the CEDPICS.

Geometric phase effects in ultracold hydrogen exchange reaction

DOE PAGES

Hazra, Jisha; Kendrick, Brian K.; Balakrishnan, Naduvalath

2016-10-14

The role of the geometric phase effect on chemical reaction dynamics is explored by examining the hydrogen exchange process in the fundamental H+HD reaction. Results are presented for vibrationally excited HD molecules in the v = 4 vibrational level and for collision energies ranging from 1 μK to 100 K. It is found that, for collision energies below 3 K, inclusion of the geometric phase leads to dramatic enhancement or suppression of the reaction rates depending on the final quantum state of the HD molecule. The effect was found to be the most prominent for rotationally resolved integral and differential cross sections but it persists to a lesser extent in the vibrationally resolved and total reaction rate coefficients. However, no significant GP effect is present in the reactive channel leading to the D+H 2 product or in the D+H 2more » $$(v=4,j=0)\\,\\to $$ HD+H reaction. A simple interference mechanism involving inelastic (nonreactive) and exchange scattering amplitudes is invoked to account for the observed GP effects. The computed results also reveal a shape resonance in the H+HD reaction near 1 K and the GP effect is found to influence the magnitude of the resonant part of the cross section. In conclusion, experimental detection of the resonance may allow a sensitive probe of the GP effect in the H+HD reaction.« less

Infrared monitoring of the Space Station environment

NASA Technical Reports Server (NTRS)

Kostiuk, Theodor; Jennings, Donald E.; Mumma, Michael J.

1988-01-01

The measurement and monitoring of infrared emission in the environment of the Space Station has a twofold importance - for the study of the phenomena itself and as an aid in planning and interpreting Station based infrared experiments. Spectral measurements of the infrared component of the spacecraft glow will, along with measurements in other spectral regions, provide data necessary to fully understand and model the physical and chemical processes producing these emissions. The monitoring of the intensity of these emissions will provide background limits for Space Station based infrared experiments and permit the determination of optimum instrument placement and pointing direction. Continuous monitoring of temporal changes in the background radiation (glow) will also permit better interpretation of Station-based infrared earth sensing and astronomical observations. The primary processes producing infrared emissions in the Space Station environment are: (1) Gas phase excitations of Station generated molecules ( e.g., CO2, H2O, organics...) by collisions with the ambient flux of mainly O and N2. Molecular excitations and generation of new species by collisions of ambient molecules with Station surfaces. They provide a list of resulting species, transition energies, excitation cross sections and relevant time constants. The modeled spectrum of the excited species occurs primarily at wavelengths shorter than 8 micrometer. Emissions at longer wavelengths may become important during rocket firing or in the presence of dust.

Hydrodynamic and Nonhydrodynamic Contributions to the Bimolecular Collision Rates of Solute Molecules in Supercooled Bulk Water

PubMed Central

2015-01-01

Bimolecular collision rate constants of a model solute are measured in water at T = 259–303 K, a range encompassing both normal and supercooled water. A stable, spherical nitroxide spin probe, perdeuterated 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl, is studied using electron paramagnetic resonance spectroscopy (EPR), taking advantage of the fact that the rotational correlation time, τR, the mean time between successive spin exchanges within a cage, τRE, and the long-time-averaged spin exchange rate constants, Kex, of the same solute molecule may be measured independently. Thus, long- and short-time translational diffusion behavior may be inferred from Kex and τRE, respectively. In order to measure Kex, the effects of dipole–dipole interactions (DD) on the EPR spectra must be separated, yielding as a bonus the DD broadening rate constants that are related to the dephasing rate constant due to DD, Wdd. We find that both Kex and Wdd behave hydrodynamically; that is to say they vary monotonically with T/η or η/T, respectively, where η is the shear viscosity, as predicted by the Stokes–Einstein equation. The same is true of the self-diffusion of water. In contrast, τRE does not follow hydrodynamic behavior, varying rather as a linear function of the density reaching a maximum at 276 ± 2 K near where water displays a maximum density. PMID:24874024

A Century of Progress in Molecular Mass Spectrometry

NASA Astrophysics Data System (ADS)

McLafferty, Fred W.

2011-07-01

The first mass spectrum of a molecule was measured by J.J. Thomson in 1910. Mass spectrometry (MS) soon became crucial to the study of isotopes and atomic weights and to the development of atomic weapons for World War II. Its notable applications to molecules began with the quantitative analysis of light hydrocarbons during World War II. When I joined the Dow Chemical Company in 1950, MS was not favored by organic chemists. This situation improved only with an increased understanding of gaseous ion chemistry, which was obtained through the use of extensive reference data. Gas chromatography-MS was developed in 1956, and tandem MS was first used a decade later. In neutralization-reionization MS, an unusual, unstable species is prepared by ion-beam neutralization and characterized by reionization. Electrospray ionization of a protein mixture produces its corresponding ionized molecules. In top-down proteomics, ions from an individual component can be mass separated and subjected to collision-activated and electron-capture dissociation to provide extensive sequence information.

Greenhouse effect in planetary atmospheres caused by molecular symmetry breaking in intermolecular interactions

NASA Astrophysics Data System (ADS)

Vigasin, A. A.; Mokhov, I. I.

2017-03-01

It is believed that the greenhouse effect is related to the parameters of absorption spectra of polyatomic molecules, usually trace gases, in planetary atmospheres. The main components of all known atmospheres of celestial bodies are symmetrical molecules that do not possess the dipole-allowed purely rotational (and in the case of diatomic molecules, vibrational-rotational) absorption spectrum. Upon increased pressure, a weak absorption appears, induced by intermolecular interaction, which can lead to a greenhouse effect. The contribution of the induced absorption in radiative forcing of a dense atmosphere may amount to a few or even tens of W/m2. In conditions typical for the atmospheres of terrestrial planets (including paleoatmospheres), the collision-induced absorption and associated greenhouse effect may lead to an increase in surface temperature above the freezing point of water. There is a correlation between the temperature of an atmosphere and the intermolecular bonding energy of gases that dominate in planetary atmospheres of the Solar System.

Kinetics and dynamics of near-resonant vibrational energy transfer in gas ensembles of atmospheric interest

NASA Astrophysics Data System (ADS)

McCaffery, Anthony J.

2018-03-01

This study of near-resonant, vibration-vibration (V-V) gas-phase energy transfer in diatomic molecules uses the theoretical/computational method, of Marsh & McCaffery (Marsh & McCaffery 2002 J. Chem. Phys. 117, 503 (doi:10.1063/1.1489998)) The method uses the angular momentum (AM) theoretical formalism to compute quantum-state populations within the component molecules of large, non-equilibrium, gas mixtures as the component species proceed to equilibration. Computed quantum-state populations are displayed in a number of formats that reveal the detailed mechanism of the near-resonant V-V process. Further, the evolution of quantum-state populations, for each species present, may be followed as the number of collision cycles increases, displaying the kinetics of evolution for each quantum state of the ensemble's molecules. These features are illustrated for ensembles containing vibrationally excited N2 in H2, O2 and N2 initially in their ground states. This article is part of the theme issue `Modern theoretical chemistry'.

A new time of flight mass spectrometer for absolute dissociative electron attachment cross-section measurements in gas phase

NASA Astrophysics Data System (ADS)

Chakraborty, Dipayan; Nag, Pamir; Nandi, Dhananjay

2018-02-01

A new time of flight mass spectrometer (TOFMS) has been developed to study the absolute dissociative electron attachment (DEA) cross section using a relative flow technique of a wide variety of molecules in gas phase, ranging from simple diatomic to complex biomolecules. Unlike the Wiley-McLaren type TOFMS, here the total ion collection condition has been achieved without compromising the mass resolution by introducing a field free drift region after the lensing arrangement. The field free interaction region is provided for low energy electron molecule collision studies. The spectrometer can be used to study a wide range of masses (H- ion to few hundreds atomic mass unit). The mass resolution capability of the spectrometer has been checked experimentally by measuring the mass spectra of fragment anions arising from DEA to methanol. Overall performance of the spectrometer has been tested by measuring the absolute DEA cross section of the ground state SO2 molecule, and the results are satisfactory.

Translational, rotational and vibrational relaxation dynamics of a solute molecule in a non-interacting solvent.

PubMed

Grubb, Michael P; Coulter, Philip M; Marroux, Hugo J B; Hornung, Balazs; McMullen, Ryan S; Orr-Ewing, Andrew J; Ashfold, Michael N R

2016-11-01

Spectroscopically observing the translational and rotational motion of solute molecules in liquid solutions is typically impeded by their interactions with the solvent, which conceal spectral detail through linewidth broadening. Here we show that unique insights into solute dynamics can be made with perfluorinated solvents, which interact weakly with solutes and provide a simplified liquid environment that helps to bridge the gap in our understanding of gas- and liquid-phase dynamics. Specifically, we show that in such solvents, the translational and rotational cooling of an energetic CN radical can be observed directly using ultrafast transient absorption spectroscopy. We observe that translational-energy dissipation within these liquids can be modelled through a series of classic collisions, whereas classically simulated rotational-energy dissipation is shown to be distinctly faster than experimentally measured. We also observe the onset of rotational hindering from nearby solvent molecules, which arises as the average rotational energy of the solute falls below the effective barrier to rotation induced by the solvent.

Electron and Ion Reactions in Molecular Solids: from astrochemistry to radiobiology

NASA Astrophysics Data System (ADS)

Huels, Michael A.

2001-05-01

Wherever ionizing radiation interacts with matter, it initiates reaction cascades involving ions, radicals, and ballistic secondary electrons; these reactions occur on fs time-scales, and may lead to substantial physical and chemical modifications of a medium. Here I present measurements of 0-80 eV electron and ion reactions in condensed films ranging from simple to complex, and astrophysical to biological in nature. Targets contain either: small molecules, hydrocarbons of increasing complexity (incl. bases, sugars, single/double stranded DNA), molecules on rare gas matrices, or mixed cryogenic films resembling astrophysical or planetary surface ices containing O2, H2O, methane, and aromatic hydrocarbons. The basic electron or ion reaction mechanisms and pathways are found to be fundamentally universal, but are modulated by the physical and chemical nature of the medium; depending on the latter, a reaction cascade may lead to different end-points, e.g. a decrease in molecular complexity via molecular fragmentations, or increases in complexity via secondary ion collision induced synthesis of larger molecules in hydrocarbon rich surface ices.

Advances in positron and electron scattering*

NASA Astrophysics Data System (ADS)

Limão-Vieira, Paulo; García, Gustavo; Krishnakumar, E.; Petrović, Zoran; Sullivan, James; Tanuma, Hajime

2016-10-01

The topical issue on Advances in Positron and Electron Scattering" combines contributions from POSMOL 2015 together with others devoted to celebrate the unprecedented scientific careers of our loyal colleagues and trusted friends Steve Buckman (Australian National University, Australia) and Michael Allan (University of Fribourg, Switzerland) on the occasion of their retirements. POSMOL 2015, the XVIII International Workshop on Low-Energy Positron and Positronium Physics and the XIX International Symposium on Electron-Molecule Collisions and Swarms, was held at Universidade NOVA de Lisboa, Lisboa, Portugal, from 17-20 July 2015. The international workshop and symposium allowed to achieve a very privileged forum of sharing and developing our scientific expertise on current aspects of positron, positronium and antiproton interactions with electrons, atoms, molecules and solid surfaces, and related topics, as well as electron interactions with molecules in both gaseous and condensed phases. Particular topics include studies of electron interactions with biomolecules, electron induced surface chemistry and the study of plasma processes. Recent developments in the study of swarms are also fully addressed.

Making a molecular gas in the quantum regime

NASA Astrophysics Data System (ADS)

Ni, Kang-Kuen

2017-04-01

Ultracold molecules are exciting systems for a large range of scientific explorations including studies of novel phases of matter and precision measurement. In this talk, I will present a brief story of the first quantum gas of molecules, KRb, created under my PhD advisor, Deborah Jin, in 2008. A complete surprise was finding ultracold chemistry in such a system through measurements of reactant losses. In particular, long-range physics that determines KRb reactant collision rates, including van der Waals interactions, quantum statistics, and dipolar interactions, were studied extensively. However, the short-range behavior of these chemical reactions remains unknown. A legacy of her work is carried out in my lab at Harvard, where we are integrating physical chemistry tools with cold atom techniques to study ultracold chemistry with KRb molecules. In particular, we aim to elucidate the four-center reaction 2 KRb ->K2 + Rb2 by detecting the reaction products through ionization - both identify the product species and mapping out their complete quantum states.

Stochastic simulation of biological reactions, and its applications for studying actin polymerization.

PubMed

Ichikawa, Kazuhisa; Suzuki, Takashi; Murata, Noboru

2010-11-30

Molecular events in biological cells occur in local subregions, where the molecules tend to be small in number. The cytoskeleton, which is important for both the structural changes of cells and their functions, is also a countable entity because of its long fibrous shape. To simulate the local environment using a computer, stochastic simulations should be run. We herein report a new method of stochastic simulation based on random walk and reaction by the collision of all molecules. The microscopic reaction rate P(r) is calculated from the macroscopic rate constant k. The formula involves only local parameters embedded for each molecule. The results of the stochastic simulations of simple second-order, polymerization, Michaelis-Menten-type and other reactions agreed quite well with those of deterministic simulations when the number of molecules was sufficiently large. An analysis of the theory indicated a relationship between variance and the number of molecules in the system, and results of multiple stochastic simulation runs confirmed this relationship. We simulated Ca²(+) dynamics in a cell by inward flow from a point on the cell surface and the polymerization of G-actin forming F-actin. Our results showed that this theory and method can be used to simulate spatially inhomogeneous events.

