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.

Coupled cluster calculations can be carried out for large molecular systems via a set of calculations that use small orbital fragments of the full molecular orbital space. The error in the correlation energy of the full molecular system is controlled by the precision in the small fragment calculations. The determination of the orbital spaces for the small orbital fragments is black box in the sense that it does not depend on any user-provided molecular fragmentation, rather orbital spaces are carefully selected and extended during the calculation to give fragment energies of a specified precision. The computational method scales linearly with the size of the molecular system and is massively parallel.

We present a thorough locality analysis of the divide-expand-consolidate amplitude equations for second-order Møller-Plesset perturbation theory and the coupled cluster singles doubles (CCSD) model, which demonstrates that the amplitude equations are local when expressed in terms of a set of local occupied and local unoccupied Hartree-Fock orbitals, such as the least-change molecular basis. The locality analysis thus shows that a CC calculation on a large molecular system may be carried out in terms of CC calculations on small orbital fragments of the total molecular system, where the sizes of the orbital fragment spaces are determined in a black box manner to ensure that the CC correlation energy is calculated to a preset energy threshold. A practical implementation of the locality analysis is described, and numerical results are presented, which demonstrate that both the orbital fragment sizes and the relative energy error compared to a full CC calculation are independent of the molecular system size.

An analysis of Dunlap's robust fitting approach reveals that the resulting two-electron integral matrix is not manifestly positive semidefinite when local fitting domains or non-Coulomb fitting metrics are used. We present a highly local approximate method for evaluating four-center two-electron integrals based on the resolution-of-the-identity (RI) approximation and apply it to the construction of the Coulomb and exchange contributions to the Fock matrix. In this pair-atomic resolutionof-the-identity (PARI) approach, atomic-orbital (AO) products are expanded in auxiliary functions centered on the two atoms associated with each product. Numerical tests indicate that in 1% or less of all Hartree-Fock and Kohn-Sham calculations, the indefinite integral matrix causes nonconvergence in the self-consistent-field iterations. In these cases, the two-electron contribution to the total energy becomes negative, meaning that the electronic interaction is effectively attractive, and the total energy is dramatically lower than that obtained with exact integrals. In the vast majority of our test cases, however, the indefiniteness does not interfere with convergence. The total energy accuracy is comparable to that of the standard Coulomb-metric RI method. The speed-up compared with conventional algorithms is similar to the RI method for Coulomb contributions; exchange contributions are accelerated by a factor of up to eight with a triple-zeta quality basis set. A positive semidefinite integral matrix is recovered within PARI by introducing local auxiliary basis functions spanning the full AO product space, as may be achieved by using Cholesky-decomposition techniques. Local completion, however, slows down the algorithm to a level comparable with or below conventional calculations.

We present a quasienergy-based formulation of damped response theory where a common effective lifetime parameter has been introduced for all excited states in terms of complex excitation energies. The introduction of finite excited state lifetimes leads to a set of (complex) damped response equations, which have the same form to all orders in the perturbation. An algorithm is presented for solving the damped response equations in Hartree-Fock theory and Kohn-Sham density functional theory. The use of the quasienergy formulation allows us to obtain directly the computationally simplest expressions for damped response functions by applying a set of response parameter elimination rules, which minimize the total number of damped response equations to be solved. In standard response theory broadened absorption spectra are obtained by ad hoc superimposing lineshape functions onto the absorption stick spectra, whereas an empirical lineshape function common to all excitations is an integrated part of damped response theory. By superimposing the lineshape functions inherent in damped response theory onto the stick spectra of standard response theory, we show that the absorption spectra obtained in standard and damped response theory calculations are identical. We demonstrate that damped response theory may be applied to obtain absorption spectra in all frequency ranges, also those that are not readily addressed using standard response theory. This makes damped response theory an effective tool, e.g., for determining absorption spectra for large molecules, where the density of the excited states may be very high, and where standard response theory therefore is not applicable in practice. A thorough comparison is given between our formulation of damped response theory and the formulation by Norman et al. [J. Chem. Phys. 123, 194103 (2005)].