Implementation and Application of the Frozen Density Embedding Theory with the Algebraic Diagrammatic Construction Scheme for the Polarization Propagator up to Third Order

Abstract

Implementation, benchmarking, and representative applications of the new FDE-ADC(3) method for describing environmental effects on excited states as a combination of frozen density embedding (FDE) and the algebraic-diagrammatic construction scheme for the polarization propagator of third order (ADC(3)) are presented. Results of FDE-ADC(3) calculations are validated with respect to supersystem calculations on test systems with varying molecule-environment interaction strengths from dispersion up to multiple hydrogen bonds. The overall deviation compared to the supersystem calculations is as small as 0.029 eV for excitation energies, which is even smaller than the intrinsic error of ADC(3). The dependence of the accuracy on the choice of method and functional for the calculation of the environment and the nonelectrostatic part of the system-environment interaction is evaluated. In three representative examples, the FDE-ADC method is applied to investigate larger systems and to analyze excited state properties using visualization of embedded densities and orbitals.

Electronic circular dichroism spectra using the algebraic diagrammatic construction schemes of the polarization propagator up to third order

“…An important aspect in the simulation of experimental ECD spectra of medium-sized to large molecules is the influence of molecular environments, as has been shown for the solution spectrum of epinephrine where the application of PCM shifted the simulated spectrum. Within the ADC framework, further different solvation models are available, for example, frozen density embedding, 98,99 effective fragment potentials, 100 or polarizable embedding. 101,102 The suitability of these environment models in combination with ADC for the simulation of ECD spectra will be investigated in the future.…”

Progress in the Theory of X-ray Spectroscopy: From Quantum Chemistry to Machine Learning and Ultrafast Dynamics

“…59 Citing their inclusion of full channel interactions, Rehn et al asserted that the implementation described in ref 59 would be better than other implementations based on few-state models in systems where several atoms contribute to the absorption edge. 59 The development of frozen-density (FD) 60 and, subsequently, polarizable embedding (PE) 61 schemes followed, enabling the inclusion of environment effects in ADC theory. The FD and PE schemes were implemented in such a way as to be generalizable to any flavor of ADC (CVS-ADC flavors included), 61 but they have yet to be trialled in the calculation of core-excited states.…”

“…The development of frozen-density (FD) and, subsequently, polarizable embedding (PE) schemes followed, enabling the inclusion of environment effects in ADC theory. The FD and PE schemes were implemented in such a way as to be generalizable to any flavor of ADC (CVS-ADC flavors included), but they have yet to be trialled in the calculation of core-excited states.…”

Algebraic diagrammatic construction for the polarisation propagator in combination with effective fragment potentials

“…Following this route, ADC has been employed within classical QM/MM schemes, 34 and it has been interfaced with many other solvent models such as PCM, [35][36][37] and frozen-density embedding (FDE). [39][40][41] This paper is organised as follows. In the next section, the basic theoretical concepts of EFP-ADC will be outlined before its accuracy is tested for three different subsets of ''solvated'' molecules.…”