We present a first principles molecular dynamics approach that is based on time-reversible ex- tended Lagrangian Born-Oppenheimer molecular dynamics [Phys. Rev. Lett. 100, 123004 (2008)] in the limit of vanishing self-consistent field optimization. T
he optimization-free dynamics keeps the computational cost to a minimum and typically provides molecular trajectories that closely follow the exact Born-Oppenheimer potential energy surface. Only one single diagonalization and Hamiltonian (or Fockian) costruction are required in each integration time step. The proposed dy- namics is derived for a general free-energy potential surface valid at finite electronic temperatures within hybrid density functional theory. Even in the event of irregular functional behavior that may cause a dynamical instability, the optimization-free limit represents an ideal starting guess for force calculations that may require a more elaborate iterative electronic ground state optimization. Our optimization-free dynamics thus represents a flexible theoretical framework for a broad and general class of ab initio molecular dynamics simulations.
In this paper we present the Uppsala Quantum Chemistry package (UQUANTCHEM), a new and versatile computational platform with capabilities ranging from simple Hartree-Fock calculations to state of the art First principles Extended Lagrangian Born Oppe
nheimer Molecular Dynamics (XL- BOMD) and diffusion quantum Monte Carlo (DMC). The UQUANTCHEM package is distributed under the general public license and can be directly downloaded from the code web-site. Together with a presentation of the different capabilities of the uquantchem code and a more technical discus- sion on how these capabilities have been implemented, a presentation of the user-friendly aspect of the package on the basis of the large number of default settings will also be presented. Furthermore, since the code has been parallelized within the framework of the message passing interface (MPI), the timing of some benchmark calculations are reported to illustrate how the code scales with the number of computational nodes for different levels of chemical theory.
We present an efficient general approach to first principles molecular dynamics simulations based on extended Lagrangian Born-Oppenheimer molecular dynamics in the limit of vanishing self-consistent field optimization. The reduction of the optimizati
on requirement reduces the computational cost to a minimum, but without causing any significant loss of accuracy or longterm energy drift. The optimization-free first principles molecular dynamics requires only one single diagonalization per time step and yields trajectories at the same level of accuracy as exact, fully converged, Born-Oppenheimer molecular dynamics simulations. The optimization-free limit of extended Lagrangian Born-Oppenheimer molecular dynamics therefore represents an ideal starting point for a robust and efficient formulation of a new generation first principles quantum mechanical molecular dynamics simulation schemes.
We here show by first principles theory that it is possible to achieve a structural and magnetic phase transition in common steel alloys like Fe$_{85}$Cr$_{15}$, by alloying with Ni or Mn. The predicted phase transition is from the ferromagnetic body
centered cubic (bcc) phase to the paramagnetic face centered cubic (fcc) phase. The relatively high average magnetic moment of $sim1.4mu_{B}$/atom predicted at the transition suggests that stainless steel potentially can present a magnetocaloric effect strong enough to make these alloys good candidates for refrigeration applications operating at and around room temperature.
Phonon lifetime calculations from first principles usually rely on time consuming molecular dynamics calculations, or density functional perturbation theory (DFPT) where the zero temperature crystal structure is assumed to be dynamically stable. Here
a new and effective method for calculating phonon lifetimes from first principles is presented, not limited to crystal structures stable at 0 K, and potentially much more effective than most corresponding molecular dynamics calculations. The method is based on the recently developed self consistent lattice dynamical method and is here tested by calculating the bcc phase phonon lifetimes of Li, Na, Ti and Zr, as representative examples.
Lattice dynamical methods used to predict phase transformations in crystals typically deal with harmonic phonon spectra and are therefore not applicable in important situations where one of the competing crystal structures is unstable in the harmonic
approximation, such as the bcc structure involved in the hcp to bcc martensitic phase transformation in Ti, Zr and Hf. Here we present an expression for the free energy that does not suffer from such shortcomings, and we show by self consistent {it ab initio} lattice dynamical calculations (SCAILD), that the critical temperature for the hcp to bcc phase transformation in Ti, Zr and Hf, can be effectively calculated from the free energy difference between the two phases. This opens up the possibility to study quantitatively, from first principles theory, temperature induced phase transitions.
Lattice dynamical methods used to predict phase-transformations in crystals typically evaluate the harmonic phonon spectra and therefore do not work in frequent and important situations where the crystal structure is unstable in the harmonic approxim
ation, such as the $beta$ structure when it appears as a high-temperature phase of the shape memory alloy (SMA) NiTi. Here it is shown by self consistent {it ab initio} lattice dynamical calculations (SCAILD) that the critical temperature for the pre-martensitic $R$ to $beta$ phase-transformation in NiTi can be effectively calculated with good accuracy, and that the $beta$-phase is a result primarily of the stabilizing interaction between different lattice vibrations.
The recently developed self consistent {it ab initio} lattice dynamical method (SCAILD) has been applied to the high temperature bcc phase of La and Th which are dynamically unstable at low temperatures. The bcc phase of these metals is found to be s
tabilized by phonon-phonon interactions. The calculated high temperature phonon frequencies for La are found to be in good agreement with the corresponding experimental data.
Conventional methods to calculate the thermodynamics of crystals evaluate the harmonic phonon spectra and therefore do not work in frequent and important situations where the crystal structure is unstable in the harmonic approximation, such as the bo
dy-centered cubic (bcc) crystal structure when it appears as a high-temperature phase of many metals. A method for calculating temperature dependent phonon spectra self consistently from first principles has been developed to address this issue. The method combines concepts from Borns inter-atomic self-consistent phonon approach with first principles calculations of accurate inter-atomic forces in a super-cell. The method has been tested on the high temperature bcc phase of Ti, Zr and Hf, as representative examples, and is found to reproduce the observed high temperature phonon frequencies with good accuracy.
We provide a complete quantitative explanation for the anisotropic thermal expansion of hcp Ti at low temperature. The observed negative thermal expansion along the c-axis is reproduced theoretically by means of a parameter free theory which involves
both the electron and phonon contributions to the free energy. The thermal expansion of titanium is calculated and found to be negative along the c-axis for temperatures below $sim$ 170 K, in good agreement with observations. We have identified a saddle-point Van Hove singularity near the Fermi level as the main reason for the anisotropic thermal expansion in $alpha-$titanium.
