Abstract
The refractive indices of benzene in the gas and liquid phase are computed employing a classical electrodynamical treatment of light propagation in continuous media and high level ab initio computations of the relevant molecular properties. We investigate various levels of complexity when deriving expressions relating the microscopic molecular optical properties and the refractive index. Different methods of accounting for the molecular environment within the framework of quantum chemical computations are scrutinized. The fundamental molecular property determining the refractivite index is the polarizability, and dynamic molecular polarizabilities of benzene are adequately computed using a triple-zeta plus double polarization basis; larger basis sets change the computed values by less than 1%. The effects of electronic correlation on the dynamic polarizabililties are discussed. For benzene vapor, computed results for the refractive index agree well with experiment. For liquid benzene, the best agreement with experiment is found using the Lorentz-Lorenz formula with computed gas-phase polarizability. We introduce the isolated molecule classical environment (IMLE) and the iterative self-consistent reaction field approach.
| Original language | English |
|---|---|
| Pages (from-to) | 8447-8457 |
| Number of pages | 11 |
| Journal | Journal of Physical Chemistry A |
| Volume | 103 |
| Issue number | 42 |
| Publication status | Published - Oct 21 1999 |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
Cite this
Refractive indices of molecules in vapor and liquid : Calculations on benzene. / Sylvester-Hvid, Kristian O.; Mikkelsen, Kurt V.; Ratner, Mark A.
In: Journal of Physical Chemistry A, Vol. 103, No. 42, 21.10.1999, p. 8447-8457.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Refractive indices of molecules in vapor and liquid
T2 - Calculations on benzene
AU - Sylvester-Hvid, Kristian O.
AU - Mikkelsen, Kurt V.
AU - Ratner, Mark A
PY - 1999/10/21
Y1 - 1999/10/21
N2 - The refractive indices of benzene in the gas and liquid phase are computed employing a classical electrodynamical treatment of light propagation in continuous media and high level ab initio computations of the relevant molecular properties. We investigate various levels of complexity when deriving expressions relating the microscopic molecular optical properties and the refractive index. Different methods of accounting for the molecular environment within the framework of quantum chemical computations are scrutinized. The fundamental molecular property determining the refractivite index is the polarizability, and dynamic molecular polarizabilities of benzene are adequately computed using a triple-zeta plus double polarization basis; larger basis sets change the computed values by less than 1%. The effects of electronic correlation on the dynamic polarizabililties are discussed. For benzene vapor, computed results for the refractive index agree well with experiment. For liquid benzene, the best agreement with experiment is found using the Lorentz-Lorenz formula with computed gas-phase polarizability. We introduce the isolated molecule classical environment (IMLE) and the iterative self-consistent reaction field approach.
AB - The refractive indices of benzene in the gas and liquid phase are computed employing a classical electrodynamical treatment of light propagation in continuous media and high level ab initio computations of the relevant molecular properties. We investigate various levels of complexity when deriving expressions relating the microscopic molecular optical properties and the refractive index. Different methods of accounting for the molecular environment within the framework of quantum chemical computations are scrutinized. The fundamental molecular property determining the refractivite index is the polarizability, and dynamic molecular polarizabilities of benzene are adequately computed using a triple-zeta plus double polarization basis; larger basis sets change the computed values by less than 1%. The effects of electronic correlation on the dynamic polarizabililties are discussed. For benzene vapor, computed results for the refractive index agree well with experiment. For liquid benzene, the best agreement with experiment is found using the Lorentz-Lorenz formula with computed gas-phase polarizability. We introduce the isolated molecule classical environment (IMLE) and the iterative self-consistent reaction field approach.
UR - http://www.scopus.com/inward/record.url?scp=0000163239&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0000163239&partnerID=8YFLogxK
M3 - Article
VL - 103
SP - 8447
EP - 8457
JO - Journal of Physical Chemistry A
JF - Journal of Physical Chemistry A
SN - 1089-5639
IS - 42
ER -