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Efficient and automatic calculation of optical band shapes and resonance Raman spectra for larger molecules within the independent mode displaced harmonic oscillator model
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10.1063/1.4771959
/content/aip/journal/jcp/137/23/10.1063/1.4771959
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/23/10.1063/1.4771959

Figures

Image of FIG. 1.
FIG. 1.

Molecular structures used in the test calculations: tetracene (1), Ni(L)2]1− (L = benzene-1,2-dithiol) (2), trans-1,3,5-hexatrien (3), rubrene (4), plastocyanin model compound LCuSR borate (L = hydrotris(3,5-diisopropyl-lpyrazoly1, R = triphenylmethyl) (5), all-trans-β-carotene (6).

Image of FIG. 2.
FIG. 2.

Experimental (black, Ref. 26) and calculated ABS and rR spectra of THT. The simulated spectra were obtained at the B3LYP/TZV(2df,p) level of theory using the global geometry optimization method (red) and gradient techniques (blue). The simulated spectra indicated by green curves correspond to the fitted displacement parameters.

Image of FIG. 3.
FIG. 3.

Calculated ABS and FL spectra of Tc. The simulated spectra were obtained at the B3LYP/TZV(2df,p) level of theory using gradient techniques (red) and global geometry optimization method (blue). The spectra presenting detailed vibrational structure in the ABS and FL were constructed using reduced values of the linewidth parameters {Γ = 2 cm-1, Θ = 0 cm−1}.

Image of FIG. 4.
FIG. 4.

Experimental (black, Ref. 6) and calculated ABS (red) and FL (blue) spectra of Tc. The simulated spectra were obtained at the B3LYP/TZV(2df,p) level of theory using the gradient techniques. The calculated spectra indicated by dashed curves correspond to the adjusted value of the excited state normal mode displacement Δ9 = 1.0 (ω = 1369 cm−1) while the other displacement parameters were obtained from the calculations using the gradient techniques.

Image of FIG. 5.
FIG. 5.

Calculated ABS and FL spectra of Rub. The simulated spectra were obtained at the B3LYP/TZV(2df,p) level of theory using the global geometry optimization method (blue) and gradient techniques (red). The spectra presenting detailed vibrational structure in the ABS and FL were constructed using reduced values of the linewidth parameters to {Γ = 1 cm−1, Θ = 0 cm−1}. For convenience of the presentation, the high- and low-resolution spectra are scaled by different factors.

Image of FIG. 6.
FIG. 6.

Experimental (black, Ref. 6) and calculated ABS nd FL spectra of Rub. The simulated spectra were obtained at the B3LYP/TZV(2df,p) level of theory using the gradient techniques (red for ABS, blue for FL), and global geometry optimization method (green). The calculated spectra indicated by dashed curves correspond to the adjusted value of the excited state normal mode displacement Δ34 = 0.95 (ω34 = 1283 cm−1) while the other displacement parameters were obtained from the calculations using the gradient techniques. The small vertical bar designates the low-energy bound of the part of the experimental fluorescence spectrum which is considered to be less reliable due to the reduced sensitivity of the detector in this range.

Image of FIG. 7.
FIG. 7.

Comparison of experimental and theoretical ABS and rR spectra of [NiII(L)(L)]1−. The corresponding excited state displacement parameters were obtained using the gradient techniques. (Left) Experimental (black) and deconvoluted (red) ABS spectrum of [NiII(L)(L)]1− in the range 9000–17 000 cm−1. The component electronic bands are represented by blue curves. The transition energies, transition moments, and linewidth parameters were varied in the fit while the values of the dimensionless normal coordinate displacements and vibrational frequencies were fixed to those obtained at the B3LYP/TZV(2df,p) level of theory. (Right) Experimental and simulated rR spectra corresponding to the fitted parameters and normal mode displacements obtained from the B3LYP/TZV(2df,p) DFT calculations. The component rR spectra are represented by blue (1b1u→2b2g) and green (1au→2b2g) curves, respectively.

Image of FIG. 8.
FIG. 8.

Comparison of experimental and theoretical ABS and rR spectra of [NiII(L)(L)]1−. The corresponding excited state displacement parameters were obtained using the global geometry optimization techniques. (Left) Experimental (black) and deconvoluted (red) ABS spectrum of [NiII(L)(L)]1− in the range 9000–17 000 cm−1. The component electronic bands are represented by blue curves. The transition energies, transition moments, and linewidth parameters were varied in the fit while the values of the dimensionless normal coordinate displacements and vibrational frequencies were fixed to those obtained at the B3LYP/TZV(2df,p) level of theory using (right) experimental and simulated rR spectra corresponding to the fitted parameters and normal mode displacements obtained from the B3LYP/TZV(2df,p) DFT calculations. The component rR spectra are represented by blue (1b1u→2b2g) and green (1au→2b2g) curves, respectively.

Image of FIG. 9.
FIG. 9.

Simulated 4th order rR spectra of Rub for T = 0 K and T = 80 K, as obtained at the B3LYP/TZV(2df,p) level of theory using the gradient techniques for calculating dimensionless normal coordinate displacements. The individual Raman bands are represented by Lorentzians, with a FWHM of 8.0 cm−1. The bars indicate the dominant contributions from various fundamental, overtone, and combination transitions to the observable peaks.

Tables

Generic image for table
Table I.

Calculated and experimental values of the vibrational frequencies (cm−1) and excited state dimensionless normal coordinate displacements corresponding to the 11Ag →11Bu transition of trans-1,3,5-hexatriene. The calculated displacements were obtained at the B3LYP/TZV(2df,p) level of theory using the gradient techniques (grad.), and global geometry optimization method (opt.).

Generic image for table
Table II.

Total wall clock times for single-point TDDFT/TDA excitation energies and excited state gradient calculations of representative dipole allowed transitions in a set of large molecules (16 processors were used for each job). All calculations were performed with the B3LYP functional. Basis set labels refer to the “def2” variants.51,58 All TDDFT calculations were performed for the first 10 roots. NA denotes the number of atoms, NBFs is the number of basis functions, NABFs is the number of auxiliary basis functions.

Generic image for table
Table III.

Total wall clock times for the simulation of ABS spectra corresponding to dipole allowed transitions in a set of large molecules.

Generic image for table
Table IV.

Total wall clock times for the simulation of rR spectra corresponding to dipole allowed transitions in a set of large molecules. The excitation energies correspond to the absorption maxima.

Generic image for table
Table V.

Total wall clock times for the simulations of zero- and finite temperature rR spectra corresponding to dipole allowed transitions in hexatriene and rubrene, using prescreening conditions for selecting initial vibrational states and Raman transitions. The excitation energies correspond to the absorption maxima. N I is the number of initial vibrational states, N R is the number of Raman transition vectors.

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/content/aip/journal/jcp/137/23/10.1063/1.4771959
2012-12-20
2014-04-20
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: Efficient and automatic calculation of optical band shapes and resonance Raman spectra for larger molecules within the independent mode displaced harmonic oscillator model
http://aip.metastore.ingenta.com/content/aip/journal/jcp/137/23/10.1063/1.4771959
10.1063/1.4771959
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