Multiconfigurational self-consistent reaction field theory for nonequilibrium solvation

Kurt V. Mikkelsen*, Amary Cesar, Hans Ågren, Hans Joørgen Aa Jensen

*Kontaktforfatter for dette arbejde

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

Resumé

We present multiconfigurational self-consistent reaction field theory and implementation for solvent effects on a solute molecular system that is not in equilibrium with the outer solvent. The approach incorporates two different polarization vectors for studying the influence of the solvent. The solute, an atom, a molecule or a supermolecule, is assumed to be surrounded by a linear, homogeneous medium described by two polarization vector fields, the optical polarization vector and the inertial polarization vector fields. The optical polarization vector is always in equilibrium with the actual electronic structure whereas the inertial polarization vector is not necessarily in equilibrium with the actual electronic structure. The electronic structure of the compound is described by a correlated electronic wave function - a multiconfigurational self-consistent field (MCSCF) wave function. This wave function is fully optimized with respect to all variational parameters in the presence of the surrounding polarizable dielectric medium having two distinct polarization vectors. We develop from a compact and simple expression a direct and second-order convergent optimization procedure for the solvent states influenced by the two types of polarization vectors. The general treatment of the correlation problem through the use of complete and restricted active space methodologies makes the present multiconfigurational self-consistent reaction field approach general in that it can handle any type of state, open-shell, excited, and transition states. We demonstrate the theory by computing solvatochromatic shifts in optical/UV spectra of some small molecules and electron ionization and electron detachment energies of the benzene molecule. It is shown that the dependency of the solvent induced affinity in benzene is nonmonotonic with respect the optical dielectric constant if inertial polarization effects also are accounted for.

OriginalsprogEngelsk
TidsskriftThe Journal of Chemical Physics
Vol/bind103
Udgave nummer20
Sider (fra-til)9010-9023
Antal sider14
ISSN0021-9606
StatusUdgivet - 1995

Fingeraftryk

Solvation
solvation
Polarization
polarization
Wave functions
Electronic structure
optical polarization
wave functions
Light polarization
electronic structure
Benzene
Molecules
solutes
benzene
molecules
ionization
Electrons
detachment
Ionization
self consistent fields

Citer dette

Mikkelsen, Kurt V. ; Cesar, Amary ; Ågren, Hans ; Jensen, Hans Joørgen Aa. / Multiconfigurational self-consistent reaction field theory for nonequilibrium solvation. I: The Journal of Chemical Physics. 1995 ; Bind 103, Nr. 20. s. 9010-9023.
@article{b5787450bbe14d708480022ddc83b407,
title = "Multiconfigurational self-consistent reaction field theory for nonequilibrium solvation",
abstract = "We present multiconfigurational self-consistent reaction field theory and implementation for solvent effects on a solute molecular system that is not in equilibrium with the outer solvent. The approach incorporates two different polarization vectors for studying the influence of the solvent. The solute, an atom, a molecule or a supermolecule, is assumed to be surrounded by a linear, homogeneous medium described by two polarization vector fields, the optical polarization vector and the inertial polarization vector fields. The optical polarization vector is always in equilibrium with the actual electronic structure whereas the inertial polarization vector is not necessarily in equilibrium with the actual electronic structure. The electronic structure of the compound is described by a correlated electronic wave function - a multiconfigurational self-consistent field (MCSCF) wave function. This wave function is fully optimized with respect to all variational parameters in the presence of the surrounding polarizable dielectric medium having two distinct polarization vectors. We develop from a compact and simple expression a direct and second-order convergent optimization procedure for the solvent states influenced by the two types of polarization vectors. The general treatment of the correlation problem through the use of complete and restricted active space methodologies makes the present multiconfigurational self-consistent reaction field approach general in that it can handle any type of state, open-shell, excited, and transition states. We demonstrate the theory by computing solvatochromatic shifts in optical/UV spectra of some small molecules and electron ionization and electron detachment energies of the benzene molecule. It is shown that the dependency of the solvent induced affinity in benzene is nonmonotonic with respect the optical dielectric constant if inertial polarization effects also are accounted for.",
author = "Mikkelsen, {Kurt V.} and Amary Cesar and Hans {\AA}gren and Jensen, {Hans Jo{\o}rgen Aa}",
year = "1995",
language = "English",
volume = "103",
pages = "9010--9023",
journal = "The Journal of Chemical Physics",
issn = "0021-9606",
publisher = "American Institute of Physics",
number = "20",

}

Multiconfigurational self-consistent reaction field theory for nonequilibrium solvation. / Mikkelsen, Kurt V.; Cesar, Amary; Ågren, Hans; Jensen, Hans Joørgen Aa.

