As an aid to the development of hydrogen separation membranes, we predict the temperature depende... more As an aid to the development of hydrogen separation membranes, we predict the temperature dependent phase diagrams using first principles calculations combined with thermodynamic principles. Our method models the phase diagram without empirical fitting parameters. By applying thermodynamic principles and solid solution models, temperature-dependent features of the Cu-Pd-S system can be explained, specifically solubility ranges for substitutions in select crystalline phases. Electronic densities of states calculations explain the relative favorability of certain chemical substitutions. In addition, we calculate sulfidization thresholds for the Pd-S2 system and activities for the Cu-Pd binary in temperature regimes where the phase diagram contains multiple solid phases.
Conventional magnetic resonance (MR) faces serious sensitivity limitations which can be overcome ... more Conventional magnetic resonance (MR) faces serious sensitivity limitations which can be overcome by hyperpolarization methods, but the most common method (dynamic nuclear polarization) is complex and expensive, and applications are limited by short spin lifetimes (typically seconds) of biologically relevant molecules. We use a recently developed method, SABRE-SHEATH, to directly hyperpolarize (15)N2 magnetization and long-lived (15)N2 singlet spin order, with signal decay time constants of 5.8 and 23 minutes, respectively. We find >10,000-fold enhancements generating detectable nuclear MR signals that last for over an hour. (15)N2-diazirines represent a class of particularly promising and versatile molecular tags, and can be incorporated into a wide range of biomolecules without significantly altering molecular function.
Using multiwavelets, we have obtained total energies and corresponding atomization energies for t... more Using multiwavelets, we have obtained total energies and corresponding atomization energies for the GGA-PBE and hybrid-PBE0 density functionals for a test set of 211 molecules with an unprecedented and guaranteed μHartree accuracy. These quasi-exact references allow us to quantify the accuracy of standard all-electron basis sets that are believed to be highly accurate for molecules, such as Gaussian-type orbitals (GTOs), all-electron numeric atom-centered orbitals (NAOs), and full-potential augmented plane wave (APW) methods. We show that NAOs are able to achieve the so-called chemical accuracy (1 kcal/mol) for the typical basis set sizes used in applications, for both total and atomization energies. For GTOs, a triple-ζ quality basis has mean errors of ∼10 kcal/mol in total energies, while chemical accuracy is almost reached for a quintuple-ζ basis. Due to systematic error cancellations, atomization energy errors are reduced by almost an order of magnitude, placing chemical accuracy within reach also for medium to large GTO bases, albeit with significant outliers. In order to check the accuracy of the computed densities, we have also investigated the dipole moments, where in general only the largest NAO and GTO bases are able to yield errors below 0.01 D. The observed errors are similar across the different functionals considered here.
As an aid to the development of hydrogen separation membranes, we predict the temperature depende... more As an aid to the development of hydrogen separation membranes, we predict the temperature dependent phase diagrams using first principles calculations combined with thermodynamic principles. Our method models the phase diagram without empirical fitting parameters. By applying thermodynamic principles and solid solution models, temperature-dependent features of the Cu-Pd-S system can be explained, specifically solubility ranges for substitutions in select crystalline phases. Electronic densities of states calculations explain the relative favorability of certain chemical substitutions. In addition, we calculate sulfidization thresholds for the Pd-S2 system and activities for the Cu-Pd binary in temperature regimes where the phase diagram contains multiple solid phases.
Conventional magnetic resonance (MR) faces serious sensitivity limitations which can be overcome ... more Conventional magnetic resonance (MR) faces serious sensitivity limitations which can be overcome by hyperpolarization methods, but the most common method (dynamic nuclear polarization) is complex and expensive, and applications are limited by short spin lifetimes (typically seconds) of biologically relevant molecules. We use a recently developed method, SABRE-SHEATH, to directly hyperpolarize (15)N2 magnetization and long-lived (15)N2 singlet spin order, with signal decay time constants of 5.8 and 23 minutes, respectively. We find >10,000-fold enhancements generating detectable nuclear MR signals that last for over an hour. (15)N2-diazirines represent a class of particularly promising and versatile molecular tags, and can be incorporated into a wide range of biomolecules without significantly altering molecular function.
Using multiwavelets, we have obtained total energies and corresponding atomization energies for t... more Using multiwavelets, we have obtained total energies and corresponding atomization energies for the GGA-PBE and hybrid-PBE0 density functionals for a test set of 211 molecules with an unprecedented and guaranteed μHartree accuracy. These quasi-exact references allow us to quantify the accuracy of standard all-electron basis sets that are believed to be highly accurate for molecules, such as Gaussian-type orbitals (GTOs), all-electron numeric atom-centered orbitals (NAOs), and full-potential augmented plane wave (APW) methods. We show that NAOs are able to achieve the so-called chemical accuracy (1 kcal/mol) for the typical basis set sizes used in applications, for both total and atomization energies. For GTOs, a triple-ζ quality basis has mean errors of ∼10 kcal/mol in total energies, while chemical accuracy is almost reached for a quintuple-ζ basis. Due to systematic error cancellations, atomization energy errors are reduced by almost an order of magnitude, placing chemical accuracy within reach also for medium to large GTO bases, albeit with significant outliers. In order to check the accuracy of the computed densities, we have also investigated the dipole moments, where in general only the largest NAO and GTO bases are able to yield errors below 0.01 D. The observed errors are similar across the different functionals considered here.
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Papers by William P Huhn