Tandem differential mobility analysis-mass spectrometry reveals partial gas-phase collapse of the GroEL complex.

PubMed

Hogan, Christopher J; Ruotolo, Brandon T; Robinson, Carol V; Fernandez de la Mora, Juan

2011-04-07

A parallel-plate differential mobility analyzer and a time-of-flight mass spectrometer (DMA-MS) are used in series to measure true mobility in dry atmospheric pressure air for mass-resolved electrosprayed GroEL tetradecamers (14-mers; ~800 kDa). Narrow mobility peaks are found (2.6-2.9% fwhm); hence, precise mobilities can be obtained for these ions without collisional activation, just following their generation by electrospray ionization. In contrast to previous studies, two conformers are found with mobilities (Z) differing by ~5% at charge state z ~ 79. By extrapolating to small z, a common mobility/charge ratio Z(0)/z = 0.0117 cm(2) V(-1) s(-1) is found for both conformers. When interpreted as if the GroEL ion surface were smooth and the gas molecule-protein collisions were perfectly elastic and specular, this mobility yields an experimental collision cross section, Ω, 11% smaller than in an earlier measurement, and close to the cross section, A(C,crystal), expected for the crystal structure (determined by a geometric approximation). However, the similarity between Ω and A(C,crystal) does not imply a coincidence between the native and gas-phase structures. The nonideal nature of protein-gas molecule collisions introduces a drag enhancement factor, ξ = 1.36, with which the true cross section A(C) is related to Ω via A(C) = Ω/ξ. Therefore, A(C) for GroEL 14-mer ions determined by DMA measurements is 0.69A(C,crystal). The factor 1.36 used here is based on the experimental Stokes-Millikan equation, as well as on prior and new numerical modeling accounting for multiple scattering events via exact hard-sphere scattering calculations. Therefore, we conclude that the gas-phase structure of the GroEL complex as electrosprayed is substantially more compact than the corresponding X-ray crystal structure.

Normal and Anomalous Diffusion: An Analytical Study Based on Quantum Collision Dynamics and Boltzmann Transport Theory.

PubMed

Mahakrishnan, Sathiya; Chakraborty, Subrata; Vijay, Amrendra

2016-09-15

Diffusion, an emergent nonequilibrium transport phenomenon, is a nontrivial manifestation of the correlation between the microscopic dynamics of individual molecules and their statistical behavior observed in experiments. We present a thorough investigation of this viewpoint using the mathematical tools of quantum scattering, within the framework of Boltzmann transport theory. In particular, we ask: (a) How and when does a normal diffusive transport become anomalous? (b) What physical attribute of the system is conceptually useful to faithfully rationalize large variations in the coefficient of normal diffusion, observed particularly within the dynamical environment of biological cells? To characterize the diffusive transport, we introduce, analogous to continuous phase transitions, the curvature of the mean square displacement as an order parameter and use the notion of quantum scattering length, which measures the effective interactions between the diffusing molecules and the surrounding, to define a tuning variable, η. We show that the curvature signature conveniently differentiates the normal diffusion regime from the superdiffusion and subdiffusion regimes and the critical point, η = ηc, unambiguously determines the coefficient of normal diffusion. To solve the Boltzmann equation analytically, we use a quantum mechanical expression for the scattering amplitude in the Boltzmann collision term and obtain a general expression for the effective linear collision operator, useful for a variety of transport studies. We also demonstrate that the scattering length is a useful dynamical characteristic to rationalize experimental observations on diffusive transport in complex systems. We assess the numerical accuracy of the present work with representative experimental results on diffusion processes in biological systems. Furthermore, we advance the idea of temperature-dependent effective voltage (of the order of 1 μV or less in a biological environment, for example) as a dynamical cause of the perpetual molecular movement, which eventually manifests as an ordered motion, called the diffusion.

Theoretical studies of solar-pumped lasers

NASA Technical Reports Server (NTRS)

Harries, W. L.

1983-01-01

Metallic vapor lasers of Na2 and Li2 are examined as solar energy converters. The absorbed photons cause transitions to vibrational-rotational levels in an upper electronic state. With broad band absorption the resultant levels can have quantum numbers considerably higher than the upper lasing level. The excited molecule then relaxes to the upper lasing level which is one of the lower vibrational levels in the upper electronic state. The relaxation occurs from collisions, provided the molecule is not quenched into the ground level electronic state. Lasing occurs with a transition to a vibrational level in the lower electronic state. Rough estimates of solar power efficiencies are 1 percent for Na2 and probably a similar figure for Li2. The nondissociative lasers from a family distinct from materials which dissociate to yield an excited atom.

Born Oppenheimer potential energy for interaction of antihydrogen with molecular hydrogen

NASA Astrophysics Data System (ADS)

Strasburger, Krzysztof

2005-09-01

Inelastic collisions with hydrogen molecules are claimed to be an important channel of antihydrogen (\\overlineH) losses (Armour and Zeman 1999 Int. J. Quantum Chem. 74 645). In the present work, interaction energies for the H_{2}\\--\\overlineH system in the ground state have been calculated within the Born-Oppenheimer approximation. The leptonic problem was solved variationally with the basis of explicitly correlated Gaussian functions. The geometry of H2 was fixed at equilibrium geometry and the \\overlineH atom approached the molecule from two directions—along or perpendicularly to the bond axis. Purely attractive potential energy curve has been obtained for the first nuclear configuration, while a local maximum (lower than the energy at infinite separation) has been found for the second one.

Method and source for producing a high concentration of positively charged molecular hydrogen or deuterium ions

DOEpatents

Ehlers, Kenneth W.; Leung, Ka-Ngo

1988-01-01

A high concentration of positive molecular ions of hydrogen or deuterium gas is extracted from a positive ion source having a short path length of extracted ions, relative to the mean free path of the gas molecules, to minimize the production of other ion species by collision between the positive ions and gas molecules. The ion source has arrays of permanent magnets to produce a multi-cusp magnetic field in regions remote from the plasma grid and the electron emitters, for largely confining the plasma to the space therebetween. The ion source has a chamber which is short in length, relative to its transverse dimensions, and the electron emitters are at an even shorter distance from the plasma grid, which contains one or more extraction apertures.

Applicability of modified effective-range theory to positron-atom and positron-molecule scattering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Idziaszek, Zbigniew; Karwasz, Grzegorz; Instytut Fizyki, Uniwersytet Mikolaja Kopernika, 87-100 Torun

2006-06-15

We analyze low-energy scattering of positrons on Ar atoms and N{sub 2} molecules using the modified effective-range theory (MERT) developed by O'Malley, et al. [J. Math. Phys. 2, 491 (1961)]. We use the formulation of MERT based on exact solutions of the Schroedinger equation with polarization potential rather than low-energy expansions of phase shifts into momentum series. We show that MERT describes the experimental data well, provided that effective-range expansion is performed both for s- and p-wave scattering, which dominate in the considered regime of positron energies (0.4-2 eV). We estimate the values of the s-wave scattering length and themore » effective range for e{sup +}-Ar and e{sup +}-N{sub 2} collisions.« less

Double photoionization of atoms

NASA Astrophysics Data System (ADS)

Wiedenhoeft, Marco

2003-10-01

Double photoionization studies of atoms and molecules are new state-of-the-art studies providing a deeper knowledge of multi-electron excitations. This type of work advances the understanding of many-body problems. Double photoionization of atoms is of great interest to learn about electron-electron correlation and relaxation effects in atoms and molecules. In order to study double photoionization processes, a new electron-electron coincidence apparatus was built to carry out the measurements. I will present the apparatus I built as well as the results of the measurement of the triply-differential-cross-section (TDCS) for the predicted interference and Post-Collision-Interaction (PCI) effects in the Xenon N5O2,3 O2,3 Auger decay after 4d5/2 photoionization. Furthermore I present measurements for direct double photoionization of Helium at various photon energies.

Vibration-rotation transfer in molecular super rotors

NASA Astrophysics Data System (ADS)

McCaffery, Anthony J.

2000-12-01

The collisional behavior of (X)6Li2 molecules in very high rotational levels of v=0 is considered. Highly efficient vibration-rotation transfer is predicted in these "super rotors" particularly when the conditions for quasiresonant transfer are fulfilled. This requires simultaneous near-resonance in energy and in angular momentum. Values of Δj for which quasiresonant vibration-rotation transfer (QRT) occurs become smaller as initial rotor state increases and transfer is likely to become particularly fast for Δj=2, predicted to occur when ji=130. This behavior is contrasted with the inefficiency of pure rotational transfer within the v=0 level for fast-rotating molecules. QRT will take place for quite cold collisions and thus will provide competition for the spinning-up process used to create the super rotors.

Vibration-translation energy transfer in anharmonic diatomic molecules. 1: A critical evaluation of the semiclassical approximation

NASA Technical Reports Server (NTRS)

Mckenzie, R. L.

1974-01-01

The semiclassical approximation is applied to anharmonic diatomic oscillators in excited initial states. Multistate numerical solutions giving the vibrational transition probabilities for collinear collisions with an inert atom are compared with equivalent, exact quantum-mechanical calculations. Several symmetrization methods are shown to correlate accurately the predictions of both theories for all initial states, transitions, and molecular types tested, but only if coupling of the oscillator motion and the classical trajectory of the incident particle is considered. In anharmonic heteronuclear molecules, the customary semiclassical method of computing the classical trajectory independently leads to transition probabilities with anomalous low-energy resonances. Proper accounting of the effects of oscillator compression and recoil on the incident particle trajectory removes the anomalies and restores the applicability of the semiclassical approximation.

Study of ice cluster impacts on amorphous silica using the ReaxFF reactive force field molecular dynamics simulation method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rahnamoun, A.; Duin, A. C. T. van

We study the dynamics of the collisions between amorphous silica structures and amorphous and crystal ice clusters with impact velocities of 1 km/s, 4 km/s, and 7 km/s using the ReaxFF reactive molecular dynamics simulation method. The initial ice clusters consist of 150 water molecules for the amorphous ice cluster and 128 water molecules for the crystal ice cluster. The ice clusters are collided on the surface of amorphous fully oxidized and suboxide silica. These simulations show that at 1 km/s impact velocities, all the ice clusters accumulate on the surface and at 4 km/s and 7 km/s impact velocities, some of the ice cluster moleculesmore » bounce back from the surface. At 4 km/s and 7 km/s impact velocities, few of the water molecules dissociations are observed. The effect of the second ice cluster impacts on the surfaces which are fully covered with ice, on the mass loss/accumulation is studied. These studies show that at 1 km/s impacts, the entire ice cluster accumulates on the surface at both first and second ice impacts. At higher impact velocities, some ice molecules which after the first ice impacts have been attached to the surface will separate from the surface after the second ice impacts at 7 km/s impact velocity. For the 4 km/s ice cluster impact, ice accumulation is observed for the crystal ice cluster impacts and ice separation is observed for the amorphous ice impacts. Observing the temperatures of the ice clusters during the collisions indicates that the possibility of electron excitement at impact velocities less than 10 km/s is minimal and ReaxFF reactive molecular dynamics simulation can predict the chemistry of these hypervelocity impacts. However, at impact velocities close to 10 km/s the average temperature of the impacting ice clusters increase to about 2000 K, with individual molecules occasionally reaching temperatures of over 8000 K and thus it will be prudent to consider the concept of electron excitation at these higher impact velocities, which goes beyond the current ReaxFF ability.« less

Ab Initio Computation of Dynamical Properties: Pressure Broadening

NASA Astrophysics Data System (ADS)

Wiesenfeld, Laurent; Drouin, Brian

2014-06-01

Rotational spectroscopy of polar molecules is the main observational tool in many areas of astrophysics, for gases of low densities (n ˜ 102 - 108 cm-3). Spectral line shapes in astrophysical media are largely dominated by turbulence-induced Doppler effects and natural line broadening are negligible. However line broadening remains an important tool for denser gases, like planetary high atmospheres. Understanding the excitation schemes of polar molecules requires the knowledge of excitation transfer rate due to collisional excitation, between the polar molecule and the ambient gas, usually H2. Transport properties in ionized media also require a precise knowledge of momentum transfer rates by elastic collisions. In order to assess the theoretically computed cross section and energy/momentum transfer rates, direct absolute experiments are scarce. The best way is to measure not individual scattering events but rather the global effect of the buffer gas, thanks to the pressure broadening cross sections, whose magnitude can be measured without any scaling parameters. At low temperatures, both elastic and inelastic scattering amplitudes are tested. At higher temperature, depending on the interaction strength, only inelastic scattering cross section are shown to play a significant role 1 ,2. Thanks to the advances of computer capabilities, it has become practical to compute spectral line parameters fromab initio quantum chemistry. In particular, the theory of rotational line broadening is readily incorporated into scattering quantum dynamical theory, like close-coupling schemes. The only approximations used in the computation are the isolated collision/isolated line approximations. We compute the non-binding interaction potential with high precision quantum chemistry and fit the resulting ab initio points onto a suitable functional. We have recently computed several such systems, for molecules in H2 buffer gas: H2O,3 H2CO,4 HCO+ .5 Detailed computations taking into account the ortho or para state of H2 were performed, at temperatures ranging from 10 K to 100K, typically. Reliable results are found, that compare favorably to experiments. In particular, the water-molecular hydrogen system has been thoroughly computed and successfully experimentally tested 6. New projects consider other simple molecules as well as heavier systems, relevant for cometary comae and planetary high atmospheres. as part of the GNU EPrints system , and is freely redistributable under the GPL .

