TY - JOUR
T1 - Linear response properties of solvated systems
T2 - a computational study
AU - Goletto, Linda
AU - Gómez, Sara
AU - Andersen, Josefine H.
AU - Koch, Henrik
AU - Giovannini, Tommaso
N1 - Publisher Copyright:
© 2022 The Royal Society of Chemistry.
PY - 2022
Y1 - 2022
N2 - We present a computational study of static and dynamic linear polarizabilities in solution. We use different theoretical approaches to describe solvent effects, ranging from quantum mechanics/molecular mechanics (QM/MM) to quantum embedding approaches. In particular, we consider non-polarizable and polarizable QM/MM methods, the latter based on the fluctuating charge (FQ) force field. In addition, we use a quantum embedding method defined in the context of multilevel Hartree-Fock (MLHF), where the system is divided into active and inactive regions, and combine it with a third layer described by means of the FQ model. The multiscale approaches are then used as reference wave functions for equation-of-motion coupled cluster (EOM-CC) response properties, allowing for the account of electron correlation. The developed models are applied to the calculation of linear response properties of two organic moieties—namely, para-nitroaniline and benzonitrile—in non-aqueous solvents—1,4-dioxane, acetonitrile, and tetrahydrofuran. The computed polarizabilities are then discussed in terms of the physico-chemical solute-solvent interactions described by each method (electrostatic, polarization and Pauli repulsion), and finally compared with the available experimental references.
AB - We present a computational study of static and dynamic linear polarizabilities in solution. We use different theoretical approaches to describe solvent effects, ranging from quantum mechanics/molecular mechanics (QM/MM) to quantum embedding approaches. In particular, we consider non-polarizable and polarizable QM/MM methods, the latter based on the fluctuating charge (FQ) force field. In addition, we use a quantum embedding method defined in the context of multilevel Hartree-Fock (MLHF), where the system is divided into active and inactive regions, and combine it with a third layer described by means of the FQ model. The multiscale approaches are then used as reference wave functions for equation-of-motion coupled cluster (EOM-CC) response properties, allowing for the account of electron correlation. The developed models are applied to the calculation of linear response properties of two organic moieties—namely, para-nitroaniline and benzonitrile—in non-aqueous solvents—1,4-dioxane, acetonitrile, and tetrahydrofuran. The computed polarizabilities are then discussed in terms of the physico-chemical solute-solvent interactions described by each method (electrostatic, polarization and Pauli repulsion), and finally compared with the available experimental references.
U2 - 10.1039/d2cp04512e
DO - 10.1039/d2cp04512e
M3 - Journal article
C2 - 36367017
AN - SCOPUS:85142695961
SN - 1463-9076
VL - 24
SP - 27866
EP - 27878
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
IS - 45
ER -