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Vibrational solvatochromism and electrochromism. II. Multipole analysis
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10.1063/1.4751477
/content/aip/journal/jcp/137/11/10.1063/1.4751477
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/11/10.1063/1.4751477

Figures

Image of FIG. 1.
FIG. 1.

The DFT-calculated frequency shifts (Δω) of the amide I’ mode and C=O stretch mode of NMA- and acetone, respectively, are compared with theoretical results (Δω). Molecular structures and atomic sites are shown here. The center of mass (COM), center of square of mass-weighted eigenvector (COE), and center of square solvatochromic charge (COS) are shown on the molecular structure. The frequency shifts calculated by using solvatochromic charge (black circles), dipole (violet circles), quadrupole (orange circles), and octupole (dark green circles) are plotted with respect to the DFT-calculated frequency shifts. The sum of solvatochromic dipole and quadrupole contributions is represented by open square.

Image of FIG. 2.
FIG. 2.

The DFT-calculated frequency shifts of the nitrile stretch modes of CHCN and CHSCN and the azido stretch mode of CHN are compared with theoretical results (see the caption of Fig. 1 for the description of symbols).

Image of FIG. 3.
FIG. 3.

The DFT-calculated frequency shift of the CHCN nitrile stretch mode in CHCN/water dimer is plotted for varying H-bond angle (see the caption of Fig. 1 for the description of symbols).

Image of FIG. 4.
FIG. 4.

The DFT-calculated frequency shifts of the nitrile stretch modes of -tolunitrile and 4-cyanopyridine are compared with theoretical results (see the caption of Fig. 1 for the description of symbols).

Image of FIG. 5.
FIG. 5.

The DFT-calculated frequency shift of the CO stretch mode is compared with theoretical results (see the caption of Fig. 1 for the description of symbols).

Image of FIG. 6.
FIG. 6.

The DFT-calculated frequency shifts of the nitrile stretch modes of CN and SCN and the azide stretch mode are compared with theoretical results (see the caption of Fig. 1 for the description of symbols).

Image of FIG. 7.
FIG. 7.

The DFT-calculated frequency shifts of the C-F stretch modes of fluorobenzene and 3-fluoropyridine are compared with theoretical results (see the caption of Fig. 1 for the description of symbols).

Tables

Generic image for table
Table I.

Solvatochromic charges () in cm−1/V. The electric potential is given in volt and the vibrational frequency is in cm−1.

Generic image for table
Table II.

Solvatochromic dipole, quadrupole, and octupole tensor elements in cm−1/(MV/cm), 10−8 cm−1/(MV/cm2), and 10−16 cm−1/(MV/cm3), respectively. The origin of a given molecule-fixed frame used in the multipole expansion is assumed to be the COE. Here, the -components of the solvatochromic dipole moments, Δμ, and the -, -, - and -elements of the solvatochromic quadrupole moments of all the modes considered here are zero or vanishingly small. Similarly, the elements of octupole moments that are not listed in this table vanish or are vanishingly small. Here, TN, CP, FB, and FP represent the p-tolunitrile, 4-cyanopyridine, fluorobenzene, and 3-fluoropyridine, respectively.

Generic image for table
Table III.

The magnitudes of the solvatochromic dipole, quadrupole, and octupole in cm−1/(MV/cm), 10−8 cm−1/(MV/cm2), and 10−16 cm−1/(MV/cm3), respectively.

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/content/aip/journal/jcp/137/11/10.1063/1.4751477
2012-09-20
2014-04-20
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Vibrational solvatochromism and electrochromism. II. Multipole analysis
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/11/10.1063/1.4751477
10.1063/1.4751477
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