I: The Journal of Chemical Physics, Bind 103, Nr. 20, 1995, s. 9010-9023.

Publikation: Bidrag til tidsskriftTidsskriftartikelForskningpeer review

TY - JOUR

T1 - Multiconfigurational self-consistent reaction field theory for nonequilibrium solvation

AU - Mikkelsen, Kurt V.

AU - Cesar, Amary

AU - Ågren, Hans

AU - Jensen, Hans Joørgen Aa

PY - 1995

Y1 - 1995

N2 - We present multiconfigurational self-consistent reaction field theory and implementation for solvent effects on a solute molecular system that is not in equilibrium with the outer solvent. The approach incorporates two different polarization vectors for studying the influence of the solvent. The solute, an atom, a molecule or a supermolecule, is assumed to be surrounded by a linear, homogeneous medium described by two polarization vector fields, the optical polarization vector and the inertial polarization vector fields. The optical polarization vector is always in equilibrium with the actual electronic structure whereas the inertial polarization vector is not necessarily in equilibrium with the actual electronic structure. The electronic structure of the compound is described by a correlated electronic wave function - a multiconfigurational self-consistent field (MCSCF) wave function. This wave function is fully optimized with respect to all variational parameters in the presence of the surrounding polarizable dielectric medium having two distinct polarization vectors. We develop from a compact and simple expression a direct and second-order convergent optimization procedure for the solvent states influenced by the two types of polarization vectors. The general treatment of the correlation problem through the use of complete and restricted active space methodologies makes the present multiconfigurational self-consistent reaction field approach general in that it can handle any type of state, open-shell, excited, and transition states. We demonstrate the theory by computing solvatochromatic shifts in optical/UV spectra of some small molecules and electron ionization and electron detachment energies of the benzene molecule. It is shown that the dependency of the solvent induced affinity in benzene is nonmonotonic with respect the optical dielectric constant if inertial polarization effects also are accounted for.

AB - We present multiconfigurational self-consistent reaction field theory and implementation for solvent effects on a solute molecular system that is not in equilibrium with the outer solvent. The approach incorporates two different polarization vectors for studying the influence of the solvent. The solute, an atom, a molecule or a supermolecule, is assumed to be surrounded by a linear, homogeneous medium described by two polarization vector fields, the optical polarization vector and the inertial polarization vector fields. The optical polarization vector is always in equilibrium with the actual electronic structure whereas the inertial polarization vector is not necessarily in equilibrium with the actual electronic structure. The electronic structure of the compound is described by a correlated electronic wave function - a multiconfigurational self-consistent field (MCSCF) wave function. This wave function is fully optimized with respect to all variational parameters in the presence of the surrounding polarizable dielectric medium having two distinct polarization vectors. We develop from a compact and simple expression a direct and second-order convergent optimization procedure for the solvent states influenced by the two types of polarization vectors. The general treatment of the correlation problem through the use of complete and restricted active space methodologies makes the present multiconfigurational self-consistent reaction field approach general in that it can handle any type of state, open-shell, excited, and transition states. We demonstrate the theory by computing solvatochromatic shifts in optical/UV spectra of some small molecules and electron ionization and electron detachment energies of the benzene molecule. It is shown that the dependency of the solvent induced affinity in benzene is nonmonotonic with respect the optical dielectric constant if inertial polarization effects also are accounted for.

UR - http://www.scopus.com/inward/record.url?scp=36449003296&partnerID=8YFLogxK

M3 - Journal article

AN - SCOPUS:36449003296

VL - 103

SP - 9010

EP - 9023

JO - The Journal of Chemical Physics

JF - The Journal of Chemical Physics

SN - 0021-9606

IS - 20

ER -