Recent measurements concerning uranium hexafluoride-electron collision processes

NASA Technical Reports Server (NTRS)

Trajmar, S.; Chutjian, A.; Srivastava, S.; Williams, W.; Cartwright, D. C.

1976-01-01

Scattering of electrons by UF6 molecules was studied at impact energies ranging from 5 to 100 eV and momentum transfer, elastic and inelastic scattering cross sections were determined. The measurements also yielded spectroscopic information which made possible to extend the optical absorption cross sections from 2000 angstroms to 435 angstroms. It was found that UF6 is a very strong absorber in the vacuum UV region. No transitions were found to lie below the onset of the optically detected 3.0 eV feature.

Proceeding of the 18th Intl. Workshop on Inelastic Ion-Surface Collisions (IISC-18)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Reinhold, Carlos O; Krstic, Predrag S; Meyer, Fred W

2011-01-01

The main topics of this proceedings were: (1) Energy loss of particles at surfaces; (2) Scattering of atoms, ions, molecules and clusters; (3) Charge exchange between particles and surfaces; (4) Ion induced desorption, electronic and kinetic sputtering; (5) Defect formation, surface modification and nanostructuring; (6) Electron, photon and secondary ion emission due to particle impact on surfaces; (7) Sputtering, fragmentation, cluster and ion formation in SIMS and SNMS; (8) Cluster/molecular and highly charged ion beams; and (9) Laser induced desorption.

Formation of Benzene in the Interstellar Medium

NASA Technical Reports Server (NTRS)

Jones, Brant M.; Zhang, Fangtong; Kaiser, Ralf I.; Jamal, Adeel; Mebel, Alexander M.; Cordiner, Martin A.; Charnley, Steven B.; Crim, F. Fleming (Editor)

2010-01-01

Polycyclic aromatic hydrocarbons and related species have been suggested to play a key role in the astrochemical evolution of the interstellar medium, but the formation mechanism of even their simplest building block-the aromatic benzene molecule-has remained elusive for decades. Here we demonstrate in crossed molecular beam experiments combined with electronic structure and statistical calculations that benzene (C6H6) can be synthesized via the barrierless, exoergic reaction of the ethynyl radical and 1,3- butadiene, C2H + H2CCHCHCH2 --> C6H6, + H, under single collision conditions. This reaction portrays the simplest representative of a reaction class in which aromatic molecules with a benzene core can be formed from acyclic precursors via barrierless reactions of ethynyl radicals with substituted 1,3-butadlene molecules. Unique gas-grain astrochemical models imply that this low-temperature route controls the synthesis of the very first aromatic ring from acyclic precursors in cold molecular clouds, such as in the Taurus Molecular Cloud. Rapid, subsequent barrierless reactions of benzene with ethynyl radicals can lead to naphthalene-like structures thus effectively propagating the ethynyl-radical mediated formation of aromatic molecules in the interstellar medium.

Development of Phase-Stable Photon Upconverters for Efficient Solar Energy Utilization

NASA Astrophysics Data System (ADS)

Murakami, Yoichi

Photon upconversion based on triplet-triplet annihilation (TTA) of excited triplet molecules is drawing attention due to its applicability for weak incident light, possessing a potential for improving efficiencies of solar energy conversion devices. Since energy transfer between triplet levels of different molecules and TTA are based on the Dexter mechanism, inter-molecular collision is necessary and hence the majority of previous studies have been done with organic solvents, which are volatile and flammable. This paper presents the development and characterization of phase-stable photon upconverters fabricated with ionic liquids, which are room temperature molten salts with negligible vapor pressure and high thermal stability. The employed aromatic molecules, which are carrier of photo-created energies and are non-polar (or weakly polar) molecules, are found to be stable in the polar environment of ionic liquids, contrary to expectation. The mechanism of the stable solvation is proposed. The upconversion quantum yields are found to rapidly saturate as the excitation light power increases. An analytical model was developed and compared with the experimental data. It is shown that ionic liquids are not viscous media for the purpose of TTA-based upconversion.

Vibronic transitions in the alkali-metal (Li, Na, K, Rb) - alkaline-earth-metal (Ca, Sr) series: A systematic analysis of de-excitation mechanisms based on the graphical mapping of Frank-Condon integrals

NASA Astrophysics Data System (ADS)

Pototschnig, Johann V.; Meyer, Ralf; Hauser, Andreas W.; Ernst, Wolfgang E.

2017-02-01

Research on ultracold molecules has seen a growing interest recently in the context of high-resolution spectroscopy and quantum computation. After forming weakly bound molecules from atoms in cold collisions, the preparation of molecules in low vibrational levels of the ground state is experimentally challenging, and typically achieved by population transfer using excited electronic states. Accurate potential energy surfaces are needed for a correct description of processes such as the coherent de-excitation from the highest and therefore weakly bound vibrational levels in the electronic ground state via couplings to electronically excited states. This paper is dedicated to the vibrational analysis of potentially relevant electronically excited states in the alkali-metal (Li, Na, K, Rb)- alkaline-earth metal (Ca,Sr) diatomic series. Graphical maps of Frank-Condon overlap integrals are presented for all molecules of the group. By comparison to overlap graphics produced for idealized potential surfaces, we judge the usability of the selected states for future experiments on laser-enhanced molecular formation from mixtures of quantum degenerate gases.

Effects of a Single Water Molecule on the Reaction Barrier of Interstellar CO2 Formation Reaction.

PubMed

Tachikawa, Hiroto; Kawabata, Hiroshi

2016-08-25

The mechanism by which CO2 is formed in the interstellar space remains a mystery. The most likely reaction is collision between CO and OH; however, previous theoretical works have shown that the activation barrier for CO2 formation is high enough to prevent the reaction at the low thermal conditions of space (∼10 K). The effects of single water molecule on the reaction barrier of CO2 formation from reaction between CO and OH have been investigated here by means of ab initio calculation. The barrier height along the lowest-energy pathway in the reaction between CO and OH in the absence of the H2O molecule was calculated to be 2.3 kcal/mol when CCSD(T) energy corrections are combined with the MP2 basis set limit. In the case of the hydrated (H2O-CO-OH) system, the inclusion of a single H2O molecule into the system significantly decreased the barrier height to 0.2 kcal/mol. This suggests that CO2 can be formed when CO and OH react in the presence of H2O, even under thermal conditions as low as 10 K.

Linking molecular models with ion mobility experiments. Illustration with a rigid nucleic acid structure

PubMed Central

D'Atri, Valentina; Porrini, Massimiliano; Rosu, Frédéric; Gabelica, Valérie

2015-01-01

Ion mobility spectrometry experiments allow the mass spectrometrist to determine an ion's rotationally averaged collision cross section ΩEXP. Molecular modelling is used to visualize what ion three-dimensional structure(s) is(are) compatible with the experiment. The collision cross sections of candidate molecular models have to be calculated, and the resulting ΩCALC are compared with the experimental data. Researchers who want to apply this strategy to a new type of molecule face many questions: (1) What experimental error is associated with ΩEXP determination, and how to estimate it (in particular when using a calibration for traveling wave ion guides)? (2) How to generate plausible 3D models in the gas phase? (3) Different collision cross section calculation models exist, which have been developed for other analytes than mine. Which one(s) can I apply to my systems? To apply ion mobility spectrometry to nucleic acid structural characterization, we explored each of these questions using a rigid structure which we know is preserved in the gas phase: the tetramolecular G-quadruplex [dTGGGGT]4, and we will present these detailed investigation in this tutorial. © 2015 The Authors. Journal of Mass Spectrometry published by John Wiley & Sons Ltd. PMID:26259654

Gas-phase ion chemistry and organic chemistry-the story of a hybrid six sector mass spectrometer--the "AutoSpec 6F".

PubMed

Gerbaux, Pascal; Lamote, Luc; Van Haverbeke, Yves; Flammang, Robert; Brown, Jeffrey M

2012-01-01

The AutoSpec 6F mass spectrometer is a large, floor standing instrument comprising a pair of commercial EBE geometry (AutoSpec) mass spectrometers coupled in series to provide an hybrid EBE-EBE configuration, (E and B being respectively electrostatic and magnetic sectors.) It was designed in close collaboration between Professor R. Flammang and VG Analytical in Manchester, UK. It was equipped with five collision cells and allowed the recording of high energy CID (collision induced dissociation), MIKES (mass analyzed ion kinetic energy spectrometry) and NRMS (neutralization re-ionization mass spectrometry) data as well as consecutive MSn analyses. The field-free regions between sectors allowed the study of unimolecular decomposition products from long-lived metastable ions. The mass spectrometer became even more versatile when an RF-only quadrupole collision cell was installed between the second and the third electric sector. This allowed the study of associative ion/molecule reactions in the low kinetic energy regime. Bimolecular chemical reactions were performed inside the quadrupole cell when a neutral reagent was introduced and the reaction products were analyzed by high energy CID in the downstream sectors. This paper tells the history and summarizes the capabilities of this versatile instrument.

Degradation spectra and ionization yields of electrons in gases

DOE Office of Scientific and Technical Information (OSTI.GOV)

Inokuti, M.; Douthat, D.A.; Rau, A.R.P.

1975-01-01

Progress in the microscopic theory of electron degradation in gases by Platzman, Fano, and co-workers is outlined. The theory consists of (1) the cataloging of all major inelastic-collision cross sections for electrons (including secondary-electron energy distribution in a single ionizing collision) and (2) the evaluation of cumulative consequences of individual electron collisions for the electrons themselves as well as for target molecules. For assessing the data consistency and reliability and extrapolating the data to the unexplored ranges of variables (such as electron energy), a series of plots devised by Platzman are very powerful. Electron degradation spectra were obtained through numericalmore » solution of the Spencer--Fano equation for all electron energies down to the first ionization thresholds for a few examples such as He and Ne. The systematics of the solutions resulted in the recognition of approximate scaling properties of the degradation spectra for different initial electron energies and pointed to new methods of more efficient treatment. Systematics of the ionization yields and their energy dependence on the initial electron energy were also recognized. Finally, the Spencer--Fano equation for the degradation spectra and the Fowler equation for the ionization and other yields are tightly linked with each other by a set of variational principles. (52 references, 7 figures) (DLC)« less

An ab initio chemical reaction model for the direct simulation Monte Carlo study of non-equilibrium nitrogen flows.

PubMed

Mankodi, T K; Bhandarkar, U V; Puranik, B P

2017-08-28

A new ab initio based chemical model for a Direct Simulation Monte Carlo (DSMC) study suitable for simulating rarefied flows with a high degree of non-equilibrium is presented. To this end, Collision Induced Dissociation (CID) cross sections for N 2 +N 2 →N 2 +2N are calculated and published using a global complete active space self-consistent field-complete active space second order perturbation theory N 4 potential energy surface and quasi-classical trajectory algorithm for high energy collisions (up to 30 eV). CID cross sections are calculated for only a selected set of ro-vibrational combinations of the two nitrogen molecules, and a fitting scheme based on spectroscopic weights is presented to interpolate the CID cross section for all possible ro-vibrational combinations. The new chemical model is validated by calculating equilibrium reaction rate coefficients that can be compared well with existing shock tube and computational results. High-enthalpy hypersonic nitrogen flows around a cylinder in the transition flow regime are simulated using DSMC to compare the predictions of the current ab initio based chemical model with the prevailing phenomenological model (the total collision energy model). The differences in the predictions are discussed.

A novel framework for molecular characterization of atmospherically relevant organic compounds based on collision cross section and mass-to-charge ratio

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Xuan; Krechmer, Jordan E.; Groessl, Michael

Here, a new metric is introduced for representing the molecular signature of atmospherically relevant organic compounds, the collision cross section (Ω), a quantity that is related to the structure and geometry of molecules and is derived from ion mobility measurements. By combination with the mass-to-charge ratio ( m/z), a two-dimensional Ω – m/z space is developed to facilitate the comprehensive investigation of the complex organic mixtures. A unique distribution pattern of chemical classes, characterized by functional groups including amine, alcohol, carbonyl, carboxylic acid, ester, and organic sulfate, is developed on the 2-D Ω – m/z space. Species of the samemore » chemical class, despite variations in the molecular structures, tend to situate as a narrow band on the space and follow a trend line. Reactions involving changes in functionalization and fragmentation can be represented by the directionalities along or across these trend lines, thus allowing for the interpretation of atmospheric transformation mechanisms of organic species. The characteristics of trend lines for a variety of functionalities that are commonly present in the atmosphere can be predicted by the core model simulations, which provide a useful tool to identify the chemical class to which an unknown species belongs on the Ω – m/z space. Within the band produced by each chemical class on the space, molecular structural assignment can be achieved by utilizing collision-induced dissociation as well as by comparing the measured collision cross sections in the context of those obtained via molecular dynamics simulations.« less

A novel framework for molecular characterization of atmospherically relevant organic compounds based on collision cross section and mass-to-charge ratio

DOE PAGES

Zhang, Xuan; Krechmer, Jordan E.; Groessl, Michael; ...

