Quantum Mechanical Study of Sulfuric Acid Hydration: Atmospheric Implications

The role of the binary nucleation of sulfuric acid in aerosol formation and its implications for global warming is one of the fundamental unsettled questions in atmospheric chemistry. We have investigated the thermodynamics of sulfuric acid hydration using ab initio quantum mechanical methods. For H2SO4(H2O)n where n = 1–6, we used a scheme combining molecular dynamics configurational sampling with high-level ab initio calculations to locate the global and many low lying local minima for each cluster size. For each isomer, we extrapolated the Møller–Plesset perturbation theory (MP2) energies to their complete basis set (CBS) limit and added finite temperature corrections within the rigid-rotor-harmonic-oscillator (RRHO) model using scaled harmonic vibrational frequencies. We found that ionic pair (HSO4–·H3O+)(H2O)n−1 clusters are competitive with the neutral (H2SO4)(H2O)n clusters for n ≥ 3 and are more stable than neutral clusters for n ≥ 4 depending on the temperature. The Boltzmann averaged Gibbs free energies for the formation of H2SO4(H2O)n clusters are favorable in colder regions of the troposphere (T = 216.65–273.15 K) for n = 1–6, but the formation of clusters with n ≥ 5 is not favorable at higher (T > 273.15 K) temperatures. Our results suggest the critical cluster of a binary H2SO4–H2O system must contain more than one H2SO4 and are in concert with recent findings(1) that the role of binary nucleation is small at ambient conditions, but significant at colder regions of the troposphere. Overall, the results support the idea that binary nucleation of sulfuric acid and water cannot account for nucleation of sulfuric acid in the lower troposphere.

Benchmark Structures and Binding Energies of Small Water Clusters with Anharmonicity Corrections

For (H2O)n where n = 1–10, we used a scheme combining molecular dynamics sampling with high level ab initio calculations to locate the global and many low lying local minima for each cluster. For each isomer, we extrapolated the RI-MP2 energies to their complete basis set limit, included a CCSD(T) correction using a smaller basis set and added finite temperature corrections within the rigid-rotor-harmonic-oscillator (RRHO) model using scaled and unscaled harmonic vibrational frequencies. The vibrational scaling factors were determined specifically for water clusters by comparing harmonic frequencies with VPT2 fundamental frequencies. We find the CCSD(T) correction to the RI-MP2 binding energy to be small (

Quantum Mechanical Study of Sulfuric Acid Hydration: Atmospheric Implications

The role of the binary nucleation of sulfuric acid in aerosol formation and its implications for global warming is one of the fundamental unsettled questions in atmospheric chemistry. We have investigated the thermodynamics of sulfuric acid hydration using ab initio quantum mechanical methods. For H2SO4(H2O)n where n = 1–6, we used a scheme combining molecular dynamics configurational sampling with high-level ab initio calculations to locate the global and many low lying local minima for each cluster size. For each isomer, we extrapolated the Møller–Plesset perturbation theory (MP2) energies to their complete basis set (CBS) limit and added finite temperature corrections within the rigid-rotor-harmonic-oscillator (RRHO) model using scaled harmonic vibrational frequencies. We found that ionic pair (HSO4–·H3O+)(H2O)n−1clusters are competitive with the neutral (H2SO4)(H2O)n clusters for n ≥ 3 and are more stable than neutral clusters for n ≥ 4 depending on the temperature. The Boltzmann averaged Gibbs free energies for the formation of H2SO4(H2O)n clusters are favorable in colder regions of the troposphere (T = 216.65–273.15 K) for n = 1–6, but the formation of clusters with n ≥ 5 is not favorable at higher (T > 273.15 K) temperatures. Our results suggest the critical cluster of a binary H2SO4–H2O system must contain more than one H2SO4 and are in concert with recent findings(1) that the role of binary nucleation is small at ambient conditions, but significant at colder regions of the troposphere. Overall, the results support the idea that binary nucleation of sulfuric acid and water cannot account for nucleation of sulfuric acid in the lower troposphere.

Quantifying the complexity of chaos in multibasin multidimensional dynamics of molecular systems

The simulated classical dynamics of a small molecule exhibiting self-organizing behavior via a fast transition between two states is analyzed by calculation of the statistical complexity of the system. It is shown that the complexity of molecular descriptors such as atom coordinates and dihedral angles have different values before and after the transition. This provides a new tool to identify metastable states during molecular self-organization. The highly concerted collective motion of the molecule is revealed. Low-dimensional subspaces dynamics is found sensitive to the processes in the whole, high-dimensional phase space of the system. © 2004 Wiley Periodicals, Inc.

Quantum diffusion in thin disordered wires

Quantum Ohmic residual resistance of a thin disordered wire, approximated as a one-dimensional multichannel conductor, is known to scale exponentially with length. This nonadditivity is shown to imply (i) a low-frequency noise-power spectrum proportional to -ln(Ω)/Ω, and (ii) a dispersive capacitative impedance proportional to tanh(√iΩ )/ √iΩ. A deep connection to the quantum Brownian motion with linear dynamical frictional coupling to a harmonic-oscillator bath is pointed out and interpreted in physical terms.

