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Intensity tracking for theoretical infrared spectroscopy of large molecules
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10.1063/1.3069834
/content/aip/journal/jcp/130/6/10.1063/1.3069834
http://aip.metastore.ingenta.com/content/aip/journal/jcp/130/6/10.1063/1.3069834

Figures

Image of FIG. 1.
FIG. 1.

Optimized structures (BP86/RI/TZVP) of -epichlorhydrin (1), -methyloxirane (2), -alanine (3), --[4]-helicene (4), all--decaalanine (5), -tris(ethylenediaminato)cobalt(III) (6), and Schrock’s dinitrogen molybdenum complex (7).

Image of FIG. 2.
FIG. 2.

Technical aspects of intensity-tracking calculations. (a) Demonstration of convergence to the exact IR spectrum in the limit of a complete basis: intensity-tracking IR spectrum (BP86/RI/TZVP) of -epichlorhydrin (1) employing and compared to the conventional full calculation. (b) Analysis of root-homing options for a given convergence threshold per mode: intensity-tracking IR spectra (BP86/RI/TZVP) of --[4]-helicene (4) obtained by applying different selection procedures and together with the reference spectrum of the complete set of normal modes given first.

Image of FIG. 3.
FIG. 3.

IR spectra (BP86/RI/TZVP) of all--decaalanine (5) for different iteration steps of the intensity-tracking calculation (bottom and middle) employing and . The reference spectrum at the top was obtained by a calculation of the complete set of normal modes. The arrow indicates the progress of the intensity-tracking iterations.

Image of FIG. 4.
FIG. 4.

Calculated IR spectra (BP86/RI/TZVP) of -tris(ethylenediaminato)cobalt(III) (6); the first spectrum at the top is the reference spectrum, while the other intensity-tracking spectra were obtained by applying or with and , respectively. Three different initial guesses were employed: two employing the finite-field method, calculated via Eq. (12) (“finite field”) and Eq. (9) (“finite-field EV”), respectively, and one employing a breathing mode, indicated by “breathing mode.” The reference spectrum at the top was obtained by a calculation of the complete set of normal modes.

Image of FIG. 5.
FIG. 5.

IR spectra (BP86/RI/TZVP) of Schrock’s dinitrogen molybdenum complex (7) obtained by a calculation of the complete set of normal modes (left-hand side; spectrum taken from Ref. 49) and by an intensity-tracking calculation employing in combination with the condition of large contributions from the metal center (right-hand side; see text for details).

Image of FIG. 6.
FIG. 6.

Vector representation of normal modes of Schrock’s dinitrogen molybdenum complex (7) obtained from a calculation of the complete set of normal modes (left-hand side) and from an intensity-tracking calculation (right-hand side; see text for details).

Tables

Generic image for table
Table I.

Results of the intensity-tracking calculations [number of basis vectors (Vectors), iterations, and converged normal modes (Conv.)] for all--decaalanine (5) (total number of normal modes: 303) with the initial guess obtained by the finite-field method applying different selection procedures and values for the maximum component of the residuum vector; the values in parentheses present the results gained with a breathing mode as the initial guess.

Generic image for table
Table II.

Results of the intensity-tracking calculations [number of basis vectors (Vectors), iterations, and converged normal modes (Conv.)] for -tris(ethylenediaminato)cobalt(III) (6) (total number of normal modes: 105) with the initial guess obtained by the finite-field method employing different selection procedures and values for the maximum component of the residuum vector; the values in parentheses show the results obtained with a breathing mode as the initial guess.

Generic image for table
Table III.

Results of the intensity-tracking calculations [number of basis vectors (Vectors), iterations, and converged normal modes (Conv.)] for -tris(ethylenediaminato)cobalt(III) (6) with the initial guess obtained by the finite-field method employing different selection procedures and values for the maximum component of the residuum vector; the values in parentheses are the results obtained with a breathing mode as the initial guess.

Generic image for table
Table IV.

Results of the intensity-tracking calculations [number of basis vectors (Vectors), iterations, and converged normal modes (Conv.)] for all--decaalanine (5) with the initial guess evaluated by the finite-field method employing different selection procedures and values for the maximum component of the residuum vector.

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/content/aip/journal/jcp/130/6/10.1063/1.3069834
2009-02-12
2014-04-25
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Intensity tracking for theoretical infrared spectroscopy of large molecules
http://aip.metastore.ingenta.com/content/aip/journal/jcp/130/6/10.1063/1.3069834
10.1063/1.3069834
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