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Complex Linear Response Functions for a Multiconfigurational Self-Consistent Field Wave Function in a High Performance Computing Environment
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DOI：10.1021/acs.jctc.3c00317.png)
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Abstract
En 中文
We present noveldevelopments for the highly efficientevaluationof complex linear response functions of a multiconfigurational self-consistentfield (MCSCF) wave function as implemented in MultiPsi. Specifically,expressions for the direct evaluation of linear response propertiesat given frequencies using the complex polarization propagator (CPP)approach have been implemented, within both the Tamm-Dancoff approximation(TDA) and the random phase approximation (RPA). Purely real algebrawith symmetric and antisymmetric trial vectors in a shared subspaceis used wherein the linear response equations are solved. Two bottlenecksof large scale MC-CPP calculations, namely, the memory footprint andcomputational time, are addressed. The former is addressed by limitingthe size of the subspace of trial vectors by using singular valuedecomposition (SVD) on either orbital or CI subspaces. The latteris addressed using an efficient parallel implementation as well as the strategy of dynamically adding linear response equations at near-convergenceto neighboring roots. Furthermore, a novel methodology for decomposingMC-CPP spectra in terms of intuitive orbital excitations in an approximatefashion is presented. The performance of the code is illustrated withseveral numerical examples, including the X-ray spectrum of a moleculewith nearly one hundred atoms. Additionally, for X-ray spectroscopy,the effect of including or excluding the core orbital in the activespace on small covalent metal complexes is discussed.
Keywords:
DOUBLE EXCITATIONS
ABSORPTION
SPECTRA
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