Intermolecular forces in globular molecules. II.
Intermolecular forces in methyl chloride and benzene calculated using spherical shell central potential theory
POTENTIAL THEORY↗
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Molecular collisions. V.
Transport coefficient expressions for collisions between rigid diatomic molecules, using perturbation method
TRANSPORT COEFFICIENT↗
Intermediate-range intermolecular forces in H sub 2 super plus.
Intermediate range intermolecular forces with overlapping wave functions and exchange effects calculated for ionized H molecule using perturbation theory
PERTURBATION THEORY↗
Estimation of rate constants of elementary processes - A review of the state of the art.
'Thermochemical kinetics,' the codification and extrapolation of empirical observations, as applied to certain elementary reactions of importance to combustion studies, is described. This approach allows the critical scrutiny of experimental data in areas where sufficient previous data exist, while, at the same time, illuminating those key areas where more experimentation is crucial. It is shown that combination of transition-state theory with an understanding of the molecular basis of entropy puts fairly rigid constraints on the values of the Arrhenius A-factor for most reactions. This, in turn, means that the activation energy is often the key datum that is missing, and that such data can be obtained with some degree of confidence, even from measurements of rate constants at only one temperature. In complex mechanisms, it is often possible to distinguish among alternate pathways and pinpoint key processes.
Golden, D. M.↗
Low-energy electron scattering from CO. 2: Ab-initio study using the frame-transformation theory
The Wigner-Eisenbud R matrix method has been combined with the frame transformation theory to study electron scattering from molecular systems. The R matrix, calculated at the boundary point of the molecular core radius, has been transformed to the space frame in order to continue the solution of the scattering equations in the outer region where rotational motion of the nuclei is taken into account. This procedure has been applied to a model calculation of thermal energy electron scattering from CO.
Chandra, N.↗
A statistical model for the initial stellar mass function
The nonlinear stages of the fragmentation of a collapsing molecular cloud are modeled by coagulation theory. Several distinct physical processes are discussed, including protostellar fragment coalescence, gas accretion, and binary formation. This work confirms and extends the earlier result of Nakano (1966) that an approximately self-similar limiting form of the mass spectrum develops after several mean initial collision times. An approximate solution to the velocity-averaged coagulation equation is given for an arbitrary power-law dependence of the coalescence rate on mass, with dimensional dependence proportional to m to the power lambda; i.e., the asymptotic mass spectrum varies as m to the -3 lambda/2 power at small masses and cuts off exponentially at large masses, the characteristic mass depending on the number of collision times elapsed. Simple physical arguments suggest that lambda may increase with increasing mass, but is restricted to the range from 2/3 to 4/3. A large fraction of collisions could result in binary formation.
Silk, J.↗
Modeling of Branched (L, T and Y) Carbon Nanotubes
Models for connecting two or three carbon nanotubes (CNT) using topological defects (i.e., pentagons and heptagons) are presented for the characterization of experimentally observed L, T and Y CNT junctions. The effects of the separation and orientation of the topological defects on the structures and energetics of these junctions are investigated using the nonlocal density function theory (DFT) and semi-empirical molecular orbital (AM1) calculations, and the Brenner empirical potential molecular mechanics simulations. The potential applications of L, Y and T CNT junctions in nanoelectronic devices are also discussed.
Han, Jie↗
Theoretical Studies of Spectroscopic Line Mixing in Remote Sensing Applications
The phenomenon of collisional transfer of intensity due to line mixing has an increasing importance for atmospheric monitoring. From a theoretical point of view, all relevant information about the collisional processes is contained in the relaxation matrix where the diagonal elements give half-widths and shifts, and the off-diagonal elements correspond to line interferences. For simple systems such as those consisting of diatom-atom or diatom-diatom, accurate fully quantum calculations based on interaction potentials are feasible. However, fully quantum calculations become unrealistic for more complex systems. On the other hand, the semi-classical Robert-Bonamy (RB) formalism, which has been widely used to calculate half-widths and shifts for decades, fails in calculating the off-diagonal matrix elements. As a result, in order to simulate atmospheric spectra where the effects from line mixing are important, semi-empirical fitting or scaling laws such as the ECS (Energy-Corrected Sudden) and IOS (Infinite-Order Sudden) models are commonly used. Recently, while scrutinizing the development of the RB formalism, we have found that these authors applied the isolated line approximation in their evaluating matrix elements of the Liouville scattering operator given in exponential form. Since the criterion of this assumption is so stringent, it is not valid for many systems of interest in atmospheric applications. Furthermore, it is this assumption that blocks the possibility to calculate the whole relaxation matrix at all. By eliminating this unjustified application, and accurately evaluating matrix elements of the exponential operators, we have developed a more capable formalism. With this new formalism, we are now able not only to reduce uncertainties for calculated half-widths and shifts, but also to remove a once insurmountable obstacle to calculate the whole relaxation matrix. This implies that we can address the line mixing with the semi-classical theory based on interaction potentials between molecular absorber and molecular perturber. We have applied this formalism to address the line mixing for Raman and infrared spectra of molecules such as N2, C2H2, CO2, NH3, and H2O. By carrying out rigorous calculations, our calculated relaxation matrices are in good agreement with both experimental data and results derived from the ECS model.
