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On the importance of excited state dynamic response electron correlation in polarizable embedding methods
Author(s) -
Eriksen Janus J.,
Sauer Stephan P. A.,
Mikkelsen Kurt V.,
Jensen Hans J. Aa.,
Kongsted Jacob
Publication year - 2012
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.23032
Subject(s) - random phase approximation , excited state , polarizability , wave function , multipole expansion , electronic correlation , ground state , chemistry , observable , quantum mechanics , physics , computational chemistry , electron , molecule
We investigate the effect of including a dynamic reaction field at the lowest possible ab inito wave function level of theory, namely the Hartree‐Fock (HF) self‐consistent field level within the polarizable embedding (PE) formalism. We formulate HF based PE within the linear response theory picture leading to the PE–random‐phase approximation (PE–RPA) and bridge the expressions to a second‐order polarization propagator approximation (SOPPA) frame such that dynamic reaction field contributions are included at the RPA level in addition to the static response described at the SOPPA level but with HF induced dipole moments. We conduct calculations on para ‐nitro‐aniline and para ‐nitro‐phenolate using said model in addition to dynamic PE–RPA and PE–CAM–B3LYP. We compare the results to recently published PE–CCSD data and demonstrate how the cost effective SOPPA‐based model successfully recovers a great portion of the inherent PE–RPA error when the observable is the solvatochromic shift. We furthermore demonstrate that whenever the change in density resulting from the ground state‐excited state electronic transition in the solute is not associated with a significant change in the electric field, dynamic response contributions formulated at the HF level of theory manage to capture the majority of the system response originating from derivative densities. © 2012 Wiley Periodicals, Inc.