2016-10-19

Here, a new metric is introduced for representing the molecular signature of atmospherically relevant organic compounds, the collision cross section (Ω), a quantity that is related to the structure and geometry of molecules and is derived from ion mobility measurements. By combination with the mass-to-charge ratio ( m/z), a two-dimensional Ω – m/z space is developed to facilitate the comprehensive investigation of the complex organic mixtures. A unique distribution pattern of chemical classes, characterized by functional groups including amine, alcohol, carbonyl, carboxylic acid, ester, and organic sulfate, is developed on the 2-D Ω – m/z space. Species of the samemore » chemical class, despite variations in the molecular structures, tend to situate as a narrow band on the space and follow a trend line. Reactions involving changes in functionalization and fragmentation can be represented by the directionalities along or across these trend lines, thus allowing for the interpretation of atmospheric transformation mechanisms of organic species. The characteristics of trend lines for a variety of functionalities that are commonly present in the atmosphere can be predicted by the core model simulations, which provide a useful tool to identify the chemical class to which an unknown species belongs on the Ω – m/z space. Within the band produced by each chemical class on the space, molecular structural assignment can be achieved by utilizing collision-induced dissociation as well as by comparing the measured collision cross sections in the context of those obtained via molecular dynamics simulations.« less

Electron transfer driven decomposition of adenine and selected analogs as probed by experimental and theoretical methods

NASA Astrophysics Data System (ADS)

Cunha, T.; Mendes, M.; Ferreira da Silva, F.; Eden, S.; García, G.; Bacchus-Montabonel, M.-C.; Limão-Vieira, P.

2018-04-01

We report on a combined experimental and theoretical study of electron-transfer-induced decomposition of adenine (Ad) and a selection of analog molecules in collisions with potassium (K) atoms. Time-of-flight negative ion mass spectra have been obtained in a wide collision energy range (6-68 eV in the centre-of-mass frame), providing a comprehensive investigation of the fragmentation patterns of purine (Pu), adenine (Ad), 9-methyl adenine (9-mAd), 6-dimethyl adenine (6-dimAd), and 2-D adenine (2-DAd). Following our recent communication about selective hydrogen loss from the transient negative ions (TNIs) produced in these collisions [T. Cunha et al., J. Chem. Phys. 148, 021101 (2018)], this work focuses on the production of smaller fragment anions. In the low-energy part of the present range, several dissociation channels that are accessible in free electron attachment experiments are absent from the present mass spectra, notably NH2 loss from adenine and 9-methyl adenine. This can be understood in terms of a relatively long transit time of the K+ cation in the vicinity of the TNI tending to enhance the likelihood of intramolecular electron transfer. In this case, the excess energy can be redistributed through the available degrees of freedom inhibiting fragmentation pathways. Ab initio theoretical calculations were performed for 9-methyl adenine (9-mAd) and adenine (Ad) in the presence of a potassium atom and provided a strong basis for the assignment of the lowest unoccupied molecular orbitals accessed in the collision process.

Bacteria survival probability in bactericidal filter paper.

PubMed

Mansur-Azzam, Nura; Hosseinidoust, Zeinab; Woo, Su Gyeong; Vyhnalkova, Renata; Eisenberg, Adi; van de Ven, Theo G M

2014-05-01

Bactericidal filter papers offer the simplicity of gravity filtration to simultaneously eradicate microbial contaminants and particulates. We previously detailed the development of biocidal block copolymer micelles that could be immobilized on a filter paper to actively eradicate bacteria. Despite the many advantages offered by this system, its widespread use is hindered by its unknown mechanism of action which can result in non-reproducible outcomes. In this work, we sought to investigate the mechanism by which a certain percentage of Escherichia coli cells survived when passing through the bactericidal filter paper. Through the process of elimination, the possibility that the bacterial survival probability was controlled by the initial bacterial load or the existence of resistant sub-populations of E. coli was dismissed. It was observed that increasing the thickness or the number of layers of the filter significantly decreased bacterial survival probability for the biocidal filter paper but did not affect the efficiency of the blank filter paper (no biocide). The survival probability of bacteria passing through the antibacterial filter paper appeared to depend strongly on the number of collision between each bacterium and the biocide-loaded micelles. It was thus hypothesized that during each collision a certain number of biocide molecules were directly transferred from the hydrophobic core of the micelle to the bacterial lipid bilayer membrane. Therefore, each bacterium must encounter a certain number of collisions to take up enough biocide to kill the cell and cells that do not undergo the threshold number of collisions are expected to survive. Copyright © 2014 Elsevier B.V. All rights reserved.

Collision-Induced Infrared Absorption by Collisional Complexes in Dense Hydrogen-Helium Gas Mixtures at Thousands of Kelvin

NASA Astrophysics Data System (ADS)

Abel, Martin; Frommhold, Lothar; Li, Xiaoping; Hunt, Katharine L. C.

2011-06-01

The interaction-induced absorption by collisional pairs of H{_2} molecules is an important opacity source in the atmospheres of the outer planets and cool stars. The emission spectra of cool white dwarf stars differ significantly in the infrared from the expected blackbody spectra of their cores, which is largely due to absorption by collisional H{_2}-H{_2}, H{_2}-He, and H{_2}-H complexes in the stellar atmospheres. Using quantum-chemical methods we compute the atmospheric absorption from hundreds to thousands of kelvin. Laboratory measurements of interaction-induced absorption spectra by H{_2} pairs exist only at room temperature and below. We show that our results reproduce these measurements closely, so that our computational data permit reliable modeling of stellar atmosphere opacities even for the higher temperatures. L. Frommhold, Collision-Induced Absorption in Gases, Cambridge University Press, Cambridge, New York, 1993 and 2006 Xiaoping Li, Katharine L. C. Hunt, Fei Wang, Martin Abel, and Lothar Frommhold, "Collision-Induced Infrared Absorption by Molecular Hydrogen Pairs at Thousands of Kelvin", International Journal of Spectroscopy, vol. 2010, Article ID 371201, 11 pages, 2010. doi: 10.1155/2010/371201 M. Abel, L. Frommhold, X. Li, and K. L. C. Hunt, "Collision-induced absorption by H{_2} pairs: From hundreds to thousands of Kelvin," J. Phys. Chem. A, published online, DOI: 10.1021/jp109441f L. Frommhold, M. Abel, F. Wang, M. Gustafsson, X. Li, and K. L. C. Hunt, "Infrared atmospheric emission and absorption by simple molecular complexes, from first principles", Mol. Phys. 108, 2265, 2010

PREFACE: XXV International Conference on Photonic, Electronic and Atomic Collisions

NASA Astrophysics Data System (ADS)

Becker, Uwe; Moshammer, Robert; Mokler, Paul; Ullrich, Joachim

2007-07-01

The XXVth ICPEAC in Freiburg marked a notable anniversary in collision physics: half a century ago the first conference in the series of International Conferences on the Physics of Electronic and Atomic Collisions (ICPEAC) was held in New York (1958). Since then, the development of electronic and atomic collision physics has seen tremendous progress. Starting during a time, when this field was regarded as somehow out-of-date, certainly not being in the main stream compared to particle and high-energy physics, it has expanded in a rather exceptional and unforeseen way. Over the years the original scope on electronic, atomic and heavy-ion collision physics was extended substantially to include upcoming expanding fields like synchrotron-radiation and strong-field laser-based atomic and molecular physics giving rise to a change of name to 'Photonic', Electronic and Atomic Collisions (ICPEAC) being used for the first time for the ICPEAC in Santa Fee in 2001. Nowadays, the ICPEAC has opened its agenda even more widely to other fields of atomic and molecular physics, such as interactions with clusters, bio-molecules and surfaces, to cold collisions, coherent control, femto- and attosecond physics and, with the Freiburg conference, to the application of free-electron lasers in the vacuum ultraviolet and soft x-ray regime, a field of potentially huge future impact in essentially all areas of science. In this larger context the XXVth ICPEAC in Freiburg with more than 800 participants set new standards. Representatives from all fields of Atomic, Molecular and Photon-based science came together and had very fruitful, inter-disciplinary discussions. This new forum of collision-based AMP physics will serve as a showcase example of future conferences, bridging not only the gap between different fields of collision physics but also, equally important, between different continents and cultures. The next ICPEAC is going to take place in Kalamazoo in North America, the one after that in Belfast back in Europe, and the subsequent one, 2013 in Lanzhou, will be the first one ever held in China. A great perspective for this ever-growing field of science! Uwe Becker (Fritz-Haber-Institut, Berlin) Robert Moshammer (Max-Planck-Institut für Kernphysik, Heidelberg) Paul Mokler (Gesellschaft für Schwerionenforschung, Darmstadt) Joachim Ullrich (Max-Planck-Institut für Kernphysik, Heidelberg) Editors Relaxed atmosphere for discussions during coffee breaks at ICPEAC XXV in Freiburg. The PDF file contains details of previous conferences, sponsors, exhibitors and committees.

Electronic spectra of 2- and 3-tolunitrile in the gas phase. I. A study of methyl group internal rotation via rovibronically resolved spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ruiz-Santoyo, José Arturo; Álvarez-Valtierra, Leonardo, E-mail: leoav@fisica.ugto.mx; Wilke, Josefin

2016-01-28

Rotationally resolved fluorescence excitation spectra of the origin bands in the S{sub 1}←S{sub 0} transition of 2-tolunitrile (2TN) and 3-tolunitrile (3TN) have been recorded in the collision-free environment of a molecular beam. Analyses of these data provide the rotational constants of each molecule and the potential energy curves governing the internal rotation of the attached methyl groups in both electronic states. 2TN exhibits much larger barriers along this coordinate than 3TN. Interestingly, the electronic transition dipole moment in both molecules is markedly influenced by the position of the attached methyl group rather than the position of the cyano group; possiblemore » reasons for this intriguing behavior are discussed.« less

Energetic Metastable Oxygen and Nitrogen Atoms in the Terrestrial Atmosphere

NASA Technical Reports Server (NTRS)

Kharchenko, Vasili

2004-01-01

We have investigated the impact of hot metastable oxygen atoms on the product yields and rate coefficients of atmospheric reactions involving O( (sup 1)D). The contribution of the metastable oxygen atoms to the thermal balance of the terrestrial atmosphere between 50 and 200 km has been determined. We found that the presence of hot O((sup l)D) atoms in the mesosphere and lower thermosphere significantly increases the production rate of the rotationally-vibrationally excited NO molecules. The computed yield of the NO molecules in N2O+ O((sup 1)D) atmospheric collisions, involving non-Maxwellian distributions of the metastable oxygen atoms, is more than two times larger than the NO-yield at a thermal equilibrium. The calculated non-equilibrium rate and yield functions are important for ozone and nitrous oxide modeling in the stratosphere, mesosphere and lower thermosphere.

A Chemical Model of the Coma of Comet C/2009 P1 (Garradd)

NASA Astrophysics Data System (ADS)

Boice, Daniel C.; Kawakita, H.; Kobayashi, H.; Naka, C.; Phelps, L.

2012-10-01

Modeling is essential to understand the important physical and chemical processes that occur in cometary comae. Photochemistry is a major source of ions and electrons that further initiate key gas-phase reactions, leading to the plethora of molecules and atoms observed in comets. The effects of photoelectrons that react via impacts are important to the overall ionization. We identify the relevant processes within a global modeling framework to understand simultaneous observations in the visible and near-IR of Comet C/2009 (Garradd) and to provide valuable insights into the intrinsic properties of its nucleus. Details of these processes are presented in the collision-dominated, inner coma of the comet to evaluate the relative chemical pathways and the relationship between parent and sibling molecules. Acknowledgements: We appreciate support from the NSF Planetary Astronomy Program.

Aerothermodynamics of Satellite During Atmospheric Reentry for the Whole Range of Gas Rarefaction: Influence of Inelastic Intermolecular Collisions

NASA Astrophysics Data System (ADS)

Kozak, Dalton Vinicius; Sharipov, Felix

2012-08-01

The aerothermodynamic characteristics of the Brazilian satellite Satélite de Reentrada Atmosférica were calculated for orbital-flight and atmospheric-reentry conditions with the direct simulation Monte Carlo method for a diatomic gas. The internal modes of molecule energy in the intermolecular interaction, such as the rotational energy, were taken into account. The numerical calculations cover a range of gas rarefactions wide enough to embrace the free-molecule and hydrodynamic regimes. Two Mach numbers were considered: 10 and 20. Numerical results include the drag force of the satellite, the energy flux, pressure coefficient, and skin friction coefficient over the satellite surface, the density and temperature distributions, and streamlines of the gas flow around the satellite. The influence of the satellite temperature upon these characteristics was evaluated at different satellite temperatures.

Accuracy of theory for calculating electron impact ionization of molecules

NASA Astrophysics Data System (ADS)

Chaluvadi, Hari Hara Kumar

The study of electron impact single ionization of atoms and molecules has provided valuable information about fundamental collisions. The most detailed information is obtained from triple differential cross sections (TDCS) in which the energy and momentum of all three final state particles are determined. These cross sections are much more difficult for theory since the detailed kinematics of the experiment become important. There are many theoretical approximations for ionization of molecules. One of the successful methods is the molecular 3-body distorted wave (M3DW) approximation. One of the strengths of the DW approximation is that it can be applied for any energy and any size molecule. One of the approximations that has been made to significantly reduce the required computer time is the OAMO (orientation averaged molecular orbital) approximation. In this dissertation, the accuracy of the M3DW-OAMO is tested for different molecules. Surprisingly, the M3DW-OAMO approximation yields reasonably good agreement with experiment for ionization of H2 and N2. On the other hand, the M3DW-OAMO results for ionization of CH4, NH3 and DNA derivative molecules did not agree very well with experiment. Consequently, we proposed the M3DW with a proper average (PA) calculation. In this dissertation, it is shown that the M3DW-PA calculations for CH4 and SF6 are in much better agreement with experimental data than the M3DW-OAMO results.

Fragmentation study of iridoid glucosides through positive and negative electrospray ionization, collision-induced dissociation and tandem mass spectrometry.

