Abstractorbkit is a toolbox for post-processing electronic structure calculations based on a highly modular and portable Python architecture. The program allows computing a multitude of electronic properties of molecular systems on arbitrary spatial grids from the basis set representation of its electronic wavefunction, as well as several gridindependent properties. The required data can be extracted directly from the standard output of a large number of quantum chemical programs. orbkit can be used as a standalone program to determine standard quantities, for example, the electron density, molecular orbitals, and derivatives thereof. The cornerstone of orbkit is its modular structure. The existing basic functions can be arranged in an individual way and can be easily extended by user-written modules to determine any other desired quantities. orbkit offers multiple output formats that can be processed by common visualization tools (VMD, Molden, etc.). Additionally, orbkit possesses routines to order molecular orbitals computed at different nuclear configurations according to their electronic character and to interpolate the wavefunction between these configurations. The program is open-source under GNU-LGPLv3 license and freely available at http://sourceforge.net/projects/orbkit/. This article provides an overview of orbkit with particular focus on its capabilities and applicability, and includes several example calculations.Keywords: quantum chemical calculation, electronic structure, molecular visualization, electron density, grid representation of one-electron quantities, molecular orbital ordering * Institut für Chemie und Biochemie, Freie Universität Berlin, Takustraße 3, 14195 Berlin, Germany † These authors contributed equally to this work. orbkit is an open-source toolbox for post-processing electronic structure calculations. Based on a highly modular and portable Python architecture, it comes both as a standalone program and a function library. The program allows computing electronic properties of molecular systems on arbitrary spatial grids from the output of standard quantum chemistry programs.2
The influence of an external flow velocity on the instability of a circular jet has been investigated by means of the inviscid linearized stability theory. The instability properties of spatially growing axisymmetric and first-order azimuthal disturbances show that the external flow inhibits the instability of the circular jet, but increases the unstable frequency range. Similarity considerations lead to the result that, in a first approximation, the disturbed flow field is independent of the external flow velocity, if the axial co-ordinate is contracted by a suitably chosen stretching factor and if the disturbance frequency is reduced by the same factor. It is concluded that the large-scale structure of jet turbulence is modified in the same manner by the external flow.
The aim of the present contribution is to provide a framework for analyzing and visualizing the correlated many-electron dynamics of molecular systems, where an explicitly time-dependent electronic wave packet is represented as a linear combination of N -electron wave functions. The central quantity of interest is the electronic flux density, which contains all information about the transient electronic density, the associated phase, and their temporal evolution. It is computed from the associated one-electron operator by reducing the multi-determinantal, many-electron wave packet using the Slater-Condon rules. Here, we introduce a general tool for post-processing multi-determinant configuration-interaction wave functions obtained at various levels of theory. It is tailored to extract directly the data from the output of standard quantum chemistry packages using atom-centered Gaussian-type basis functions. The procedure is implemented in the open-source Python program detCI@ORBKIT, which shares and builds upon the modular design of our recently published post-processing toolbox [J. Comput. Chem. 37 (2016) 1511]. The new procedure is applied to ultrafast charge migration processes in different molecular systems, demonstrating its broad applicability.Convergence of the N -electron dynamics with respect to the electronic structure theory level and basis set size is investigated. This provides an assessment of the robustness of qualitative and quantitative statements that can be made concerning dynamical features observed in charge migration simulations.
In this contribution, we extend our framework for analyzing and visualizing correlated many-electron dynamics to non-variational, highly scalable electronic structure method. Specifically, an explicitly time-dependent electronic wave packet is written as a linear combination of N-electron wave functions at the configuration interaction singles (CIS) level, which are obtained from a reference time-dependent density functional theory (TDDFT) calculation. The procedure is implemented in the open-source Python program detCI@ORBKIT, which extends the capabilities of our recently published post-processing toolbox (Hermann et al., J. Comput. Chem. 2016, 37, 1511). From the output of standard quantum chemistry packages using atom-centered Gaussian-type basis functions, the framework exploits the multideterminental structure of the hybrid TDDFT/CIS wave packet to compute fundamental one-electron quantities such as difference electronic densities, transient electronic flux densities, and transition dipole moments. The hybrid scheme is benchmarked against wave function data for the laser-driven state selective excitation in LiH. It is shown that all features of the electron dynamics are in good quantitative agreement with the higher-level method provided a judicious choice of functional is made. Broadband excitation of a medium-sized organic chromophore further demonstrates the scalability of the method. In addition, the time-dependent flux densities unravel the mechanistic details of the simulated charge migration process at a glance. © 2017 Wiley Periodicals, Inc.
Recently, adiabatic attosecond charge migration (AACM) has been monitored and simulated for the first time, with application to the oriented iodoacetylene cation where AACM starts from the initial superposition of the ground state (φ0) and an electronic excited state (φ1). Here, we develop the theory for electronic fluxes during AACM in ring-shaped molecules, with application to oriented benzene prepared in the superposition of the ground and first excited singlet states. The initial state and its time evolution are analogous to coherent tunneling where φ0 and φ1 have different meanings; however, they denote the wave functions of the lowest tunneling doublet. This analogy suggests to transfer the theory of electronic fluxes during coherent tunneling to AACM, with suitable modifications which account for (i) the different time scales and (ii) the different electronic states, and which make use of (iii) the preparation of the initial state for AACM by a linearly polarized laser pulse. Application to benzene yields the multidirectional angular electronic flux with a pincer-motion type pattern during AACM: this unequivocal result confirms a previous working hypothesis. Moreover, the theory of AACM allows quantification of the electronic flux; that is, the maximum number of electrons (out of 42) which flow concertedly during AACM in benzene is 6 × 0.08 = 0.48.
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