On the importance of excited state dynamic response electron correlation in polarizable embedding methods

TY - JOUR

T1 - On the importance of excited state dynamic response electron correlation in polarizable embedding methods

AU - Eriksen, Janus J.

AU - Sauer, Stephan P. A.

AU - Mikkelsen, Kurt Valentin

AU - Jensen, Hans Jørgen Aagaard

AU - Kongsted, Jacob

PY - 2012/9/30

Y1 - 2012/9/30

N2 - 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.

AB - 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.

KW - Faculty of Science

KW - Quantum Chemistry

KW - Computational Chemistry

KW - UV-VIS

KW - SOLVATOCHROMISM

KW - solvent effects

KW - spectroscopy

U2 - 10.1002/jcc.23032

DO - 10.1002/jcc.23032

M3 - Journal article

C2 - 22685085

SN - 0192-8651

VL - 33

SP - 2012

EP - 2022

JO - Journal of Computational Chemistry

JF - Journal of Computational Chemistry

IS - 25

ER -