PubMed

Es-Safi, Nour-Eddine; Kerhoas, Lucien; Ducrot, Paul-Henri

2007-01-01

Mass spectrometric methodology based on the combined use of positive and negative electrospray ionization, collision-induced dissociation (CID) and tandem mass spectrometry (MS/MS) has been applied to the mass spectral study of a series of six naturally occurring iridoids through in-source fragmentation of the protonated [M+H]+, deprotonated [M--H]- and sodiated [M+Na]+ ions. This led to the unambiguous determination of the molecular masses of the studied compounds and allowed CID spectra of the molecular ions to be obtained. Valuable structural information regarding the nature of both the glycoside and the aglycone moiety was thus obtained. Glycosidic cleavage and ring cleavages of both aglycone and sugar moieties were the major fragmentation pathways observed during CID, where the losses of small molecules, the cinnamoyl and the cinnamate parts were also observed. The formation of the ionized aglycones, sugars and their product ions was thus obtained giving information on their basic skeleton. The protonated, i.e. [M+H]+ and deprotonated [M--H]-, ions were found to fragment mainly by glycosidic cleavages. MS/MS spectra of the [M+Na]+ ions gave complementary information for the structural characterization of the studied compounds. Unlike the dissociation of protonated molecular ions, that of sodiated molecules also provided sodiated sugar fragments where the C0+ fragment corresponding to the glucose ion was obtained as base peak for all the studied compounds. Copyright (c) 2007 John Wiley & Sons, Ltd.

Isomer and Fluorination Effects among Fluorine Substituted Hydrocarbon C3/C4 Molecules in Electron Impact Ionization

NASA Astrophysics Data System (ADS)

Patel, U. R.; Joshipura, K. N.

2015-05-01

Electron collision processes are very important in both man-made and natural plasmas, for determining the energy balances and transport properties of electrons. Electron -molecule scattering leading to ionization represents one of the most fundamental processes in collision physics. In the gas phase, the total efficiency of the process is described by the absolute total electron impact ionization cross section. Carbon based materials are some of the widely used materials for a divertor plate and magnetically confined fusion devices. In the ``ITER,'' it is very important for steady state operation to have an estimate of the lifetime of carbon plasma facing components. Apart from fusion plasma relevance, the present theoretical study is very important in modeling and controlling other electron assisted processes in many areas. Hydrocarbons play an important role for plasma diagnostics as impurities in the Tokamak fusion divertor, as seed gases for the production of radicals and ions in low temperature plasma processing. Fluorine substituted hydrocarbons (perfluorocarbons) are important as reactants in plasma assisted fabrication processes. In the present work, we have calculated total ionization cross sections Qion for C3/C4 Hydrocarbon isomers by electron impact, and comparisons are made mutually to observe isomer effect. Comparisons are also made by substituting H atom by F atom and revealing fluorination effect. The present calculations are quite significant owing to the lack of experimental data, with just an isolated previous theoretical work in some cases.

Report on the 18th International Conference on X-ray and Inner-Shell Processes (X99).

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gemmell, D. S.; Physics

2000-01-01

The 18th conference of the series served as a forum for discussing fundamental issues in the field of x-ray and inner-shell processes and their application in various disciplines of science and technology. Special emphasis was given to the opportunities offered by modern synchrotron x-ray sources. The program included plenary talks, progress reports and poster presentations relating to new developments in the field of x-ray and inner-shell processes. The range of topics included: X-ray interactions with atoms, molecules, clusters, surfaces and solids; Decay processes for inner-shell vacancies; X-ray absorption and emission spectroscopy - Photoionization processes; Phenomena associated with highly charged ionsmore » and collisions with energetic particles; Electron-spin and -momentum spectroscopy; X-ray scattering and spectroscopy in the study of magnetic systems; Applications in materials science, biology, geosciences, and other disciplines; Elastic and inelastic x-ray scattering processes in atoms and molecules; Threshold phenomena (post-collision interaction, resonant Raman processes, etc.); Nuclear absorption and scattering of x-rays; 'Fourth-generation' x-ray sources; Processes exploiting the polarization and coherence properties of x-ray beams; Developments in experimental techniques (x-ray optics, temporal techniques, detectors); Microscopy, spectromicroscopy, and various imaging techniques; Non-linear processes and x-ray lasers; Ionization and excitation induced by charged particles and by x-rays; and Exotic atoms (including 'hollow' atoms and atoms that contain 'exotic' particles).« less

Conformational ordering of biomolecules in the gas phase: nitrogen collision cross sections measured on a prototype high resolution drift tube ion mobility-mass spectrometer.

PubMed

May, Jody C; Goodwin, Cody R; Lareau, Nichole M; Leaptrot, Katrina L; Morris, Caleb B; Kurulugama, Ruwan T; Mordehai, Alex; Klein, Christian; Barry, William; Darland, Ed; Overney, Gregor; Imatani, Kenneth; Stafford, George C; Fjeldsted, John C; McLean, John A

2014-02-18

Ion mobility-mass spectrometry measurements which describe the gas-phase scaling of molecular size and mass are of both fundamental and pragmatic utility. Fundamentally, such measurements expand our understanding of intrinsic intramolecular folding forces in the absence of solvent. Practically, reproducible transport properties, such as gas-phase collision cross-section (CCS), are analytically useful metrics for identification and characterization purposes. Here, we report 594 CCS values obtained in nitrogen drift gas on an electrostatic drift tube ion mobility-mass spectrometry (IM-MS) instrument. The instrument platform is a newly developed prototype incorporating a uniform-field drift tube bracketed by electrodynamic ion funnels and coupled to a high resolution quadrupole time-of-flight mass spectrometer. The CCS values reported here are of high experimental precision (±0.5% or better) and represent four chemically distinct classes of molecules (quaternary ammonium salts, lipids, peptides, and carbohydrates), which enables structural comparisons to be made between molecules of different chemical compositions for the rapid "omni-omic" characterization of complex biological samples. Comparisons made between helium and nitrogen-derived CCS measurements demonstrate that nitrogen CCS values are systematically larger than helium values; however, general separation trends between chemical classes are retained regardless of the drift gas. These results underscore that, for the highest CCS accuracy, care must be exercised when utilizing helium-derived CCS values to calibrate measurements obtained in nitrogen, as is the common practice in the field.

Conformational Ordering of Biomolecules in the Gas Phase: Nitrogen Collision Cross Sections Measured on a Prototype High Resolution Drift Tube Ion Mobility-Mass Spectrometer

PubMed Central

2014-01-01

Ion mobility-mass spectrometry measurements which describe the gas-phase scaling of molecular size and mass are of both fundamental and pragmatic utility. Fundamentally, such measurements expand our understanding of intrinsic intramolecular folding forces in the absence of solvent. Practically, reproducible transport properties, such as gas-phase collision cross-section (CCS), are analytically useful metrics for identification and characterization purposes. Here, we report 594 CCS values obtained in nitrogen drift gas on an electrostatic drift tube ion mobility-mass spectrometry (IM-MS) instrument. The instrument platform is a newly developed prototype incorporating a uniform-field drift tube bracketed by electrodynamic ion funnels and coupled to a high resolution quadrupole time-of-flight mass spectrometer. The CCS values reported here are of high experimental precision (±0.5% or better) and represent four chemically distinct classes of molecules (quaternary ammonium salts, lipids, peptides, and carbohydrates), which enables structural comparisons to be made between molecules of different chemical compositions for the rapid “omni-omic” characterization of complex biological samples. Comparisons made between helium and nitrogen-derived CCS measurements demonstrate that nitrogen CCS values are systematically larger than helium values; however, general separation trends between chemical classes are retained regardless of the drift gas. These results underscore that, for the highest CCS accuracy, care must be exercised when utilizing helium-derived CCS values to calibrate measurements obtained in nitrogen, as is the common practice in the field. PMID:24446877

Water interactions with condensed organic phases: a combined experimental and theoretical study of molecular-level processes

NASA Astrophysics Data System (ADS)

Johansson, Sofia M.; Kong, Xiangrui; Thomson, Erik S.; Papagiannakopoulos, Panos; Pettersson, Jan B. C.; Lovrić, Josip; Toubin, Céline

2016-04-01

Water uptake on aerosol particles modifies their chemistry and microphysics with important implications for air quality and climate. A large fraction of the atmospheric aerosol consists of organic aerosol particles or inorganic particles with condensed organic components. Here, we combine laboratory studies using the environmental molecular beam (EMB) method1 with molecular dynamics (MD) simulations to characterize water interactions with organic surfaces in detail. The over-arching aim is to characterize the mechanisms that govern water uptake, in order to guide the development of physics-based models to be used in atmospheric modelling. The EMB method enables molecular level studies of interactions between gases and volatile surfaces at near ambient pressure,1 and the technique may provide information about collision dynamics, surface and bulk accommodation, desorption and diffusion kinetics. Molecular dynamics simulations provide complementary information about the collision dynamics and initial interactions between gas molecules and the condensed phase. Here, we focus on water interactions with condensed alcohol phases that serve as highly simplified proxies for systems in the environment. Gas-surface collisions are in general found to be highly inelastic and result in efficient surface accommodation of water molecules. As a consequence, surface accommodation of water can be safely assumed to be close to unity under typical ambient conditions. Bulk accommodation is inefficient on solid alcohol and the condensed materials appear to produce hydrophobic surface structures, with limited opportunities for adsorbed water to form hydrogen bonds with surface molecules. Accommodation is significantly more efficient on the dynamic liquid alcohol surfaces. The results for n-butanol (BuOH) are particularly intriguing where substantial changes in water accommodation taking place over a 10 K interval below and above the BuOH melting point.2 The governing mechanisms for the observed water accommodation are discussed based on the combined EMB and MD results. The studies illustrate that the detailed surface properties of the condensed organic phase may substantially modify water uptake, with potential implications for the properties and action of aerosols and clouds in the Earth system. References: 1. X.R. Kong, E. S. Thomson, P. Papagiannakopoulos, S.M. Johansson, and J.B.C. Pettersson, Water Accommodation on Ice and Organic Surfaces: Insights from Environmental Molecular Beam Experiments. J. Phys. Chem. B 118 (2014) 13378-13386. 2. P. Papagiannakopoulos, X. Kong, E. S. Thomson, N. Marković, and J. B. C. Pettersson, Surface Transformations and Water Uptake on Liquid and Solid Butanol near the Melting Temperature. J. Phys. Chem. C 117 (2013) 6678-6685.

Dynamic molecular oxygen production in cometary comae.

PubMed

Yao, Yunxi; Giapis, Konstantinos P

2017-05-08

Abundant molecular oxygen was discovered in the coma of comet 67P/Churyumov-Gerasimenko. Its origin was ascribed to primordial gaseous O 2 incorporated into the nucleus during the comet's formation. This thesis was put forward after discounting several O 2 production mechanisms in comets, including photolysis and radiolysis of water, solar wind-surface interactions and gas-phase collisions. Here we report an original Eley-Rideal reaction mechanism, which permits direct O 2 formation in single collisions of energetic water ions with oxidized cometary surface analogues. The reaction proceeds by H 2 O + abstracting a surface O-atom, then forming an excited precursor state, which dissociates to produce O 2 - . Subsequent photo-detachment leads to molecular O 2 , whose presence in the coma may thus be linked directly to water molecules and their interaction with the solar wind. This abiotic O 2 production mechanism is consistent with reported trends in the 67P coma and raises awareness of the role of energetic negative ions in comets.

Non-parametric wall model and methods of identifying boundary conditions for moments in gas flow equations

NASA Astrophysics Data System (ADS)

Liao, Meng; To, Quy-Dong; Léonard, Céline; Monchiet, Vincent

2018-03-01

In this paper, we use the molecular dynamics simulation method to study gas-wall boundary conditions. Discrete scattering information of gas molecules at the wall surface is obtained from collision simulations. The collision data can be used to identify the accommodation coefficients for parametric wall models such as Maxwell and Cercignani-Lampis scattering kernels. Since these scattering kernels are based on a limited number of accommodation coefficients, we adopt non-parametric statistical methods to construct the kernel to overcome these issues. Different from parametric kernels, the non-parametric kernels require no parameter (i.e. accommodation coefficients) and no predefined distribution. We also propose approaches to derive directly the Navier friction and Kapitza thermal resistance coefficients as well as other interface coefficients associated with moment equations from the non-parametric kernels. The methods are applied successfully to systems composed of CH4 or CO2 and graphite, which are of interest to the petroleum industry.

Accretion growth of water-ice grains in astrophysically-relevant dusty plasma experiment

NASA Astrophysics Data System (ADS)

Chai, Kil-Byoung; Marshall, Ryan; Bellan, Paul

2016-10-01

The grain growth process in the Caltech water-ice dusty plasma experiment has been studied using a high-speed camera equipped with a long-distance microscope lens. It is found that (i) the ice grain number density decreases four-fold as the average grain length increases from 20 to 80 um, (ii) the ice grain length has a log-normal distribution rather than a power-law dependence, and (iii) no collisions between ice grains are apparent. The grains have a large negative charge so the agglomeration growth is prevented by their strong mutual repulsion. It is concluded that direct accretion of water molecules is in good agreement with the observed ice grain growth. The volumetric packing factor of the ice grains must be less than 0.25 in order for the grain kinetic energy to be sufficiently small to prevent collisions between ice grains; this conclusion is consistent with ice grain images showing a fractal character.

Electron transport parameters in NF3

NASA Astrophysics Data System (ADS)

Lisovskiy, V.; Yegorenkov, V.; Ogloblina, P.; Booth, J.-P.; Martins, S.; Landry, K.; Douai, D.; Cassagne, V.

