Ab initio calculation of vibrational absorption and circular dichroism spectra: 6,8-Dioxabicyclo[3.2.1]octane

CS Ashvar; FJ Devlin; KL Bak; PR Taylor; PJ Stephens

Ab initio calculation of vibrational absorption and circular dichroism spectra: 6,8-Dioxabicyclo[3.2.1]octane

CS Ashvar, FJ Devlin, KL Bak, PR Taylor, PJ Stephens

Publikation: Bidrag til tidsskrift/Konferencebidrag i tidsskrift /Bidrag til avis › Tidsskriftartikel › Forskning › peer review

Abstract

Predictions of the unpolarized vibrational absorption and vibrational circular dichroism (VCD) spectra of the chiral molecule 6,8-dioxabicyclo[3.2.1]octane (1) are reported. Harmonic force fields and atomic polar tensors are obtained using the density functional theory (DFT), MP2 and SCF methodologies, and the 3-21G and 6-31G* basis sets. Three functionals, LSDA, BLYP, and B3LYP, are used in DFT calculations. Atomic axial tensors are obtained using the Distribution Origin gauge; distributed atomic axial tensors are calculated using gauge-invariant atomic orbitals (GIAOs) at the SCF level of approximation. The quality of the predicted spectra is highly dependent on the methodology and the basis set is employed. Spectra calculated using 6-31G* MP2 and DFT/B3LYP force fields are very similar and in excellent agreement with experimental spectra. 6-31G* SCF, DFT/LSDA and DFT/BLYP calculations are in significantly worse agreement with experiment, as are 3-21G MP2 and DFT/B3LYP calculations. When both accuracy and computational effort are considered, at this time, predictions of vibrational absorption and VCD spectra of molecules comparable to 1 in size are optimally performed using 6-31G* or equivalent basis sets and (i) harmonic force fields and atomic polar tensors calculated via DFT and a hybrid density functional; (ii) Distributed Origin gauge atomic axial tensors; and (iii) SCF GIAO-based distributed atomic axial tensors.

Originalsprog	Engelsk
Tidsskrift	Journal of Physical Chemistry
Vol/bind	100
Nummer	22
Sider (fra-til)	9262-9270
Antal sider	9
ISSN	0022-3654
Status	Udgivet - 30 maj 1996

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title = "Ab initio calculation of vibrational absorption and circular dichroism spectra: 6,8-Dioxabicyclo[3.2.1]octane",

abstract = "Predictions of the unpolarized vibrational absorption and vibrational circular dichroism (VCD) spectra of the chiral molecule 6,8-dioxabicyclo[3.2.1]octane (1) are reported. Harmonic force fields and atomic polar tensors are obtained using the density functional theory (DFT), MP2 and SCF methodologies, and the 3-21G and 6-31G* basis sets. Three functionals, LSDA, BLYP, and B3LYP, are used in DFT calculations. Atomic axial tensors are obtained using the Distribution Origin gauge; distributed atomic axial tensors are calculated using gauge-invariant atomic orbitals (GIAOs) at the SCF level of approximation. The quality of the predicted spectra is highly dependent on the methodology and the basis set is employed. Spectra calculated using 6-31G* MP2 and DFT/B3LYP force fields are very similar and in excellent agreement with experimental spectra. 6-31G* SCF, DFT/LSDA and DFT/BLYP calculations are in significantly worse agreement with experiment, as are 3-21G MP2 and DFT/B3LYP calculations. When both accuracy and computational effort are considered, at this time, predictions of vibrational absorption and VCD spectra of molecules comparable to 1 in size are optimally performed using 6-31G* or equivalent basis sets and (i) harmonic force fields and atomic polar tensors calculated via DFT and a hybrid density functional; (ii) Distributed Origin gauge atomic axial tensors; and (iii) SCF GIAO-based distributed atomic axial tensors.",

keywords = "DENSITY FUNCTIONAL THEORY, NMR CHEMICAL-SHIFTS, ABSOLUTE-CONFIGURATION, ROTATIONAL STRENGTHS, PERTURBATION-THEORY, PROPYLENE-OXIDE, FORCE-FIELDS",

author = "CS Ashvar and FJ Devlin and KL Bak and PR Taylor and PJ Stephens",

year = "1996",

month = may,

day = "30",

language = "English",

volume = "100",

pages = "9262--9270",

journal = "Journal of Physical Chemistry",

issn = "0022-3654",

publisher = "ACS American Chemical Society",

number = "22",

}

TY - JOUR

T1 - Ab initio calculation of vibrational absorption and circular dichroism spectra

