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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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| Zeitschriftentitel: | The Journal of Chemical Physics |
|---|---|
| Personen und Körperschaften: | , |
| In: | The Journal of Chemical Physics, 137, 2012, 23 |
| Format: | E-Article |
| Sprache: | Englisch |
| veröffentlicht: |
AIP Publishing
|
| Schlagwörter: |
| author_facet |
Petrenko, Taras Neese, Frank Petrenko, Taras Neese, Frank |
|---|---|
| author |
Petrenko, Taras Neese, Frank |
| spellingShingle |
Petrenko, Taras Neese, Frank The Journal of Chemical Physics Efficient and automatic calculation of optical band shapes and resonance Raman spectra for larger molecules within the independent mode displaced harmonic oscillator model Physical and Theoretical Chemistry General Physics and Astronomy |
| author_sort |
petrenko, taras |
| spelling |
Petrenko, Taras Neese, Frank 0021-9606 1089-7690 AIP Publishing Physical and Theoretical Chemistry General Physics and Astronomy http://dx.doi.org/10.1063/1.4771959 <jats:p>In this work, an improved method for the efficient automatic simulation of optical band shapes and resonance Raman (rR) intensities within the “independent mode displaced harmonic oscillator” is described. Despite the relative simplicity of this model, it is able to account for the intensity distribution in absorption (ABS), fluorescence, and rR spectra corresponding to strongly dipole allowed electronic transitions with high accuracy. In order to include temperature-induced effects, we propose a simple extension of the time dependent wavepacket formalism developed by Heller which enables one to derive analytical expressions for the intensities of hot bands in ABS and rR spectra from the dependence of the wavepacket evolution on its initial coordinate. We have also greatly optimized the computational procedures for numerical integration of complicated oscillating integrals. This is important for efficient simulations of higher-order rR spectra and excitation profiles, as well as for the fitting of experimental spectra of large molecules. In particular, the multimode damping mechanism is taken into account for efficient reduction of the upper time limit in the numerical integration. Excited state energy gradient as well as excited state geometry optimization calculations are employed in order to determine excited state dimensionless normal coordinate displacements. The gradient techniques are highly cost-effective provided that analytical excited state derivatives with respect to nuclear displacements are available. Through comparison with experimental spectra of some representative molecules, we illustrate that the gradient techniques can even outperform the geometry optimization method if the harmonic approximation becomes inadequate.</jats:p> Efficient and automatic calculation of optical band shapes and resonance Raman spectra for larger molecules within the independent mode displaced harmonic oscillator model The Journal of Chemical Physics |
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| title |
Efficient and automatic calculation of optical band shapes and resonance Raman spectra for larger molecules within the independent mode displaced harmonic oscillator model |
| title_unstemmed |
Efficient and automatic calculation of optical band shapes and resonance Raman spectra for larger molecules within the independent mode displaced harmonic oscillator model |
| title_full |
Efficient and automatic calculation of optical band shapes and resonance Raman spectra for larger molecules within the independent mode displaced harmonic oscillator model |
| title_fullStr |
Efficient and automatic calculation of optical band shapes and resonance Raman spectra for larger molecules within the independent mode displaced harmonic oscillator model |
| title_full_unstemmed |
Efficient and automatic calculation of optical band shapes and resonance Raman spectra for larger molecules within the independent mode displaced harmonic oscillator model |
| title_short |
Efficient and automatic calculation of optical band shapes and resonance Raman spectra for larger molecules within the independent mode displaced harmonic oscillator model |
| title_sort |
efficient and automatic calculation of optical band shapes and resonance raman spectra for larger molecules within the independent mode displaced harmonic oscillator model |
| topic |
Physical and Theoretical Chemistry General Physics and Astronomy |
| url |
http://dx.doi.org/10.1063/1.4771959 |
| publishDate |
2012 |
| physical |
|
| description |
<jats:p>In this work, an improved method for the efficient automatic simulation of optical band shapes and resonance Raman (rR) intensities within the “independent mode displaced harmonic oscillator” is described. Despite the relative simplicity of this model, it is able to account for the intensity distribution in absorption (ABS), fluorescence, and rR spectra corresponding to strongly dipole allowed electronic transitions with high accuracy. In order to include temperature-induced effects, we propose a simple extension of the time dependent wavepacket formalism developed by Heller which enables one to derive analytical expressions for the intensities of hot bands in ABS and rR spectra from the dependence of the wavepacket evolution on its initial coordinate. We have also greatly optimized the computational procedures for numerical integration of complicated oscillating integrals. This is important for efficient simulations of higher-order rR spectra and excitation profiles, as well as for the fitting of experimental spectra of large molecules. In particular, the multimode damping mechanism is taken into account for efficient reduction of the upper time limit in the numerical integration. Excited state energy gradient as well as excited state geometry optimization calculations are employed in order to determine excited state dimensionless normal coordinate displacements. The gradient techniques are highly cost-effective provided that analytical excited state derivatives with respect to nuclear displacements are available. Through comparison with experimental spectra of some representative molecules, we illustrate that the gradient techniques can even outperform the geometry optimization method if the harmonic approximation becomes inadequate.</jats:p> |