2014-03-01

We present electron transport parameters (the first Townsend coefficient, the dissociative attachment coefficient, the fraction of electron energy lost by collisions with NF3 molecules, the average and characteristic electron energy, the electron mobility and the drift velocity) in NF3 gas calculated from published elastic and inelastic electron-NF3 collision cross-sections using the BOLSIG+ code. Calculations were performed for the combined RB (Rescigno 1995 Phys. Rev. E 52 329, Boesten et al 1996 J. Phys. B: At. Mol. Opt. Phys. 29 5475) momentum-transfer cross-section, as well as for the JB (Joucoski and Bettega 2002 J. Phys. B: At. Mol. Opt. Phys. 35 783) momentum-transfer cross-section. In addition, we have measured the radio frequency (rf) breakdown curves for various inter-electrode gaps and rfs, and from these we have determined the electron drift velocity in NF3 from the location of the turning point in these curves. These drift velocity values are in satisfactory agreement with those calculated by the BOLSIG+ code employing the JB momentum-transfer cross-section.

Molecular dynamics simulation of a needle-sphere binary mixture

NASA Astrophysics Data System (ADS)

Raghavan, Karthik

This paper investigates the dynamic behaviour of a hard needle-sphere binary system using a novel numerical technique called the Newton homotopy continuation (NHC) method. This mixture is representative of a polymer melt where both long chain molecules and monomers coexist. Since the intermolecular forces are generated from hard body interactions, the consequence of missed collisions or incorrect collision sequences have a significant bearing on the dynamic properties of the fluid. To overcome this problem, in earlier work NHC was chosen over traditional Newton-Raphson methods to solve the hard body dynamics of a needle fluid in random media composed of overlapping spheres. Furthermore, the simplicity of interactions and dynamics allows us to focus our research directly on the effects of particle shape and density on the transport behaviour of the mixture. These studies are also compared with earlier works that examined molecular chains in porous media primarily to understand the differences in molecular transport in the bulk versus porous systems.

Electron collisions—experiment, theory, and applications

NASA Astrophysics Data System (ADS)

Bartschat, Klaus

2018-07-01

Electron collisions with atoms, ions, and molecules have represented an important area of ‘applied quantum mechanics’ for more than a century. This Topical Review is the write-up of the Allis Prize Lecture given by the author at the 2016 meeting of the Division of Atomic, Molecular, and Optical Physics of the American Physical Society and the 2017 Gaseous Electronics Conference. In light of the enormous size of the field, the examples presented were selected in order to tell the story of how experimental and theoretical/numerical methods have developed over time, how fruitful collaborations between data producers (experimentalists and theorists) and data users have led to significant progress, and how the results of these studies, which were often designed for fundamental research in order to push both experiment and theory to new frontiers, continue to be highly sought after for modeling applications in a variety of fields. The impact of electron collision studies on other fields, such as photoinduced processes and quantum information, is also discussed.

Dynamic molecular oxygen production in cometary comae

NASA Astrophysics Data System (ADS)

Yao, Yunxi; Giapis, Konstantinos P.

2017-05-01

Abundant molecular oxygen was discovered in the coma of comet 67P/Churyumov-Gerasimenko. Its origin was ascribed to primordial gaseous O2 incorporated into the nucleus during the comet's formation. This thesis was put forward after discounting several O2 production mechanisms in comets, including photolysis and radiolysis of water, solar wind-surface interactions and gas-phase collisions. Here we report an original Eley-Rideal reaction mechanism, which permits direct O2 formation in single collisions of energetic water ions with oxidized cometary surface analogues. The reaction proceeds by H2O+ abstracting a surface O-atom, then forming an excited precursor state, which dissociates to produce O2-. Subsequent photo-detachment leads to molecular O2, whose presence in the coma may thus be linked directly to water molecules and their interaction with the solar wind. This abiotic O2 production mechanism is consistent with reported trends in the 67P coma and raises awareness of the role of energetic negative ions in comets.

The Binary Collision-Induced Second Overtone Band of Gaseous Hydrogen: Modelling and Laboratory Measurements

NASA Technical Reports Server (NTRS)

Brodbeck, C.; Bouanich, J.-P.; Nguyen, Van Thanh; Borysow, Aleksandra

1999-01-01

Collision-induced absorption (CIA) is the major source of the infrared opacity of dense planetary atmospheres which are composed of nonpolar molecules. Knowledge of CIA absorption spectra of H2-H2 pairs is important for modelling the atmospheres of planets and cold stars that are mainly composed of hydrogen. The spectra of hydrogen in the region of the second overtone at 0.8 microns have been recorded at temperatures of 298 and 77.5 K for gas densities ranging from 100 to 800 amagats. By extrapolation to zero density of the absorption coefficient measured every 10 cm(exp -1) in the spectral range from 11100 to 13800 cm(exp -1), we have determined the binary absorption coefficient. These extrapolated measurements are compared with calculations based on a model that was obtained by using simple computer codes and lineshape profiles. In view of the very weak absorption of the second overtone band, we find the agreement between results of the model and experiment to be reasonable.

Radio-Frequency-Controlled Cold Collisions and Universal Properties of Unitary Bose Gases

NASA Astrophysics Data System (ADS)

Ding, Yijue

This thesis investigates two topics: ultracold atomic collisions in a radio-frequency field and universal properties of a degenerate unitary Bose gas. One interesting point of the unitary Bose gas is that the system has only one length scale, that is, the average interparticle distance. This single parameter determines all properties of the gas, which is called the universality of the system. We first introduce a renormalized contact interaction to extend the validity of the zero-range interaction to large scattering lengths. Then this renormalized interaction is applied to many-body theories to determined those universal relations of the system. From the few-body perspective, we discuss the scattering between atoms in a single-color radio-frequency field. Our motivation is proposing the radio-frequency field as an effective tool to control interactions between cold atoms. Such a technique may be useful in future experiments such as creating phase transitions in spinor condensates. We also discuss the formation of ultracold molecules using radio-freqency fields from a time-dependent approach.

Giant plasmon excitation in single and double ionization of C60 by fast highly charged Si and O ions

NASA Astrophysics Data System (ADS)

Kelkar, A. H.; Kadhane, U.; Misra, D.; Tribedi, L. C.

2007-09-01

Se have investigated single and double ionization of C60 molecule in collisions with 2.33 MeV/u Siq+ (q=6-14) and 3.125 MeV/u Oq+ (q=5-8) projectiles. The projectile charge state dependence of the single and double ionization yields of C60 are then compared to those for an ion-atom collision system using Ne gas as a target. A large difference between the gas and the cluster target behaviour was partially explained in terms of a model based on collective excitation namely the giant dipole plasmon resonance (GDPR). The qualitative agreement between the data and GDPR model prediction for single and double ionization signifies the importance of single and double plasmon excitations in the ionization process. A large deviation of the GDPR model for triple and quadruple ionization from the experimental data imply the importance of the other low impact parameter processes such as evaporation, fragmentation and a possible solid-like dynamical screening.

Entropy and chemical change. 1: Characterization of product (and reactant) energy distributions in reactive molecular collisions: Information and enthropy deficiency

NASA Technical Reports Server (NTRS)

Bernstein, R. B.; Levine, R. D.

1972-01-01

Optimal means of characterizing the distribution of product energy states resulting from reactive collisions of molecules with restricted distributions of initial states are considered, along with those for characterizing the particular reactant state distribution which yields a given set of product states at a specified total energy. It is suggested to represent the energy-dependence of global-type results in the form of square-faced bar plots, and of data for specific-type experiments as triangular-faced prismatic plots. The essential parameters defining the internal state distribution are isolated, and the information content of such a distribution is put on a quantitative basis. The relationship between the information content, the surprisal, and the entropy of the continuous distribution is established. The concept of an entropy deficiency, which characterizes the specificity of product state formation, is suggested as a useful measure of the deviance from statistical behavior. The degradation of information by experimental averaging is considered, leading to bounds on the entropy deficiency.

Single-Nanoparticle Photoelectrochemistry at a Nanoparticulate TiO2 -Filmed Ultramicroelectrode.

PubMed

Peng, Yue-Yi; Ma, Hui; Ma, Wei; Long, Yi-Tao; Tian, He

2018-03-26

An ultrasensitive photoelectrochemical method for achieving real-time detection of single nanoparticle collision events is presented. Using a micrometer-thick nanoparticulate TiO 2 -filmed Au ultra-microelectrode (TiO 2 @Au UME), a sub-millisecond photocurrent transient was observed for an individual N719-tagged TiO 2 (N719@TiO 2 ) nanoparticle and is due to the instantaneous collision process. Owing to a trap-limited electron diffusion process as the rate-limiting step, a random three-dimensional diffusion model was developed to simulate electron transport dynamics in TiO 2 film. The combination of theoretical simulation and high-resolution photocurrent measurement allow electron-transfer information of a single N719@TiO 2 nanoparticle to be quantified at single-molecule accuracy and the electron diffusivity and the electron-collection efficiency of TiO 2 @Au UME to be estimated. This method provides a test for studies of photoinduced electron transfer at the single-nanoparticle level. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Double Molecular Photoswitch Driven by Light and Collisions

NASA Astrophysics Data System (ADS)

Bull, James N.; Scholz, Michael S.; Carrascosa, Eduardo; da Silva, Gabriel; Bieske, Evan J.

2018-06-01

The shapes of many molecules can be transformed by light or heat. Here we investigate collision- and photon-induced interconversions of E E , E Z , and Z Z isomers of the isolated Congo red (CR) dianion, a double molecular switch containing two - N ═ N - azo groups, each of which can have the E or Z configuration. We find that collisional activation of CR dianions drives a one-way Z Z →E Z →E E cascade towards the lowest-energy isomer, whereas the absorption of a single photon over the 270-600 nm range can switch either azo group from E to Z or Z to E , driving the CR dianion to lower- or higher-energy forms. The experimental results, which are interpreted with the aid of calculated statistical isomerization rates, indicate that photoisomerization of CR in the gas phase involves a passage through conical intersection seams linking the excited and ground state potential energy surfaces rather than through isomerization on the ground state potential energy surface following internal conversion.

Dynamics of pulsed expansion of polyatomic gas cloud: Internal-translational energy transfer contribution

NASA Astrophysics Data System (ADS)

Morozov, A. A.

2007-08-01

Polyatomic gas cloud expansion under pulsed laser evaporation is studied on the basis of one-dimensional direct Monte Carlo simulation. The effect of rotational-translational (RT) and vibrational-translational (VT) energy transfer on dynamics of the cloud expansion is considered. Efficiency of VT energy transfer dependence on the amount of evaporated matter is discussed. To analyze VT energy transfer impact, the number of collisions per molecule during the expansion is calculated. The data are generally in good agreement with available analytical and numerical predictions. Dependencies of the effective number of vibrational degrees of freedom on the number of vibrationally inelastic collisions are obtained and generalized. The importance of the consideration of energy transfer from the internal degrees of freedom to the translational ones is illustrated by an example of pulsed laser evaporation of polytetrafluoroethylene (PTFE). Based on the obtained regularities, analysis of experimental data on pulsed laser evaporation of aniline is performed. The calculated aniline vibrational temperature correlates well with the experimentally measured one.

Clusters of DNA induced by ionizing radiation: formation of short DNA fragments. I. Theoretical modeling

NASA Technical Reports Server (NTRS)

Holley, W. R.; Chatterjee, A.

1996-01-01

We have developed a general theoretical model for the interaction of ionizing radiation with chromatin. Chromatin is modeled as a 30-nm-diameter solenoidal fiber comprised of 20 turns of nucleosomes, 6 nucleosomes per turn. Charged-particle tracks are modeled by partitioning the energy deposition between primary track core, resulting from glancing collisions with 100 eV or less per event, and delta rays due to knock-on collisions involving energy transfers >100 eV. A Monte Carlo simulation incorporates damages due to the following molecular mechanisms: (1) ionization of water molecules leading to the formation of OH, H, eaq, etc.; (2) OH attack on sugar molecules leading to strand breaks: (3) OH attack on bases; (4) direct ionization of the sugar molecules leading to strand breaks; (5) direct ionization of the bases. Our calculations predict significant clustering of damage both locally, over regions up to 40 bp and over regions extending to several kilobase pairs. A characteristic feature of the regional damage predicted by our model is the production of short fragments of DNA associated with multiple nearby strand breaks. The shapes of the spectra of DNA fragment lengths depend on the symmetries or approximate symmetries of the chromatin structure. Such fragments have subsequently been detected experimentally and are reported in an accompanying paper (B. Rydberg, Radiat, Res. 145, 200-209, 1996) after exposure to both high- and low-LET radiation. The overall measured yields agree well quantitatively with the theoretical predictions. Our theoretical results predict the existence of a strong peak at about 85 bp, which represents the revolution period about the nucleosome. Other peaks at multiples of about 1,000 bp correspond to the periodicity of the particular solenoid model of chromatin used in these calculations. Theoretical results in combination with experimental data on fragmentation spectra may help determine the consensus or average structure of the chromatin fibers in mammalian DNA.

Pressure effects on the relaxation of an excited nitromethane molecule in an argon bath

NASA Astrophysics Data System (ADS)

Rivera-Rivera, Luis A.; Wagner, Albert F.; Sewell, Thomas D.; Thompson, Donald L.

