On the importance of excited state dynamic response electron correlation in polarizable embedding methods
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On the importance of excited state dynamic response electron correlation in polarizable embedding methods. / Eriksen, Janus J.; Sauer, Stephan P. A.; Mikkelsen, Kurt Valentin; Jensen, Hans Jørgen Aagaard; Kongsted, Jacob.
In: Journal of Computational Chemistry, Vol. 33, No. 25, 2012, p. 2012-2022.Research output: Contribution to journal › Journal article › Research › peer-review
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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
Y1 - 2012
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 (SCF) 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 (SCF) 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
VL - 33
SP - 2012
EP - 2022
JO - Journal of Computational Chemistry
JF - Journal of Computational Chemistry
SN - 0192-8651
IS - 25
ER -
ID: 38102962