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| description | <jats:p>In this work, an improved method for the efficient automatic simulation of optical band shapes and resonance Raman (rR) intensities within the “independent mode displaced harmonic oscillator” is described. Despite the relative simplicity of this model, it is able to account for the intensity distribution in absorption (ABS), fluorescence, and rR spectra corresponding to strongly dipole allowed electronic transitions with high accuracy. In order to include temperature-induced effects, we propose a simple extension of the time dependent wavepacket formalism developed by Heller which enables one to derive analytical expressions for the intensities of hot bands in ABS and rR spectra from the dependence of the wavepacket evolution on its initial coordinate. We have also greatly optimized the computational procedures for numerical integration of complicated oscillating integrals. This is important for efficient simulations of higher-order rR spectra and excitation profiles, as well as for the fitting of experimental spectra of large molecules. In particular, the multimode damping mechanism is taken into account for efficient reduction of the upper time limit in the numerical integration. Excited state energy gradient as well as excited state geometry optimization calculations are employed in order to determine excited state dimensionless normal coordinate displacements. The gradient techniques are highly cost-effective provided that analytical excited state derivatives with respect to nuclear displacements are available. Through comparison with experimental spectra of some representative molecules, we illustrate that the gradient techniques can even outperform the geometry optimization method if the harmonic approximation becomes inadequate.</jats:p> |
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| spelling | Petrenko, Taras Neese, Frank 0021-9606 1089-7690 AIP Publishing Physical and Theoretical Chemistry General Physics and Astronomy http://dx.doi.org/10.1063/1.4771959 <jats:p>In this work, an improved method for the efficient automatic simulation of optical band shapes and resonance Raman (rR) intensities within the “independent mode displaced harmonic oscillator” is described. Despite the relative simplicity of this model, it is able to account for the intensity distribution in absorption (ABS), fluorescence, and rR spectra corresponding to strongly dipole allowed electronic transitions with high accuracy. In order to include temperature-induced effects, we propose a simple extension of the time dependent wavepacket formalism developed by Heller which enables one to derive analytical expressions for the intensities of hot bands in ABS and rR spectra from the dependence of the wavepacket evolution on its initial coordinate. We have also greatly optimized the computational procedures for numerical integration of complicated oscillating integrals. This is important for efficient simulations of higher-order rR spectra and excitation profiles, as well as for the fitting of experimental spectra of large molecules. In particular, the multimode damping mechanism is taken into account for efficient reduction of the upper time limit in the numerical integration. Excited state energy gradient as well as excited state geometry optimization calculations are employed in order to determine excited state dimensionless normal coordinate displacements. The gradient techniques are highly cost-effective provided that analytical excited state derivatives with respect to nuclear displacements are available. Through comparison with experimental spectra of some representative molecules, we illustrate that the gradient techniques can even outperform the geometry optimization method if the harmonic approximation becomes inadequate.</jats:p> Efficient and automatic calculation of optical band shapes and resonance Raman spectra for larger molecules within the independent mode displaced harmonic oscillator model The Journal of Chemical Physics |
| spellingShingle | Petrenko, Taras, Neese, Frank, The Journal of Chemical Physics, Efficient and automatic calculation of optical band shapes and resonance Raman spectra for larger molecules within the independent mode displaced harmonic oscillator model, Physical and Theoretical Chemistry, General Physics and Astronomy |
| title | Efficient and automatic calculation of optical band shapes and resonance Raman spectra for larger molecules within the independent mode displaced harmonic oscillator model |
| title_full | Efficient and automatic calculation of optical band shapes and resonance Raman spectra for larger molecules within the independent mode displaced harmonic oscillator model |
| title_fullStr | Efficient and automatic calculation of optical band shapes and resonance Raman spectra for larger molecules within the independent mode displaced harmonic oscillator model |
| title_full_unstemmed | Efficient and automatic calculation of optical band shapes and resonance Raman spectra for larger molecules within the independent mode displaced harmonic oscillator model |
| title_short | Efficient and automatic calculation of optical band shapes and resonance Raman spectra for larger molecules within the independent mode displaced harmonic oscillator model |
| title_sort | efficient and automatic calculation of optical band shapes and resonance raman spectra for larger molecules within the independent mode displaced harmonic oscillator model |
| title_unstemmed | Efficient and automatic calculation of optical band shapes and resonance Raman spectra for larger molecules within the independent mode displaced harmonic oscillator model |
| topic | Physical and Theoretical Chemistry, General Physics and Astronomy |
| url | http://dx.doi.org/10.1063/1.4771959 |