Formalism↗
Ambient pressure determination at high altitudes by use of free-molecule theory
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GASES - DYNAMICS↗
Photochemistry and molecular ions in oxygen-rich circumstellar envelopes
A theory for the ionization of the circumstellar envelopes around O-rich red giants is developed from the photochemical model. The main source of ionization is photoionization of H2O, OH, and C by the interstellar UV radiation field, supplemented by cosmic-ray ionization of hydrogen. Significant amounts of H3O(+) and HCO(+) are produced, with peak abundances of about 10 to the -7th at intermediate distances from the star. Although H3O(+) may be difficult to detect with current instrumentation, HCO(+) is probably detectable in nearby O-rich envelopes with large millimeter-wave telescopes.
Mamon, G. A.↗
Formation of Silicate Grains in Circumstellar Environments: Experiment, Theory and Observations
Amongst chemical reactions (1) in the molecular universe (2), condensation reaction is probably the most poorly understood. The condensation of a solid from its components in the gas phase occurs in many parts of our galaxy such as stellar mass outflows, the terrestrial region of protoplanetary disks and in primordial solar nebula (3). But how does the transition occur from molecules to intermediate clusters to macroscopic grains? The major focus of the present work is the identification of chemical condensation reaction pathways that lead to the formation of stoichiometry, composition and crystallinity of cosmic silicates from vapor phase species.
Castleman, A., Jr.↗
Identifying Molecules as Biosignatures with Assembly Theory and Mass Spectrometry
The search for evidence of life elsewhere in the universe is hard because it is not obvious what signatures are unique to life. Here we postulate that complex molecules found in high abundance are universal biosignatures as they cannot form by chance. To explore this, we developed the first intrinsic measure of molecular complexity that can be experimentally determined, and this is based upon a new approach called assembly theory which gives the molecular assembly number (MA) of a given molecule. MA allows us to compare the intrinsic complexity of molecules using the minimum number of steps required to construct the molecular graph starting from basic objects, and a probabilistic model shows how the probability of any given molecule forming randomly drops dramatically as its MA increases. To map chemical space, we calculated the MA of ca. 2.5 million compounds, and collected data which showed the complexity of a molecule can be experimentally determined by using three independent techniques including infra-red spectroscopy, nuclear magnetic resonance, and by fragmentation in a mass spectrometer, and this data has an excellent corelation with the values predicted from our assembly theory. We then set out to see if this approach could allow us to identify molecular biosignatures with a set of diverse samples from around the world, outer space, and the laboratory including prebiotic soups. The results show that there is a non-living to living threshold in MA complexity and the higher the MA for a given molecule, the more likely that it had to be produced by a biological process. This work demonstrates it is possible to use this approach to build a life detection instrument that could be deployed on missions to extra-terrestrial locations to detect biosignatures, map the extent of life on Earth, and be used as a molecular complexity scale to quantify the constraints needed to direct prebiotically plausible processes in the laboratory. Such an approach is vital if we are going to find new life elsewhere in the universe or create de-novo life in the lab.
Stuart M Marshall↗
Application of exchange perturbation theories to the delta-function model of H sub 2 ion
Exchange perturbation theories applied to delta function model of molecular hydrogen ion, discussing EL-HAV second order energy at large internuclear separations
Certain, P. R.↗
Simple collision theory of reactive hard spheres
Hard sphere model for reactive molecular collisions based on energy and momentum of reactants and products
Marron, M. T.↗
Kerr response of nematic liquids.
Description of the results of recent observations of the Kerr effect in nematic liquid crystals in a temperature range just above their nematic-isotropic transition. These results indicate that the intermolecular ordering forces in a nematic substance can enhance the Kerr effect just above the nematic transition in their isotropic state. It is felt that existing theory provides a useful approximation for relating molecular size to response time.
Johnston, A. R.↗
Vibration-translation energy transfer in anharmonic diatomic molecules. 1: A critical evaluation of the semiclassical approximation
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.
Mckenzie, R. L.↗
Vibration-translation energy transfer in anharmonic diatomic molecules. I - A comparative evaluation of the semiclassical approximation
The semiclassical approximation (quantum oscillator, classical path) 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.
Mckenzie, R. L.↗
Vibrational dependence of pressure induced spectral linewidths and line shifts - Application of the infinite order sudden scattering approximation
The infinite order sudden (IOS) approximation to molecular rotation is applied to simplify the theory of linewidths and shifts in vibration-rotation spectra. This approximation is expected to be most accurate for hard, short-range collisions and is therefore complementary to Anderson theory which is best for weak, glancing collisions. The IOS approximation predicts identical linewidths and shifts for P- and R-branch transitions with the same line number. It also predicts zero line shifts for pure rotational spectra. The dependence of linewidths and shifts on vibrational band is seen to be due mainly to variation in diagonal vibrational matrix elements of the intermolecular potential. Calculations are performed for the 0-0, 0-1, and 0-2 bands of CO perturbed by He, using a theoretical interaction potential with no semiempirical or adjustable parameters; results are in satisfactory accord with experimental data.
Green, S.↗