TY - JOUR

T1 - The second-order polarization propagator approximation (SOPPA) method coupled to the polarizable continuum model

AU - Eriksen, Janus Juul

AU - Solanko, Lukasz Michal

AU - Nåbo, Lina J.

AU - Wüstner, Daniel

AU - Sauer, Stephan P. A.

AU - Kongsted, Jacob

N1 - Excited states: From isolated molecules to complex environments — Excited states

PY - 2014

Y1 - 2014

N2 - We present an implementation of the Polarizable Continuum Model (PCM) in combination with the Second–Order Polarization Propagator Approximation (SOPPA) electronic structure method. In analogy with the most common way of designing ground state calculations based on a Second–Order Møller-Plesset (MP2) wave function coupled to PCM, we introduce dynamical PCM solvent effects only in the Random Phase Approximation (RPA) part of the SOPPA response equations while the static solvent contribution is kept in both the RPA terms as well as in the higher order correlation matrix components of the SOPPA response equations. By dynamic terms, we refer to contributions that describe a change in environmental polarization which, in turn, reflects a change in the core molecular charge distribution upon an electronic excitation. This new combination of methods is termed PCM-SOPPA/RPA. We apply this newly defined method to the challenging cases of solvent effects on the lowest and intense electronic transitions in o-, m- and p-nitroaniline and o-, m- and p-nitrophenol and compare the performance of PCM-SOPPA/RPA with more conventional approaches. Compared to calculations based on time-dependent density functional theory employing a range-separated exchange-correlation functional, we find the PCM-SOPPA/RPA approach to be slightly superior with respect to systematicity. On the other hand, the absolute values of the predicted excitation energies are largely underestimated. This – however – is a well-know feature of the SOPPA model itself and is not connected to its combination with the PCM.

AB - We present an implementation of the Polarizable Continuum Model (PCM) in combination with the Second–Order Polarization Propagator Approximation (SOPPA) electronic structure method. In analogy with the most common way of designing ground state calculations based on a Second–Order Møller-Plesset (MP2) wave function coupled to PCM, we introduce dynamical PCM solvent effects only in the Random Phase Approximation (RPA) part of the SOPPA response equations while the static solvent contribution is kept in both the RPA terms as well as in the higher order correlation matrix components of the SOPPA response equations. By dynamic terms, we refer to contributions that describe a change in environmental polarization which, in turn, reflects a change in the core molecular charge distribution upon an electronic excitation. This new combination of methods is termed PCM-SOPPA/RPA. We apply this newly defined method to the challenging cases of solvent effects on the lowest and intense electronic transitions in o-, m- and p-nitroaniline and o-, m- and p-nitrophenol and compare the performance of PCM-SOPPA/RPA with more conventional approaches. Compared to calculations based on time-dependent density functional theory employing a range-separated exchange-correlation functional, we find the PCM-SOPPA/RPA approach to be slightly superior with respect to systematicity. On the other hand, the absolute values of the predicted excitation energies are largely underestimated. This – however – is a well-know feature of the SOPPA model itself and is not connected to its combination with the PCM.

KW - Faculty of Science

KW - Quantum Chemistry

KW - Computational Chemistry

KW - SOPPA

KW - PCM

KW - solvent effects

KW - electronic excitation

U2 - 10.1016/j.comptc.2014.02.034

DO - 10.1016/j.comptc.2014.02.034

M3 - Journal article

VL - 1040-1041

SP - 54

EP - 60

JO - Computational and Theoretical Chemistry

JF - Computational and Theoretical Chemistry

SN - 2210-271X

ER -