Dalton is a powerful general-purpose program system for the study of molecular electronic structure at the Hartree–Fock, Kohn–Sham, multiconfigurational self-consistent-field, Møller–Plesset, configuration-interaction, and coupled-cluster levels of theory. Apart from the total energy, a wide variety of molecular properties may be calculated using these electronic-structure models. Molecular gradients and Hessians are available for geometry optimizations, molecular dynamics, and vibrational studies, whereas magnetic resonance and optical activity can be studied in a gauge-origin-invariant manner. Frequency-dependent molecular properties can be calculated using linear, quadratic, and cubic response theory. A large number of singlet and triplet perturbation operators are available for the study of one-, two-, and three-photon processes. Environmental effects may be included using various dielectric-medium and quantum-mechanics/molecular-mechanics models. Large molecules may be studied using linear-scaling and massively parallel algorithms. Dalton is distributed at no cost from http://www.daltonprogram.org for a number of UNIX platforms.

We demonstrate how the functional derivatives appearing in perturbative time-dependent density functional theory can be calculated using automatic differentiation. The approach starts from a computer implementation of the exchange-correlation energy functional, from which arbitrary-order derivatives are generated automatically. Automatic differentiation is shown to provide an accurate, general, and efficient implementation of higher-order exchange-correlation functional derivatives that is easy to maintain. When used in combination with an arbitrary-order response solver, the methodology allows us to generate arbitrary-order response functions from time-dependent density functional theory.

Note: This article is part of the JCP Special Topic on Electronic Structure Software.

The selection of basic variables in current-density functional theory and formal properties of the resulting formulations are critically examined. Focus is placed on the extent to which the HohenbergKohn theorem, constrained-search approach and Lieb's formulation (in terms of convex and concave conjugation) of standard density-functional theory can be generalized to provide foundations for current-density functional theory. For the well-known case with the gauge-dependent paramagnetic current density as a basic variable, we find that the resulting total energy functional is not concave. It is shown that a simple redefinition of the scalar potential restores concavity and enables the application of convex analysis and convex/concave conjugation. As a result, the solution sets arising in potential-optimization problems can be given a simple characterization. We also review attempts to establish theories with the physical current density as a basic variable. Despite the appealing physical motivation behind this choice of basic variables, we find that the mathematical foundations of the theories proposed to date are unsatisfactory. Moreover, the analogy to standard densityfunctional theory is substantially weaker as neither the constrained-search approach nor the convex analysis framework carry over to a theory making use of the physical current density.

The performance of the time-dependent density functional theory (TDDFT) approach has been evaluated for the electronic spectrum of the UO(2)(2+), NUO(+) and NUN molecules. Different exchange-correlation functionals (LDA, PBE, BLYP, B3LYP, PBE0, M06, M06-L, M06-2X, CAM-B3LYP) and the SAOP model potential have been investigated, as has the relative importance of the adiabatic local density approximation (ALDA) to the exchange-correlation kernel. The vertical excitation energies have been compared with reference data obtained using accurate wave-function theory (WFT) methods.

We present a novel implementation of Kohn-Sham density-functional theory utilizing London atomic orbitals as basis functions. External magnetic fields are treated non-perturbatively, which enable the study of both magnetic response properties and the effects of strong fields, using either standard density functionals or current-density functionals-the implementation is the first fully self-consistent implementation of the latter for molecules. Pilot applications are presented for the finite-field calculation of molecular magnetizabilities, hypermagnetizabilities, and nuclear magnetic resonance shielding constants, focusing on the impact of current-density functionals on the accuracy of the results. Existing current-density functionals based on the gauge-invariant vorticity are tested and found to be sensitive to numerical details of their implementation. Furthermore, when appropriately regularized, the resulting magnetic properties show no improvement over standard density-functional results. An advantage of the present implementation is the ability to apply density-functional theory to molecules in very strong magnetic fields, where the perturbative approach breaks down. Comparison with high accuracy full-configuration-interaction results show that the inadequacies of current-density approximations are exacerbated with increasing magnetic field strength. Standard density-functionals remain well behaved but fail to deliver high accuracy. The need for improved current-dependent density-functionals, and how they may be tested using the presented implementation, is discussed in light of our findings.

The C K-edge photoabsorption and 1s core-level photoemission of pentacene (C22H14) free molecules are experimentally measured, and calculated by self-consistent-field and static-exchange approximation ab initio methods. Six nonequivalent C atoms present in the molecule contribute to the C 1s photoemission spectrum. The complex near-edge structures of the carbon K-edge absorption spectrum present two main groups of discrete transitions between 283 and 288 eV photon energy, due to absorption to pi* virtual orbitals, and broader structures at higher energy, involving sigma* virtual orbitals. The sharp absorption structures to the pi* empty orbitals lay well below the thresholds for the C 1s ionizations, caused by strong excitonic and localization effects. We can definitely explain the C K-edge absorption spectrum as due to both final (virtual) and initial (core) orbital effects, mainly involving excitations to the two lowest-unoccupied molecular orbitals of pi* symmetry, from the six chemically shifted C 1s core orbitals.

ObjectivesTo examine the association between workload and kidney injury in a fieldworker cohort with different levels of physically demanding work over a sugarcane harvest, and to assess whether the existing heat prevention efforts at a leading occupational safety and health programme are sufficient to mitigate kidney injury.MethodsBiological and questionnaire data were collected before (n=545) and at the end (n=427) of harvest among field support staff (low workload), drip irrigation workers (moderate), seed cutters (high) and burned sugarcane cutters (very high). Dropouts were contacted (87%) and reported the reason for leaving work. Cross-harvest incident kidney injury (IKI) was defined as serum creatinine increase ≥0.30 mg/dL or ≥1.5 times the baseline value, or among dropouts reporting kidney injury leading to leaving work.ResultsMean cross-harvest estimated glomerular filtration rate change was significantly associated with workload, increasing from 0 mL/min/1.73 m2 in the low-moderate category to −5 mL/min/1.73 m2 in the high and −9 mL/min/1.73 m2 in the very high workload group. A similar pattern occurred with IKI, where low-moderate workload had 2% compared with 27% in the very high workload category. A healthy worker selection effect was detected, with 32% of dropouts reporting kidney injury. Fever and C reactive protein elevation were associated with kidney injury.ConclusionsWorkers considered to have the highest workload had more cross-harvest kidney damage than workers with less workload. Work practices preventing heat stress should be strengthened and their role in preventing kidney damage examined further. Future occupational studies on chronic kidney disease of unknown aetiology should account for a healthy worker effect by pursuing those lost to follow-up.