The Hamilton-Jacobi equation revisited

A new analysis of the nature of the solutions of the Hamilton-Jacobi equation of classical dynamics is presented based on Caratheodory’s theorem concerning canonical transformations. The special role of a principal set of solutions is stressed, and the existence of analogous results in quantum mechanics is outlined.

Rotational cut-off and anharmonicity effects on thermodynamic properties of gases at high temperatures

The exact expressions for the partition function (Q) and the coefficient of specific heat at constant volume (Cv) for a rotating-anharmonic oscillator molecule, including coupling and rotational cut-off, have been formulated and values of Q and Cv have been computed in the temperature range of 100 to 100,000 K for O2, N2 and H2 gases. The exact Q and Cv values are also compared with the corresponding rigid-rotator harmonic-oscillator (infinite rotational and vibrational levels) and rigid-rotator anharmonic-oscillator (infinite rotational levels) values. The rigid-rotator harmonic-oscillator approximation can be accepted for temperatures up to about 5000 K for O2 and N2. Beyond these temperatures the error in Cv will be significant, because of anharmonicity and rotational cut-off effects. For H2, the rigid-rotator harmonic-oscillator approximation becomes unacceptable even for temperatures as low as 2000 K.

Force constants and thermodynamic functions of iodine heptafluoride

Normal coordinate analysis of a molecule of the type XY7 (point group D5h) has been carried out using Wilson's FG, matrix method and the results have been utilized to calculate the force constants of IF7 from the available Raman and infrared data. Some of the assignments made previously by Lord and others have been revised and with the revised assignments the thermodynamic quantities of IF7 have been computed from 300°K to 1000°K under rigid rotator and harmonic oscillator approximation.

Undamped oscillations of homogeneous collisionless stellar systems

The Lewis (1968) invariant of the time-dependent harmonic oscillator is used to construct exact time-dependent, uniform density solutions of the collisionless Boltzmann equation. The spatially bound solutions are time-periodic.

Partially conserved axial-vector current inS-matrix theory

Mandelstam�s argument that PCAC follows from assigning Lorentz quantum numberM=1 to the massless pion is examined in the context of multiparticle dual resonance model. We construct a factorisable dual model for pions which is formulated operatorially on the harmonic oscillator Fock space along the lines of Neveu-Schwarz model. The model has bothm ? andm ? as arbitrary parameters unconstrained by the duality requirement. Adler self-consistency condition is satisfied if and only if the conditionm?2?m?2=1/2 is imposed, in which case the model reduces to the chiral dual pion model of Neveu and Thorn, and Schwarz. The Lorentz quantum number of the pion in the dual model is shown to beM=0.

A matrix identity and perturbation expressions

An identity expressing formally the diagonal and off-diagonal elements of an inverse of a matrix is deduced employing operator techniques. Several well-known perturbation expressions for the self-energy are deduced as special cases. A new approximation and other applications following from the above formalism are briefly indicated through illustrations from a perturbed harmonic oscillator, chemisorption approximations and Kelly's result in the problem of electron correlation.

Exact nonlinear travelling hydromagnetic wave solutions

Exact travelling wave solutions for hydromagnetic waves in an exponentially stratified incompressible medium are obtained. With the help of two integrals it becomes possible to reduce the system of seven nonlinear PDE's to a second order nonlinear ODE which describes an one dimensional harmonic oscillator with a nonlinear friction term. This equation is studied in detail in the phase plane. The travelling waves are periodic only when they propagate either horizontally or vertically. The reduced second order nonlinear differential equation describing the travelling waves in inhomogeneous conducting media has rather ubiquitous nature in that it also appears in other geophysical systems such as internal waves, Rossby waves and topographic Rossby waves in the ocean.

Ground State of N Harmonically Bound Anyons in a Magnetic Field

The properties of the ground state of N anyons in an external magnetic field and a harmonic oscillator potential are computed in the large-N limit using the Thomas-Fermi approximation. The number of level crossings in the ground state as a function of the harmonic frequency, the strength and the direction of the magnetic field and N are also studied.

Time-dependent transitions with time-space noncommutativity and its implications in quantum optics

We study the time-dependent transitions of a quantum-forced harmonic oscillator in noncommutative R(1,1) perturbatively to linear order in the noncommutativity theta. We show that the Poisson distribution gets modified, and that the vacuum state evolves into a `squeezed' state rather than a coherent state. The time evolutions of uncertainties in position and momentum in vacuum are also studied and imply interesting consequences for modeling nonlinear phenomena in quantum optics.

Noncommutative vortices and instantons from generalized Bose operators

Generalized Bose operators correspond to reducible representations of the harmonic oscillator algebra. We demonstrate their relevance in the construction of topologically non-trivial solutions in noncommutative gauge theories, focusing our attention to flux tubes, vortices, and instantons. Our method provides a simple new relation between the topological charge and the number of times the basic irreducible representation occurs in the reducible representation underlying the generalized Bose operator. When used in conjunction with the noncommutative ADHM construction, we find that these new instantons are in general not unitarily equivalent to the ones currently known in literature.