Accurate vibrational-rotational partition functions and standard-state free energy values for H2O2 from Monte Carlo path-integral calculations

Accurate quantum mechanical partition functions and absolute free energies of H(2)O(2) are determined using a realistic potential energy surface [J. Koput, S. Carter, and N. C. Handy, J. Phys. Chem. A 102, 6325 (1998)] for temperatures ranging from 300 to 2,400 K by using Monte Carlo path integral calculations with new, efficient polyatomic importance sampling methods. The path centroids are sampled in Jacobi coordinates via a set of independent ziggurat schemes. The calculations employed enhanced-same-path extrapolation of trapezoidal Trotter Fourier path integrals, and the paths were constructed using fast Fourier sine transforms. Importance sampling was also used in Fourier coefficient space, and adaptively optimized stratified sampling was used in configuration space. The free energy values obtained from the path-integral calculations are compared to separable-mode approximations, to the Pitzer-Gwinn approximation, and to values in thermodynamic tables. Our calculations support the recently proposed revisions to the JANAF tables.     

Variational Convergence of Gradient Flows and Rate-Independent Evolutions in Metric Spaces

We study the asymptotic behaviour of families of gradient flows in a general metric setting, when the metric-dissipation potentials degenerate in the limit to a dissipation with linear growth. We present a general variational definition of BV solutions to metric evolutions, showing the different characterization of the solution in the absolutely continuous regime, on the singular Cantor part, and along the jump transitions. By using tools of metric analysis, BV functions and blow-up by time rescaling, we show that this variational notion is stable with respect to a wide class of perturbations involving energies, distances, and dissipation potentials. As a particular application, we show that BV solutions to rate-independent problems arise naturally as a limit of p-gradient flows, p >?1, when the exponents p converge to 1.     

Practical methods for including torsional anharmonicity in thermochemical calculations on complex molecules: the internal-coordinate multi-structural approximation

Many methods for correcting harmonic partition functions for the presence of torsional motions employ some form of one-dimensional torsional treatment to replace the harmonic contribution of a specific normal mode. However, torsions are often strongly coupled to other degrees of freedom, especially other torsions and low-frequency bending motions, and this coupling can make assigning torsions to specific normal modes problematic. Here, we present a new class of methods, called multi-structural (MS) methods, that circumvents the need for such assignments by instead adjusting the harmonic results by torsional correction factors that are determined using internal coordinates. We present three versions of the MS method: (i) MS-AS based on including all structures (AS), i.e., all conformers generated by internal rotations; (ii) MS-ASCB based on all structures augmented with explicit conformational barrier (CB) information, i.e., including explicit calculations of all barrier heights for internal-rotation barriers between the conformers; and (iii) MS-RS based on including all conformers generated from a reference structure (RS) by independent torsions. In the MS-AS scheme, one has two options for obtaining the local periodicity parameters, one based on consideration of the nearly separable limit and one based on strongly coupled torsions. The latter involves assigning the local periodicities on the basis of Voronoi volumes. The methods are illustrated with calculations for ethanol, 1-butanol, and 1-pentyl radical as well as two one-dimensional torsional potentials. The MS-AS method is particularly interesting because it does not require any information about conformational barriers or about the paths that connect the various structures.