T2 - 6,8-Dioxabicyclo[3.2.1]octane

AU - Ashvar, CS

AU - Devlin, FJ

AU - Bak, KL

AU - Taylor, PR

AU - Stephens, PJ

PY - 1996/5/30

Y1 - 1996/5/30

N2 - Predictions of the unpolarized vibrational absorption and vibrational circular dichroism (VCD) spectra of the chiral molecule 6,8-dioxabicyclo[3.2.1]octane (1) are reported. Harmonic force fields and atomic polar tensors are obtained using the density functional theory (DFT), MP2 and SCF methodologies, and the 3-21G and 6-31G* basis sets. Three functionals, LSDA, BLYP, and B3LYP, are used in DFT calculations. Atomic axial tensors are obtained using the Distribution Origin gauge; distributed atomic axial tensors are calculated using gauge-invariant atomic orbitals (GIAOs) at the SCF level of approximation. The quality of the predicted spectra is highly dependent on the methodology and the basis set is employed. Spectra calculated using 6-31G* MP2 and DFT/B3LYP force fields are very similar and in excellent agreement with experimental spectra. 6-31G* SCF, DFT/LSDA and DFT/BLYP calculations are in significantly worse agreement with experiment, as are 3-21G MP2 and DFT/B3LYP calculations. When both accuracy and computational effort are considered, at this time, predictions of vibrational absorption and VCD spectra of molecules comparable to 1 in size are optimally performed using 6-31G* or equivalent basis sets and (i) harmonic force fields and atomic polar tensors calculated via DFT and a hybrid density functional; (ii) Distributed Origin gauge atomic axial tensors; and (iii) SCF GIAO-based distributed atomic axial tensors.

AB - Predictions of the unpolarized vibrational absorption and vibrational circular dichroism (VCD) spectra of the chiral molecule 6,8-dioxabicyclo[3.2.1]octane (1) are reported. Harmonic force fields and atomic polar tensors are obtained using the density functional theory (DFT), MP2 and SCF methodologies, and the 3-21G and 6-31G* basis sets. Three functionals, LSDA, BLYP, and B3LYP, are used in DFT calculations. Atomic axial tensors are obtained using the Distribution Origin gauge; distributed atomic axial tensors are calculated using gauge-invariant atomic orbitals (GIAOs) at the SCF level of approximation. The quality of the predicted spectra is highly dependent on the methodology and the basis set is employed. Spectra calculated using 6-31G* MP2 and DFT/B3LYP force fields are very similar and in excellent agreement with experimental spectra. 6-31G* SCF, DFT/LSDA and DFT/BLYP calculations are in significantly worse agreement with experiment, as are 3-21G MP2 and DFT/B3LYP calculations. When both accuracy and computational effort are considered, at this time, predictions of vibrational absorption and VCD spectra of molecules comparable to 1 in size are optimally performed using 6-31G* or equivalent basis sets and (i) harmonic force fields and atomic polar tensors calculated via DFT and a hybrid density functional; (ii) Distributed Origin gauge atomic axial tensors; and (iii) SCF GIAO-based distributed atomic axial tensors.

KW - DENSITY FUNCTIONAL THEORY

KW - NMR CHEMICAL-SHIFTS

KW - ABSOLUTE-CONFIGURATION

KW - ROTATIONAL STRENGTHS

KW - PERTURBATION-THEORY

KW - PROPYLENE-OXIDE

KW - FORCE-FIELDS

M3 - Journal article

SN - 0022-3654

VL - 100

SP - 9262

EP - 9270

JO - Journal of Physical Chemistry

JF - Journal of Physical Chemistry

IS - 22

ER -

Ab initio calculation of vibrational absorption and circular dichroism spectra: 6,8-Dioxabicyclo[3.2.1]octane

Abstract

Fingeraftryk

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