Ab initio determination of the nuclear relaxation contribution to the second hyperpolarizability of carbon disulfide

Research output: Contribution to journalArticle

Abstract

Although basis set saturation, electron correlation and frequency dispersion have been addressed thoroughly, the electronic second hyperpolarizability of carbon disulfide computed by K. Ohta, T. Sakaguchi, K. Kamada and T. Fukumi (Chem. Phys. Lett. 274 (1997) 306) is not in agreement with experiment. In this Letter the potentially substantial nuclear relaxation contribution is evaluated within the Møller-Plesset scheme limited to second order by using the 6-31G* basis set augmented by three diffuse functions (1p and 2d). Within the enhanced approximation, the nuclear relaxation contribution to the static, dc-Kerr and ESHG second hyperpolarizability turns out to amount to 26.5%, 6.8% and -0.8% of the pure static electronic counterpart, respectively. The remaining gap between theory and experiment suggests new experiments should be carried out.

Original languageEnglish
Pages (from-to)185-188
Number of pages4
JournalChemical Physics Letters
Volume287
Issue number1-2
Publication statusPublished - 24 Apr 1998

Fingerprint

Carbon Disulfide
nuclear relaxation
carbon disulfide
electronics
Electron correlations
Experiments
saturation
approximation
electrons

Cite this

@article{e0492fb0c9954f18bbf8e413113d6e1b,
title = "Ab initio determination of the nuclear relaxation contribution to the second hyperpolarizability of carbon disulfide",
abstract = "Although basis set saturation, electron correlation and frequency dispersion have been addressed thoroughly, the electronic second hyperpolarizability of carbon disulfide computed by K. Ohta, T. Sakaguchi, K. Kamada and T. Fukumi (Chem. Phys. Lett. 274 (1997) 306) is not in agreement with experiment. In this Letter the potentially substantial nuclear relaxation contribution is evaluated within the M{\o}ller-Plesset scheme limited to second order by using the 6-31G* basis set augmented by three diffuse functions (1p and 2d). Within the enhanced approximation, the nuclear relaxation contribution to the static, dc-Kerr and ESHG second hyperpolarizability turns out to amount to 26.5{\%}, 6.8{\%} and -0.8{\%} of the pure static electronic counterpart, respectively. The remaining gap between theory and experiment suggests new experiments should be carried out.",
author = "Beno{\^i}t Champagne",
year = "1998",
month = "4",
day = "24",
language = "English",
volume = "287",
pages = "185--188",
journal = "Chemical Physics Letters",
issn = "0009-2614",
publisher = "Elsevier",
number = "1-2",

}

TY - JOUR

T1 - Ab initio determination of the nuclear relaxation contribution to the second hyperpolarizability of carbon disulfide

AU - Champagne, Benoît

PY - 1998/4/24

Y1 - 1998/4/24

N2 - Although basis set saturation, electron correlation and frequency dispersion have been addressed thoroughly, the electronic second hyperpolarizability of carbon disulfide computed by K. Ohta, T. Sakaguchi, K. Kamada and T. Fukumi (Chem. Phys. Lett. 274 (1997) 306) is not in agreement with experiment. In this Letter the potentially substantial nuclear relaxation contribution is evaluated within the Møller-Plesset scheme limited to second order by using the 6-31G* basis set augmented by three diffuse functions (1p and 2d). Within the enhanced approximation, the nuclear relaxation contribution to the static, dc-Kerr and ESHG second hyperpolarizability turns out to amount to 26.5%, 6.8% and -0.8% of the pure static electronic counterpart, respectively. The remaining gap between theory and experiment suggests new experiments should be carried out.

AB - Although basis set saturation, electron correlation and frequency dispersion have been addressed thoroughly, the electronic second hyperpolarizability of carbon disulfide computed by K. Ohta, T. Sakaguchi, K. Kamada and T. Fukumi (Chem. Phys. Lett. 274 (1997) 306) is not in agreement with experiment. In this Letter the potentially substantial nuclear relaxation contribution is evaluated within the Møller-Plesset scheme limited to second order by using the 6-31G* basis set augmented by three diffuse functions (1p and 2d). Within the enhanced approximation, the nuclear relaxation contribution to the static, dc-Kerr and ESHG second hyperpolarizability turns out to amount to 26.5%, 6.8% and -0.8% of the pure static electronic counterpart, respectively. The remaining gap between theory and experiment suggests new experiments should be carried out.

UR - http://www.scopus.com/inward/record.url?scp=0032562316&partnerID=8YFLogxK

M3 - Article

AN - SCOPUS:0032562316

VL - 287

SP - 185

EP - 188

JO - Chemical Physics Letters

JF - Chemical Physics Letters

SN - 0009-2614

IS - 1-2

ER -