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Daniel M Chipman

Publications and source records attributed to Daniel M Chipman.

8 recordsLinked to original sources
PubMed2006

New formulation and implementation for volume polarization in dielectric continuum theory.

In the use of dielectric continuum theory to model bulk solvation effects on the electronic structure and properties of a solute, volume polarization contributions due to quantum mechanical penetration of the solute charge density outside the cavity nominally enclosing it are known to be significant. This work provides a new formulation and implementation of methods for solution of the requisite Poisson equation. In previous formulations the determination of the surface polarization contribution required evaluation of the difficult to calculate electric field generated by the volume polarization. It is shown that this problematic quantity can be eliminated in favor of other more easily evaluated quantities. That formal advance also opens the way for a more efficient apparatus to be implemented for calculation of the direct contribution of volume polarization to the solvation energy. The new formulation and its practical implementation are described, and illustrative numerical results are given for several neutral and ionic solutes to study the convergence and precision in practice.

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PubMed2006

Advances in methods and algorithms in a modern quantum chemistry program package.

Advances in theory and algorithms for electronic structure calculations must be incorporated into program packages to enable them to become routinely used by the broader chemical community. This work reviews advances made over the past five years or so that constitute the major improvements contained in a new release of the Q-Chem quantum chemistry package, together with illustrative timings and applications. Specific developments discussed include fast methods for density functional theory calculations, linear scaling evaluation of energies, NMR chemical shifts and electric properties, fast auxiliary basis function methods for correlated energies and gradients, equation-of-motion coupled cluster methods for ground and excited states, geminal wavefunctions, embedding methods and techniques for exploring potential energy surfaces.

Algorithms↗
PubMed2006

Cation electric field is related to hydration energy.

Electronic structure calculations on ions that use dielectric continuum theory to mimic solvent around the bare ionic solutes are often prone to make large errors in the hydration energies. It is found for cations that much of the error can be accounted for by a simple linear correlation with the maximum value found anywhere on the dielectric cavity surface of the solute potential or, even better, the outgoing normal electric field, thus mirroring analogous results previously obtained for anions. This correlation allows for significantly improved estimates of cation hydration energies while still retaining cavities of physically reasonable size in determination of the bulk dielectric contributions.

Journal Article↗
PubMed2006

Stretching of hydrogen-bonded OH in the lowest singlet excited electronic state of water dimer.

The lowest singlet excited electronic state of water monomer in the gas phase is strictly dissociative along a OH stretch coordinate but changes its nature when the stretched OH moiety is hydrogen bonded to a neighboring water molecule. This work extends previous exploration of the water dimer excited singlet potential-energy surface, using computational methods that are reliable even at geometries well removed from the ground-state equilibrium. First, the hydrogen-bonded OH moiety is stretched far enough to establish the existence of a barrier that is sufficient to support a quasibound vibrational state of the OH oscillator near the Franck-Condon region. Second, the constraint of an icelike structure is relaxed, and it is found that a substantial fraction of liquidlike structures also supports a quasibound vibrational state. These potential-energy explorations on stretching of the hydrogen-bonded OH moiety in a water dimer are discussed as a model for understanding the initial dynamics upon excitation into the lowest excited singlet state of condensed water. The possibility is raised that the excited-state lifetime may be long enough to allow for exciton migration, which would provide a mechanism for energy transport in condensed water phases.

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PubMed2005

Structures and energetics of hydrated oxygen anion clusters.

Hydration of the atomic oxygen radical anion is studied with computational electronic structure methods, considering (O(-))(H(2)O)(n) clusters and related proton-transferred (OH(-))(OH)(H(2)O)(n)(-)(1) clusters having n = 1-5. A total of 67 distinct local-minimum structures having various interesting hydrogen bonding motifs are obtained and analyzed. On the basis of the most stable form of each type, (O(-))(H(2)O)(n)) clusters are energetically favored, although for n > or = 3, there is considerable overlap in energy between other members of the (O(-))(H(2)O)(n) family and various members of the (OH(-))(OH)(H(2)O)(n)(-)(1) family. In the lower-energy (O(-))(H(2)O)(n) clusters, the hydrogen bonding arrangement about the oxygen anion center tends to be planar, leaving the oxygen anion p-like orbital containing the unpaired electron uninvolved in hydrogen bonding with any water molecule. In (OH(-))(OH)(H(2)O)(n)(-)(1) clusters, on the other hand, nonplanar arrangements are the rule about the anionic oxygen center that accepts hydrogen bonds. No instances are found of OH(-) acting as a hydrogen bond donor. Those OH bonds that form hydrogen bonds to an anionic O(-) or OH(-) center are significantly stretched from their equilibrium value in isolated water or hydroxyl. A quantitative inverse correlation is established for all hydrogen bonds between the amount of the OH bond stretch and the distance to the other oxygen involved in the hydrogen bond.

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PubMed2005

Excited electronic states of small water clusters.

The lowest electronic states that are initially formed upon excitation of small water clusters having a central water molecule with one stretched OH bond are studied with electronic structure methods. It is found that in water dimer, trimer, and pentamer the lowest excited singlet and triplet states are each nondissociative for stretching of an OH bond that is hydrogen bonded in an icelike configuration to a neighboring water molecule. This is in marked contrast to the behavior of an isolated gas phase water monomer, where it is well known that the lowest excited state is strongly dissociative upon OH stretching. The conclusions of this study may serve as a basis to interpret recent experimental evidence that suggests a significant lifetime for excited water in irradiated thin ice films, and may also have important implications for the behavior of excitation of liquid water.

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PubMed2004

Solution of the linearized Poisson-Boltzmann equation.

Improved methods are formulated for solution of the linearized Poisson-Boltzmann equation, to be used in conjunction with electronic structure calculation on a solute together with dielectric continuum representation of the salt-containing solvent. Volume polarization effects due to quantum mechanical penetration of solute charge density outside the cavity that excludes solvent are treated by exact and by approximate methods analogous to those previously developed for the salt-free case. With boundary element approaches, exact solutions lead to coupled equations for a pair of cavity surface distributions that mimic the polarization of the solvent dielectric and the ionic atmosphere. A novel means is found to effectively decouple these equations, yielding more efficient practical methods for their numerical solution. Detailed comparisons are given to related boundary element formulations previously reported in the literature, which neglect volume polarization, and analogous decoupling is also found for the pair of surface distributions invoked there. Illustrative results are provided for a simple spherical example.

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