2015-01-01

Classical molecular dynamics simulations were performed to study the relaxation of nitromethane in an Ar bath (of 1000 atoms) at 300 K and pressures 10, 50, 75, 100, 125, 150, 300, and 400 atm. The molecule was instantaneously excited by statistically distributing 50 kcal/mol among the internal degrees of freedom. At each pressure, 1000 trajectories were integrated for 1000 ps, except for 10 atm, for which the integration time was 5000 ps. The computed ensemble-averaged rotational energy decay is ˜100 times faster than the vibrational energy decay. Both rotational and vibrational decay curves can be satisfactorily fit with the Lendvay-Schatz function, which involves two parameters: one for the initial rate and one for the curvature of the decay curve. The decay curves for all pressures exhibit positive curvature implying the rate slows as the molecule loses energy. The initial rotational relaxation rate is directly proportional to density over the interval of simulated densities, but the initial vibrational relaxation rate decreases with increasing density relative to the extrapolation of the limiting low-pressure proportionality to density. The initial vibrational relaxation rate and curvature are fit as functions of density. For the initial vibrational relaxation rate, the functional form of the fit arises from a combinatorial model for the frequency of nitromethane "simultaneously" colliding with multiple Ar atoms. Roll-off of the initial rate from its low-density extrapolation occurs because the cross section for collision events with L Ar atoms increases with L more slowly than L times the cross section for collision events with one Ar atom. The resulting density-dependent functions of the initial rate and curvature represent, reasonably well, all the vibrational decay curves except at the lowest density for which the functions overestimate the rate of decay. The decay over all gas phase densities is predicted by extrapolating the fits to condensed-phase densities.

Pressure effects on the relaxation of an excited nitromethane molecule in an argon bath

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rivera-Rivera, Luis A.; Wagner, Albert F.; Sewell, Thomas D.

2015-01-07

Classical molecular dynamics simulations were performed to study the relaxation of nitromethane in an Ar bath (of 1000 atoms) at 300 K and pressures 10, 50, 75, 100, 125, 150, 300, and 400 atm. The molecule was instantaneously excited by statistically distributing 50 kcal/mol among the internal degrees of freedom. At each pressure, 1000 trajectories were integrated for 1000 ps, except for 10 atm, for which the integration time was 5000 ps. The computed ensemble-averaged rotational energy decay is similar to 100 times faster than the vibrational energy decay. Both rotational and vibrational decay curves can be satisfactorily fit withmore » the Lendvay-Schatz function, which involves two parameters: one for the initial rate and one for the curvature of the decay curve. The decay curves for all pressures exhibit positive curvature implying the rate slows as the molecule loses energy. The initial rotational relaxation rate is directly proportional to density over the interval of simulated densities, but the initial vibrational relaxation rate decreases with increasing density relative to the extrapolation of the limiting low-pressure proportionality to density. The initial vibrational relaxation rate and curvature are fit as functions of density. For the initial vibrational relaxation rate, the functional form of the fit arises from a combinatorial model for the frequency of nitromethane "simultaneously" colliding with multiple Ar atoms. Roll-off of the initial rate from its low-density extrapolation occurs because the cross section for collision events with L Ar atoms increases with L more slowly than L times the cross section for collision events with one Ar atom. The resulting density-dependent functions of the initial rate and curvature represent, reasonably well, all the vibrational decay curves except at the lowest density for which the functions overestimate the rate of decay. The decay over all gas phase densities is predicted by extrapolating the fits to condensed-phase densities. (C) 2015 AIP Publishing LLC.« less

Pressure effects on the relaxation of an excited nitromethane molecule in an argon bath.

PubMed

Rivera-Rivera, Luis A; Wagner, Albert F; Sewell, Thomas D; Thompson, Donald L

2015-01-07

Classical molecular dynamics simulations were performed to study the relaxation of nitromethane in an Ar bath (of 1000 atoms) at 300 K and pressures 10, 50, 75, 100, 125, 150, 300, and 400 atm. The molecule was instantaneously excited by statistically distributing 50 kcal/mol among the internal degrees of freedom. At each pressure, 1000 trajectories were integrated for 1000 ps, except for 10 atm, for which the integration time was 5000 ps. The computed ensemble-averaged rotational energy decay is ∼100 times faster than the vibrational energy decay. Both rotational and vibrational decay curves can be satisfactorily fit with the Lendvay-Schatz function, which involves two parameters: one for the initial rate and one for the curvature of the decay curve. The decay curves for all pressures exhibit positive curvature implying the rate slows as the molecule loses energy. The initial rotational relaxation rate is directly proportional to density over the interval of simulated densities, but the initial vibrational relaxation rate decreases with increasing density relative to the extrapolation of the limiting low-pressure proportionality to density. The initial vibrational relaxation rate and curvature are fit as functions of density. For the initial vibrational relaxation rate, the functional form of the fit arises from a combinatorial model for the frequency of nitromethane "simultaneously" colliding with multiple Ar atoms. Roll-off of the initial rate from its low-density extrapolation occurs because the cross section for collision events with L Ar atoms increases with L more slowly than L times the cross section for collision events with one Ar atom. The resulting density-dependent functions of the initial rate and curvature represent, reasonably well, all the vibrational decay curves except at the lowest density for which the functions overestimate the rate of decay. The decay over all gas phase densities is predicted by extrapolating the fits to condensed-phase densities.

Pressure effects on the relaxation of an excited nitromethane molecule in an argon bath

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rivera-Rivera, Luis A.; Sewell, Thomas D.; Thompson, Donald L.

2015-01-07

Classical molecular dynamics simulations were performed to study the relaxation of nitromethane in an Ar bath (of 1000 atoms) at 300 K and pressures 10, 50, 75, 100, 125, 150, 300, and 400 atm. The molecule was instantaneously excited by statistically distributing 50 kcal/mol among the internal degrees of freedom. At each pressure, 1000 trajectories were integrated for 1000 ps, except for 10 atm, for which the integration time was 5000 ps. The computed ensemble-averaged rotational energy decay is ∼100 times faster than the vibrational energy decay. Both rotational and vibrational decay curves can be satisfactorily fit with the Lendvay-Schatzmore » function, which involves two parameters: one for the initial rate and one for the curvature of the decay curve. The decay curves for all pressures exhibit positive curvature implying the rate slows as the molecule loses energy. The initial rotational relaxation rate is directly proportional to density over the interval of simulated densities, but the initial vibrational relaxation rate decreases with increasing density relative to the extrapolation of the limiting low-pressure proportionality to density. The initial vibrational relaxation rate and curvature are fit as functions of density. For the initial vibrational relaxation rate, the functional form of the fit arises from a combinatorial model for the frequency of nitromethane “simultaneously” colliding with multiple Ar atoms. Roll-off of the initial rate from its low-density extrapolation occurs because the cross section for collision events with L Ar atoms increases with L more slowly than L times the cross section for collision events with one Ar atom. The resulting density-dependent functions of the initial rate and curvature represent, reasonably well, all the vibrational decay curves except at the lowest density for which the functions overestimate the rate of decay. The decay over all gas phase densities is predicted by extrapolating the fits to condensed-phase densities.« less

Electronic excitation cross section in positron scattering by H2 molecules using distorted-wave method

NASA Astrophysics Data System (ADS)

Weiss, Luciara I.; Pinho, Adriane S. F.; Michelin, Sergio E.; Fujimoto, Milton M.

2018-02-01

In this work we have applied for the first time the distorted-wave approximation (DWA) combined with Schwinger Variational Iterative Method (SVIM) to describe electronic excitation of H2 molecules by positron collisions. The integral (ICS) and differential (DCS) excitation cross sections for X 1 Σ g + → B 1 Σ u + transition of H2 molecule, in the range from near threshold up to 45 eV of positron energies, were reported in static (ST) and static-correlation-polarization (STPOL) levels. Our two-state ICS in DWA-ST level have quantitative agreement with experimental measurement at energies from threshold up to 18 eV and the inclusion of polarization effects increases the cross sections. Comparison with 2-state close-coupling approximation (CCA), 2-state Schwinger Multichannel (SMC), 5-state SMC and 1013-state from Convergent Close-Coupling (CCC) methods are done and is encouraging. The relative steeper drop above 22 eV in experimental ICS was not observed by any theoretical calculations indicating that new measurements would be interesting for this transition in this energy range.

Electron beams in research and technology

NASA Astrophysics Data System (ADS)

Mehnert, R.

1995-11-01

Fast electrons lose their energy by inelastic collisions with electrons of target molecules forming secondary electrons and excited molecules. Coulomb interaction of secondary electrons with valence electrons of neighboring molecules leads to the formation of radical cations, thermalized electrons, excited molecular states and radicals. The primary reactive species initiate chemical reactions in the materials irradiated. Polymer modifications using accelerated electrons such as cross-linking of cable insulation, tubes, pipes and moldings, vulcanization of elastomers, grafting of polymer surfaces, processing of foamed plastics and heat shrinkable materials have gained wide industrial acceptance. A steadily growing electron beam technology is curing of paints, lacquers, printing inks and functional coatings. Electron beam processing offers high productivity, the possibility to treat the materials at normal temperature and pressure, excellent process control and clean production conditions. On an industrial scale the most important application of fast electrons is curing of 100% reactive monomer/prepolymer systems. Mainly acrylates and epoxides are used to formulate functional coatings on substrates such as paper, foil, wood, fibre board and high pressure laminates. A survey is given about the reaction mechanism of curing, the characterization of cured coatings, and of some industrial application.

Three-Dimensional Tracking of Interfacial Hopping Diffusion

NASA Astrophysics Data System (ADS)

Wang, Dapeng; Wu, Haichao; Schwartz, Daniel K.

2017-12-01

Theoretical predictions have suggested that molecular motion at interfaces—which influences processes including heterogeneous catalysis, (bio)chemical sensing, lubrication and adhesion, and nanomaterial self-assembly—may be dominated by hypothetical "hops" through the adjacent liquid phase, where a diffusing molecule readsorbs after a given hop according to a probabilistic "sticking coefficient." Here, we use three-dimensional (3D) single-molecule tracking to explicitly visualize this process for human serum albumin at solid-liquid interfaces that exert varying electrostatic interactions on the biomacromolecule. Following desorption from the interface, a molecule experiences multiple unproductive surface encounters before readsorption. An average of approximately seven surface collisions is required for the repulsive surfaces, decreasing to approximately two and a half for surfaces that are more attractive. The hops themselves are also influenced by long-range interactions, with increased electrostatic repulsion causing hops of longer duration and distance. These findings explicitly demonstrate that interfacial diffusion is dominated by biased 3D Brownian motion involving bulk-surface coupling and that it can be controlled by influencing short- and long-range adsorbate-surface interactions.

Heating of Ejecta from a Meteorite Crater by the Perturbed Atmosphere

NASA Astrophysics Data System (ADS)

Kuz'micheva, M. Yu.

2018-03-01

Numerical simulation methods are used to investigate the thermal evolution of ejecta from a meteorite crater in the interaction with the perturbed atmosphere in the first few minutes after the impact. The study considers the role of air radiation, collisions of air molecules with the body's surface, and the heat transfer into the interior in the heat exchange of the ejecta and reveals the possibility of additional heating (compared with that at the time of the impact), which affects the geochemical and paleomagnetic properties of the ejecta.

Open-source Software for Exoplanet Atmospheric Modeling

NASA Astrophysics Data System (ADS)

Cubillos, Patricio; Blecic, Jasmina; Harrington, Joseph

2018-01-01

I will present a suite of self-standing open-source tools to model and retrieve exoplanet spectra implemented for Python. These include: (1) a Bayesian-statistical package to run Levenberg-Marquardt optimization and Markov-chain Monte Carlo posterior sampling, (2) a package to compress line-transition data from HITRAN or Exomol without loss of information, (3) a package to compute partition functions for HITRAN molecules, (4) a package to compute collision-induced absorption, and (5) a package to produce radiative-transfer spectra of transit and eclipse exoplanet observations and atmospheric retrievals.

More on molecular excitations: Dark matter detection in ice

DOE PAGES

Va'vra, J.

2016-08-10

In this paper we investigate di-atomic molecules embedded in ice crystals under strain. In this environment coherent vibrations of many OH-bonds may be generated by one WIMP collision. The detection of such multiple-photon signals may provide a signature of a 100 GeV/c 2 WIMP. To do a proper lab test of “WIMP-induced” multi-photon emission is very difficult. As a result, we suggest that Ice Cube make a search for multi-photon events, and investigate whether the rate of such events exhibits yearly modulation.

The Spatial and Temporal Variations in High Latitude Cosmic Noise Absorption and Their Relation to Luminous Aurora

DTIC Science & Technology

1963-05-01

extracted is essentially qual- itative in nature. Ideally one should supplement all-sky camera data with those obtained by means of photometers which...oscillating charges do not collide with each other and with neutral molecules, the energy extracted from the wave by ions and electrons is reradiated...collision frequency Sen & Wyller showed that the couplex index of refraction in the generalized theory is given by 2 20± VB2 sn02cS20 n - i c k A+B

Quantum fluctuations increase the self-diffusive motion of para-hydrogen in narrow carbon nanotubes.

