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A multilayer MCTDH study on the full dimensional vibronic dynamics of naphthalene and anthracene cations
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10.1063/1.4772779
/content/aip/journal/jcp/138/1/10.1063/1.4772779
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/1/10.1063/1.4772779

Figures

Image of FIG. 1.
FIG. 1.

The ML-MCTDH wavefunction structure (ML-tree structure) for the 48D ML-MCTDH simulations of naphthalene which is excited to the or state of Np+. The maxima depth of the trees are six layers, and the first layer separates the 48 vibrational coordinates from the discrete electronic DOF. The number of SPFs are also given. The numbers of primitive basis sets to represent SPFs of the deepest layer are given next to the lines connecting with the squares. The vibrational modes with a star are the ones which are included in the reduced dimensional Hamitonian.

Image of FIG. 2.
FIG. 2.

Comparison of the 48D ML-MCTDH and 29D MCTDH theoretical (lower panel) vs experimental 14 PE (upper panel) (reprinted with permission from Related Article(s): R. S. Sanchez-Carrera, V. Coropceanu, D. A. da Silva Filho, R. Friedlein, W. Osikowicz, R. Murdey, C. Suess, W. R. Salaneck, and J.-L. Bredas, J. Phys. Chem. B110, 18908 (Year: 2006)10.1021/jp057462p

; copyright 2006 American Chemical Society) spectra of naphthalene radical cation. The 48D ML-MCTDH and 29D MCTDH theoretical spectra are obtained by a Fourier-transform of the autocorrelation function. These spectra are then broadened by convoluting them with a Gaussian. The resulting resolution of the computed spectra is 33 meV FWHM.

Image of FIG. 3.
FIG. 3.

Same as Figure 2 , except for anthracene radical cation. Note that the full and reduced dimensionalities in the present simulations for anthracene radical cation are 66D and 31D, respectively. The resolution of the computed spectra is set to 64 meV FWHM. (Upper panel) Reprinted with permission from Related Article(s): R. S. Sanchez-Carrera, V. Coropceanu, D. A. da Silva Filho, R. Friedlein, W. Osikowicz, R. Murdey, C. Suess, W. R. Salaneck, and J.-L. Bredas, J. Phys. Chem. B110, 18908 (Year: 2006)10.1021/jp057462p

. Copyright 2006 American Chemical Society.

Image of FIG. 4.
FIG. 4.

Comparison of the 48D ML-MCTDH and 29D MCTDH theoretical (the lowest panel) vs the experimental absorption spectra based on the MIS technique 18 (the middle two panels, reprinted with permission from Related Article(s): F. Salama and L. J. Allamandola, J. Chem. Phys.94, 6964 (Year: 1991)10.1063/1.460230

; copyright 1991 American Institute of Physics) and the experimental PE spectrum 13 (the uppermost panel, reprinted with permission from D. A. da Silva Filho, R. Friedlein, V. Coropceanu, G. Öhrwall, W. Osikowicz, C. Suess, S. L. Sorensen, S. Svensson, W. R. Salaneck, and J.-L. Bredas, Chem. Commun. 2004, 1702; copyright 2004 The Royal Society of Chemistry) of the third ionization band of naphthalene. The 48D ML-MCTDH and 29D MCTDH theoretical spectra are obtained by a Fourier-transform of the autocorrelation function. These spectra are then broadened by convoluting them with a Gaussian. The resulting resolution is 14 meV FWHM. The solid line (——) represents the full dimensional ML-MCTDH simulated spectra while the dashed line (– – –) represents the reduced dimensional MCTDH simulated spectra.

Image of FIG. 5.
FIG. 5.

Comparison of the 66D ML-MCTDH and 31D MCTDH theoretical (the lowest panel) vs the REMPD absorption spectrum 20 (reprinted with permission from Related Article(s): D. Rolland, A. A. Specht, M. W. Blades, and J. W. Hepburn, Chem. Phys. Lett.373, 292 (Year: 2003)10.1016/S0009-2614(03)00517-7

; copyright 2003 Elsevier), Ar matrix absorption spectrum 19 (reprinted with permission from Related Article(s): J. Szczepanski, M. Vala, D. Talbi, O. Parisel, and Y. Ellinger, J. Chem. Phys.98, 4494 (Year: 1993)10.1063/1.465009

; copyright 1993 American Institute of Physics) both in the middle panel, and gas-phase PE spectrum 14 (reprinted with permission from Related Article(s): R. S. Sanchez-Carrera, V. Coropceanu, D. A. da Silva Filho, R. Friedlein, W. Osikowicz, R. Murdey, C. Suess, W. R. Salaneck, and J.-L. Bredas, J. Phys. Chem. B110, 18908 (Year: 2006)10.1021/jp057462p

; copyright 2006 American Chemical Society) of the third ionization band of anthracene. The 66D ML-MCTDH and 31D MCTDH theoretical spectra are obtained by a Fourier-transform of the autocorrelation function. These spectra are then broadened by convoluting them with a Gaussian. The resulting resolution is 14 meV FWHM. The solid line (——) represents the full dimensional ML-MCTDH simulated spectra while the dashed line (– – –) represents the reduced dimensional MCTDH simulated spectra.

Tables

Generic image for table
Table I.

Normal mode combination schemes and sizes of primitive and single particle basis sets used in the reduced dimensional MCTDH calculations on Np+ and An+. The first column contains the vibrational modes combinations to define multi-dimensional particles, i.e., combined modes. The vibrational modes and frequencies of Np and An neutral molecules are given in supporting information 1 in the supplemental material. 58 The second column shows the number of harmonic oscillator discrete variable representation (DVR) functions (primitive basis sets) used to represent the single particle functions (SPFs). The order is the same as in the first column. The right most column gives the SPF sizes, which indicate the number of SPFs on different electronic states in the order of [ , , , , , ].

Generic image for table
Table II.

Numerical resources used by the various full and reduced dimensional calculations for Np+ and An+. The third column contains the single-core time of each of ML-MCTDH or MCTDH simulation using a total propagation time of 400 fs. All simulations were run on the same machine and CPU type (AMD Opteron Processor 246, 2000 MHz). The fourth column shows the total number of time-dependent coefficients propagated in each case. The right most column shows the total memory (in megabyte, Mb) used during the calculations.

Generic image for table
Table III.

Theoretical and experimental vibronic energy-levels position of Np+ relative to the ionization energy (8.15 eV) 60 of (in nm wavelength). Given in the first and second columns are the 48D ML-MCTDH and 29D MCTDH results, respectively. The third column shows the DIBs observed by observatories. The other columns contain the experimental PE results observed using different kinds of spectroscopy. The right most column gives possible experimental assignments. Comparisons of the theoretical and experimental spectra of Np+ ( ) are shown in Figure 4 .

Generic image for table
Table IV.

Theoretical and experimental vibronic energy-levels position of An+ relative to the ionization energy (7.42 eV) 12,14 of (in nm wavelength). Given in the first and second columns are the 66D ML-MCTDH and 31D MCTDH results, respectively. The third column shows the DIBs observed by observatories. The other columns contain the experimental PE results observed using different kinds of spectroscopy. The right most column gives possible experimental assignments. Comparisons of the theoretical and experimental spectra of An+ ( ) are shown in Figure 5 .

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2013-01-07
2014-04-20
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752b84549af89a08dbdd7fdb8b9568b5 journal.articlezxybnytfddd
Scitation: A multilayer MCTDH study on the full dimensional vibronic dynamics of naphthalene and anthracene cations
http://aip.metastore.ingenta.com/content/aip/journal/jcp/138/1/10.1063/1.4772779
10.1063/1.4772779
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