Set the minimum contribution percentage to include in individual orbital population analysis. For open shell calculations, both alpha and beta orbitals are included. AllOrbitals may also be specified instead of Orbitals= N to request analysis of all orbitals. Perform a population analysis of the highest N occupied and lowest N virtual orbitals (see the examples below). Perform a population analysis at every optimization step rather than just the initial and final ones. Same as the Regular population analysis, except that all orbitals are printed. Since the size of the output depends on the square of the size of the molecule, it can become quite substantial for larger molecules.
#Charge transfer calculation using muliken quantumwise full
The five highest occupied and five lowest virtual orbitals are printed, along with the density matrices and a full (orbital by orbital and atom by atom) Mulliken population analysis. This is the default for all job types and methods except Guess=Only and/or ZIndo. Total atomic charges and orbital energies are printed. This is the default for all calculations using the ZIndo method. No orbitals are printed, and no population analysis is done. Multipole moments: dipole through hexadecapole.ĪPT charges are also computed by default during vibrational frequency calculations. The total charge per fragment is also reported if applicable. By default, all orbitals are included, but the output can be limited to a specific orbital range with the Orbital option.Ītomic charge distribution. Output controlled by the Pop keyword includes: Population analysis results are given in the standard orientation.
If several combinations are of interest, additional jobs steps can be added by specifying Guess=Only Density=Check, to avoid repeating any costly calculations. Note that only one density and method of charge fitting can be used in a job step. The density that is used for the population analysis is controlled by the Density keyword. Note that the Population keyword requires an option. Populations are done once for single-point calculations and at the first and last points of geometry optimizations. The default is to print just the total atomic charges and orbital energies, except for Guess=Only jobs, for which the default is Pop=Full (see below). This properties keyword controls printing of molecular orbitals and several types of population analysis and atomic charge assignments. The implementation presented opens up the possibility to compute electronic coupling matrix elements for extended systems where donor, acceptor, and the environment are treated at the quantum mechanical (QM) level.G09 Keyword: Population Population DESCRIPTION While CDFT in combination with generalized gradient approximation (GGA) functionals describes the intermolecular electron transfer in the studied systems well, exact exchange is required for Q-TTF-Q(-) in order to obtain coupling matrix elements in agreement with experiment (3.9 mH). The thermal average, ()(1/2)=6.7 mH, is significantly higher than the value obtained for the minimum energy structure, |H(ab)|=3.8 mH. Sampling the electronic coupling along density functional based molecular dynamics trajectories, we find that thermal fluctuations, in particular the slow bending motion of the molecule, can lead to changes in the instantaneous electron transfer rate by more than an order of magnitude. The effect of thermal fluctuations on the coupling matrix element is demonstrated for intramolecular electron transfer in the tetrathiafulvalene-diquinone (Q-TTF-Q(-)) anion. Our results for intermolecular electron transfer in small systems agree very well with high-level ab initio calculations based on generalized Mulliken-Hush theory, and with previous local basis set CDFT calculations. Following the work of Wu and Van Voorhis, the diabatic wavefunctions are approximated by the Kohn-Sham determinants obtained from CDFT calculations, and the coupling matrix element calculated by an efficient integration scheme. We present a plane wave basis set implementation for the calculation of electronic coupling matrix elements of electron transfer reactions within the framework of constrained density functional theory (CDFT).
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