PubMed

Kowalczyk, Piotr; Gauden, Piotr A; Terzyk, Artur P; Furmaniak, Sylwester

2011-05-28

Quantum fluctuations significantly increase the self-diffusive motion of para-hydrogen adsorbed in narrow carbon nanotubes at 30 K comparing to its classical counterpart. Rigorous Feynman's path integral calculations reveal that self-diffusive motion of para-hydrogen in a narrow (6,6) carbon nanotube at 30 K and pore densities below ∼29 mmol cm(-3) is one order of magnitude faster than the classical counterpart. We find that the zero-point energy and tunneling significantly smoothed out the free energy landscape of para-hydrogen molecules adsorbed in a narrow (6,6) carbon nanotube. This promotes a delocalization of the confined para-hydrogen at 30 K (i.e., population of unclassical paths due to quantum effects). Contrary the self-diffusive motion of classical para-hydrogen molecules in a narrow (6,6) carbon nanotube at 30 K is very slow. This is because classical para-hydrogen molecules undergo highly correlated movement when their collision diameter approached the carbon nanotube size (i.e., anomalous diffusion in quasi-one dimensional pores). On the basis of current results we predict that narrow single-walled carbon nanotubes are promising nanoporous molecular sieves being able to separate para-hydrogen molecules from mixtures of classical particles at cryogenic temperatures. This journal is © the Owner Societies 2011

Differentiation of protonated aromatic regioisomers related to lignin by reactions with trimethylborate in a fourier-transform ion cyclotron resonance mass spectrometer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Somuramasami, J; Duan, P; Amundson, Lucas M

2011-04-06

Several lignin model compounds were examined to test whether gas-phase ion–molecule reactions of trimethylborate (TMB) in a FTICR can be used to differentiate the ortho-, meta-, and para-isomers of protonated aromatic compounds, such as those formed during degradation of lignin. All three regioisomers could be differentiated for methoxyphenols and hydroxyphenols. However, only the differentiation of the ortho-isomer from the meta- and para-isomers was possible for hydroxyacetophenones and hydroxybenzoic acids. Consideration of the previously reported proton affinities at all basic sites in the isomeric hydroxyphenols, and the calculated proton affinities at all basic sites in the three methoxyphenol isomers, revealed thatmore » the proton affinities of the analytes relative to that of TMB play an important role in determining whether and how they react with TMB. The loss of two methanol molecules (instead of one) from the adducts formed with TMB either during ion–molecule reactions, or during sustained-off resonance irradiated collision-activated dissociation of the ion–molecule reaction products, revealed the presence of two functionalities in almost all the isomers. This finding supports earlier results suggesting that TMB can be used to count the functionalities in unknown oxygen-containing analytes.« less

Long-range interactions between polar bialkali ground-state molecules in arbitrary vibrational levels

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vexiau, R.; Lepers, M., E-mail: maxence.lepers@u-psud.fr; Aymar, M.

2015-06-07

We have calculated the isotropic C{sub 6} coefficients characterizing the long-range van der Waals interaction between two identical heteronuclear alkali-metal diatomic molecules in the same arbitrary vibrational level of their ground electronic state X{sup 1}Σ{sup +}. We consider the ten species made up of {sup 7}Li, {sup 23}Na, {sup 39}K, {sup 87}Rb, and {sup 133}Cs. Following our previous work [Lepers et al., Phys. Rev. A 88, 032709 (2013)], we use the sum-over-state formula inherent to the second-order perturbation theory, composed of the contributions from the transitions within the ground state levels, from the transition between ground-state and excited state levels,more » and from a crossed term. These calculations involve a combination of experimental and quantum-chemical data for potential energy curves and transition dipole moments. We also investigate the case where the two molecules are in different vibrational levels and we show that the Moelwyn-Hughes approximation is valid provided that it is applied for each of the three contributions to the sum-over-state formula. Our results are particularly relevant in the context of inelastic and reactive collisions between ultracold bialkali molecules in deeply bound or in Feshbach levels.« less

Utilization of UV and IR Supercontinua in Gas-Phase Subpicosecond Kinetic Spectroscopy

NASA Astrophysics Data System (ADS)

Glownia, J. H.; Misewich, J.; Sorokin, P. P.

Through the work of photochemists extending over many decades, there now exists a wealth of information on the various reactions that photoexcited gas phase molecules undergo. Most of this information relates to the product molecules that are formed, either as the direct result of a primary photochemical act, such as photodissociation, or through subsequent secondary reactions, involving collisions with other molecules in the gas. Recently, there has been an extensive effort directed at determining the exact energy distributions of the primary products formed in photodissociation. With the use of nanosecond tunable-laser techniques, such as laser-induced fluorescence (LIF) and coherent anti-Stokes Raman spectroscopy (CARS), scientists have successfully determined the nascent electronic, vibrational, and rotational energy distributions of various diatomic fragments such as CN, OH, NO, and O2 that are directly formed in the photodissociation of many kinds of molecules. The ready availability of high-quality, tunable, nanosecond lasers has made determination of the above-mentioned collisionless energy distributions a relatively straightforward process. The determination of product translational energies has long effectively been handled by angularly resolved time-of-flight (TOF) spectroscopy, or by sub-Doppler resolution spectroscopy, including a recently improved version of the latter, velocity-aligned Doppler spectroscopy (Xu et al., 1986).

Astrophysical Applications for Charge-Exchange with H, He, and H2 Targets

NASA Astrophysics Data System (ADS)

Cumbee, Renata S.; Mullen, Patrick D.; Shelton, Robin L.; Schultz, David R.; Stancil, Phillip C.

2018-01-01

When a hot plasma collides with a cold neutral gas, interactions occur between the constituents at the interface of the collision, including charge exchange (CX). CX is a process in which an electron can be transferred from a neutral atom or molecule into an excited energy level of an ion. Following this transfer, the excited electron relaxes to lower energy levels, emitting X-rays. This process has been established as a primary source of X-ray emission within our solar system, such as when the solar wind interacts with cometary and planetary atmospheres, and outside of our solar system, such as in the hot outflows of starburst galaxies.As the CX X-ray emission spectrum varies greatly with collision velocity, it is critical that realistic CX data are included in X-ray spectral models in regions in which CX might be significant so that the ion abundance and plasma velocities can be estimated most accurately. Here, a set of CX X-ray line ratios and spectra will be shown for a variety of collision velocities for C-Cl ions colliding with H, He, and H2. An X-ray emission model including these line ratios performed in XSPEC will be presented for a region of the Cygnus Loop supernova remnant and the starburst galaxy M82 in order to highlight the variation in CX spectral models with collision energy and neutral target species.R. Cumbee’s research was partially supported by an appointment to the NASA Postdoctoral Program at NASA GSFC, administered by Universities Space Research Association under contract with NASA. Work at UGA was partially supported by NASA grants NNX09AC46G and NNG09WF24I.

Observation of CO2 and solvent adduct ions during negative mode electrospray ionization Fourier transform ion cyclotron resonance mass spectrometric analysis of monohydric alcohols.

PubMed

Zhou, Xibin; Zhang, Yahe; Zhao, Suoqi; Hsu, Chang Samuel; Shi, Quan

2013-12-15

Monohydric alcohols are common in natural products, bio-oils, and medicine. We have found that monohydric alcohols can form O3 (ions containing three oxygen atoms) and O4 adduct ions in negative electrospray ionization (ESI) Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS), which would significantly affect the composition analysis of alcohols, especially in a complex mixture. It is necessary to study the reaction pathways and the method to eliminate or reduce the 'artifact' adducts. Octadecanol, cholesterol, squalanol and two complex monohydric alcohol mixtures were selected as model compounds. These samples were subjected to negative ion ESI FT-ICR MS analysis. The composition and formation mechanism of adducts were studied by the ultrahigh-resolution accurate mass measurement for elemental composition, along with the MS(2) isolation and collision-induced dissociation (CID) experiments for structural determination. The reaction pathway of O3 adduct formation is the coupling of a monohydric alcohol ion with a CO2 to form a stable O3 ionic species by likely a covalent bond (source of CO2 is not clear). The O4 species are formed by O3 ionic species adducted with an alcohol molecule of the solvent, such as methanol or ethanol, by likely a hydrogen bond. These adduct ions could be eliminated or reduced by increasing collision energy. However, excessive collision energy would fragment monohydric alcohol ions. The formation mechanisms of O3 and O4 adducts from monohydric alcohols in negative ion ESI FT-ICR MS were proposed. The solvent adduction effects can be eliminated or reduced by optimizing the collision energy of CID in FT-ICR MS. Copyright © 2013 John Wiley & Sons, Ltd.

Inelastic rate coefficients for collisions of C6H- with H2 and He

NASA Astrophysics Data System (ADS)

Walker, Kyle M.; Lique, François; Dumouchel, Fabien; Dawes, Richard

2017-04-01

The recent detection of anions in the interstellar medium has shown that they exist in a variety of astrophysical environments - circumstellar envelopes, cold dense molecular clouds and star-forming regions. Both radiative and collisional processes contribute to molecular excitation and de-excitation in these regions so that the 'local thermodynamic equilibrium' approximation, where collisions cause the gas to behave thermally, is not generally valid. Therefore, along with radiative coefficients, collisional excitation rate coefficients are needed to accurately model the anionic emission from these environments. We focus on the calculation of state-to-state rate coefficients of the C6H- molecule in its ground vibrational state in collisions with para-H2, ortho-H2 and He using new potential energy surfaces. Dynamical calculations for the pure rotational excitation of C6H- were performed for the first 11 rotational levels (up to j1 = 10) using the close-coupling method, while the coupled-states approximation was used to extend the H2 rate coefficients to j1 = 30, where j1 is the angular momentum quantum number of C6H-. State-to-state rate coefficients were obtained for temperatures ranging from 2 to 100 K. The rate coefficients for H2 collisions for Δj1 = -1 transitions are of the order of 10-10 cm3 s-1, a factor of 2 to 3 greater than those of He. Propensity rules are discussed. The collisional excitation rate coefficients produced here impact astrophysical modelling since they are required for obtaining accurate C6H- level populations and line emission for regions that contain anions.

Chemical dynamics simulations of the monohydrated OH-(H2O) + CH3I reaction. Atomic-level mechanisms and comparison with experiment

NASA Astrophysics Data System (ADS)

Xie, Jing; Otto, Rico; Wester, Roland; Hase, William L.

2015-06-01

Direct dynamics simulations, with B97-1/ECP/d theory, were performed to study the role of microsolvation for the OH-(H2O) + CH3I reaction. The SN2 reaction dominates at all reactant collision energies, but at higher collision energies proton transfer to form CH2I-, and to a lesser extent CH2I- (H2O), becomes important. The SN2 reaction occurs by direct rebound and stripping mechanisms, and 28 different indirect atomistic mechanisms, with the latter dominating. Important components of the indirect mechanisms are the roundabout and formation of SN2 and proton transfer pre-reaction complexes and intermediates, including [CH3--I--OH]-. In contrast, for the unsolvated OH- + CH3I SN2 reaction, there are only seven indirect atomistic mechanisms and the direct mechanisms dominate. Overall, the simulation results for the OH-(H2O) + CH3IߙSN2 reaction are in good agreement with experiment with respect to reaction rate constant, product branching ratio, etc. Differences between simulation and experiment are present for the SN2 velocity scattering angle at high collision energies and the proton transfer probability at low collision energies. Equilibrium solvation by the H2O molecule is unimportant. The SN2 reaction is dominated by events in which H2O leaves the reactive system as CH3OH is formed or before CH3OH formation. Formation of solvated products is unimportant and participation of the (H2O)CH3OH---I- post-reaction complex for the SN2 reaction is negligible.

Water absorption lines, 931-961 nm - Selected intensities, N2-collision-broadening coefficients, self-broadening coefficients, and pressure shifts in air

NASA Technical Reports Server (NTRS)

Giver, L. P.; Gentry, B.; Schwemmer, G.; Wilkerson, T. D.

1982-01-01

Intensities were measured for 97 lines of H2O vapor between 932 and 961 nm. The lines were selected for their potential usefulness for remote laser measurements of H2O vapor in the earth's atmosphere. The spectra were obtained with several different H2O vapor abundances and N2 broadening gas pressures; the spectral resolution was 0.046/cm FWHM. Measured H2O line intensities range from 7 x 10 to the -25th to 7 x 10 to the -22nd/cm per (molecules/sq cm). H2O self-broadening coefficients were measured for 13 of these strongest lines; the mean value was 0.5/cm per atm. N2-collision-broadening coefficients were measured for 73 lines, and the average was 0.11 cm per atm HWHM. Pressure shifts in air were determined for a sample of six lines between 948 and 950 nm; these lines shift to lower frequency by an amount comparable to 0.1 of the collision-broadened widths measured in air or N2. The measured intensities of many lines of 300-000 band are much larger than expected from prior computations, in some cases by over an order of magnitude. Coriolis interactions with the stronger 201-000 band appear to be the primary cause of the enhancement of these line intensities.

Collision-induced dissociation of protonated water clusters

NASA Astrophysics Data System (ADS)

Berthias, F.; Buridon, V.; Abdoul-Carime, H.; Farizon, B.; Farizon, M.; Dinh, P. M.; Reinhard, P.-G.; Suraud, E.; Märk, T. D.

2014-06-01

Collision-induced dissociation (CID) has been studied for protonated water clusters H+(H2O)n, with n = 2-8, colliding with argon atoms at a laboratory energy of 8 keV. The experimental data have been taken with an apparatus (Device for Irradiation of Molecular Clusters, `Dispositif d'Irradiation d'Agrégats Moléculaire,' DIAM) that has been recently constructed at the Institut de Physique Nucléaire de Lyon. It includes an event-by-event mass spectrometry detection technique, COINTOF (correlated ion and neutral fragment time of flight). The latter device allows, for each collision event, to detect and identify in a correlated manner all produced neutral and charged fragments. For all the studied cluster ions, it has allowed us to identify branching ratios for the loss of i = 1 to i = n water molecules, leading to fragment ions ranging from H+(H2O)i=n-1 all the way down to the production of protons. Using a corresponding calibration technique we determine total charged fragment production cross sections for incident protonated water clusters H+(H2O)n, with n = 2-7. Observed trends for branching ratios and cross sections, and a comparison with earlier data on measured attenuation cross sections for water clusters colliding with other noble gases (He and Xe), give insight into the underlying dissociation mechanisms.