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A second-order perturbation theory route to vibrational averages and transition properties of molecules: General formulation and application to infrared and vibrational circular dichroism spectroscopies
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10.1063/1.3695210
/content/aip/journal/jcp/136/12/10.1063/1.3695210
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/12/10.1063/1.3695210

Figures

Image of FIG. 1.
FIG. 1.

Mid-IR absorption spectra of R-methyloxirane in arbitrary units. Harmonic (green dashed line) and anharmonic (blue solid line) molar extinction coefficients (ε) were computed at the B3LYP/aug-N07D. Absorption lines were broadened with a Lorentzian function and a half-width at half-maximum of 4 cm−1. Experimental data (orange dotted line) have been taken from Ref. 88 and normalized so that the highest peak has the same height as its anharmonic counterpart.

Image of FIG. 2.
FIG. 2.

Mid-IR VCD spectra of R-methyloxirane in arbitrary units. Harmonic (green dashed line) and anharmonic (blue solid line) differential molar extinction coefficients (Δε) were computed at the B3LYP/aug-N07D. Peaks were broadened with a Lorentzian function and a half-width at half-maximum of 4 cm−1. Experimental data (orange dotted line) have been taken from Ref. 88 and normalized so that the highest peak has the same height as its anharmonic counterpart.

Image of FIG. 3.
FIG. 3.

Mid-IR absorption spectra of R-deuterated methyloxirane. Harmonic (green dashed line) and anharmonic (blue solid line) molar extinction coefficients (ε, in dm3 mol−1 cm−1) were computed at the B3LYP/aug-N07D. Absorption lines were broadened with a Lorentzian function and a half-width at half-maximum of 4 cm−1.

Image of FIG. 4.
FIG. 4.

VCD spectra of R-deuterated methyloxirane. Harmonic (green dashed line) and anharmonic (blue solid line) differential molar extinction coefficients (Δε in dm3 mol−1 cm−1) were computed at the B3LYP/aug-N07D. Peaks were broadened with a Lorentzian function and a half-width at half-maximum of 4 cm−1.

Image of FIG. 5.
FIG. 5.

Absorption spectra of R-norcamphor. Harmonic (green dashed line) and anharmonic (blue solid line) molar extinction coefficients (ε, in dm3 mol−1 cm−1) were computed at the B3LYP/aug-N07D. Peaks were broadened with a Lorentzian function and a half-width at half-maximum of 4 cm−1.

Image of FIG. 6.
FIG. 6.

VCD spectra of R-norcamphor. Harmonic (green dashed line) and anharmonic (blue solid line) differential molar extinction coefficients (Δε in dm3 mol−1 cm−1) were computed at the B3LYP/aug-N07D. Absorption lines were broadened with a Lorentzian function and a half-width at half-maximum of 4 cm−1.

Tables

Generic image for table
Table I.

Equivalency relations for different properties.

Generic image for table
Table II.

Comparison of frequencies (in cm−1), dipole strengths (in 10−39esu2 cm2), rotatory strengths (in 10−44esu2 cm2) for S,S-trans-2,3-dideuteriooxirane. MP2/TZ2P calculations were done in Refs. 63 and 64 and experimental data come from Ref. 83. The superscript “F” indicates that Fermi resonances were present in the calculation of the datum at the anharmonic level. The superscript “D” stands for Darling-Dennison resonance.

Generic image for table
Table III.

Comparison of frequencies (in cm−1), dipole strengths (in 10−40esu2 cm2), rotatory strengths (in 10−44esu2 cm2) for R-methyloxirane. The superscript “F” indicates that Fermi resonances were present in the calculation of the datum at the anharmonic level. The superscript “D” stands for Darling-Dennison resonance and “1” for a 1-1 resonance.

Generic image for table
Table IV.

Energies (in cm−1), dipole strengths (in 10−40esu2 cm2) and rotatory strengths (in 10−44 esu2 cm2) for some vibrational transitions of R-methyloxirane from the ground state to overtones and combinations bands below 4000 cm−1. The transitions were chosen based on the associated peak of molar extinction coefficient (at least 40 dm3 mol−1 cm−1) or difference in molar extinction coefficients (|Δε| ⩾ 10dm3 mol−1 cm−1). The last column indicates that Fermi resonances were present for the calculation of the anharmonic data.

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/content/aip/journal/jcp/136/12/10.1063/1.3695210
2012-03-27
2014-04-24
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: A second-order perturbation theory route to vibrational averages and transition properties of molecules: General formulation and application to infrared and vibrational circular dichroism spectroscopies
http://aip.metastore.ingenta.com/content/aip/journal/jcp/136/12/10.1063/1.3695210
10.1063/1.3695210
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