Calculation and interpretation of vibronic absorption and fluorescence spectra of the first electronic nπ* transitions of pyridine and pyrimidine

Ten, G. N.; Kadrov, D. M.; Berezin, M. K.; Баранов, В. И.

doi:10.1134/s0030400x14100221

Cited by 4 publications

(3 citation statements)

References 17 publications

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“…Pyridine has been the subject of numerous studies applying Raman and IR spectroscopy. − In 1974, Fleischmann et al discovered the surface enhancement effect by bringing pyridine in the vicinity of silver electrodes . Thereafter, a large effort was made to investigate pyridine–metal complexes in both quantum-mechanical and experimental investigations.…”

Section: Introductionmentioning

confidence: 99%

Fundamental SERS Investigation of Pyridine and Its Derivates as a Function of Functional Groups, Their Substitution Position, and Their Interaction with Silver Nanoparticles

2017

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The Raman and surface-enhanced Raman spectroscopy (SERS) spectra of pyridine, 2-, 3-, and 4pyridinemethanol and 2-, 3-, and 4-picolylamine were comprehensively studied using two different types of silver nanoparticles as SERS substrates, namely citrate-reduced and hydroxylamine-reduced silver nanoparticles, which are the most commonly used silver colloids. For a robust band assignment, Raman spectra of the investigated molecules were simulated, applying Møller−Plesset perturbation theory in conjunction with the 6 311++G(d, p) basis set. Subsequently, the observed changes in the spectra were interpreted and discussed in detail, taking into account the simulated Raman spectra. Furthermore, differences in the spectral information resulting from the two different analyzed functional groups, the altering of the substitution position and the molecular orientation relative to the metal surface were discussed, and general conclusions for an application of those molecules as Raman reporters were derived.

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Section: Introductionmentioning

confidence: 99%

Fundamental SERS Investigation of Pyridine and Its Derivates as a Function of Functional Groups, Their Substitution Position, and Their Interaction with Silver Nanoparticles

2017

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“…In this study, we describe a general approach for simulating spectral intensities based on an accurate representation of the ground and excited PESs. Within anharmonic calculations, − it is the proper representation of extended regions of the PES, which render these calculations expensive . The theoretical level for calculating the PES of the excited or ionized state(s) has the most impact on the accuracy of the simulated spectra.…”

Section: Introductionmentioning

confidence: 99%

“…However, in this study we employ a single-reference approach, in which the reference occupation numbers are determined in an average way according to the CFCFs values, as explained below. We define the modal-contracted Franck−Condon factor (MCFCF) for modal φ i m (e) as (25) where {k(i m )} are the indices of the configurations involving modal φ i m (e) . It is straightforward to show that if the configuration basis is complete then…”

Section: Introductionmentioning

confidence: 99%

A General Approach for Calculating Strongly Anharmonic Vibronic Spectra with a High Density of States: The X̃²B₁ ← X̃¹A₁ Photoelectron Spectrum of Difluoromethane

Petrenko¹,

Rauhut²

2017

J. Chem. Theory Comput.

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Due to a low-lying fragmentation channel, the X̃B ← X̃A photoelectron spectrum of difluoromethane is dominated by strong anharmonicity effects. We have used a time-independent eigenstate-free Raman wave function approach (RWF) to calculate the entire spectrum. Vibronic transitions with the most significant Franck-Condon factors were determined by employing our recently developed residual-based algorithm for the calculation of eigenpairs (RACE). An analysis of the factors controlling the accuracy of the predicted band shape is provided. The calculated spectrum is in very close agreement with experimental results.

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Time-independent eigenstate-free calculation of vibronic spectra beyond the harmonic approximation

Petrenko

Rauhut

2015

The Journal of Chemical Physics

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The calculation of vibronic spectra and resonance Raman intensities can be performed on the basis of the Raman wavefunction (RWF) formalism. In general, the well-known sum-over-states (SOS) and time-dependent methods can be applied for calculating the RWF. We present an alternative route in which the RWF is determined pointwise in a spectral range on the basis of the inhomogeneous Schrödinger equation using an iterative subspace method, in which explicit state-by-state calculations of vibrational eigenstates are bypassed. We study this approach within the framework of vibrational configuration interaction theory in conjunction with high-level electronic structure calculations for the multidimensional Born-Oppenheimer potential energy surface. The method benefits from an implicit account of interference effects between vibrational states, so that its computational cost correlates with the required resolution in the spectra. The accuracy and efficiency of the method with respect to comparable SOS calculations are tested for the simulation of the photoelectron spectra of ClO2, HS2 (-), ZnOH(-), and Zn(H2O)(+).

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Calculation and interpretation of vibronic absorption and fluorescence spectra of the first electronic nπ* transitions of pyridine and pyrimidine

Cited by 4 publications

References 17 publications

Fundamental SERS Investigation of Pyridine and Its Derivates as a Function of Functional Groups, Their Substitution Position, and Their Interaction with Silver Nanoparticles

Fundamental SERS Investigation of Pyridine and Its Derivates as a Function of Functional Groups, Their Substitution Position, and Their Interaction with Silver Nanoparticles

A General Approach for Calculating Strongly Anharmonic Vibronic Spectra with a High Density of States: The X̃²B₁ ← X̃¹A₁ Photoelectron Spectrum of Difluoromethane

Time-independent eigenstate-free calculation of vibronic spectra beyond the harmonic approximation

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Calculation and interpretation of vibronic absorption and fluorescence spectra of the first electronic nπ* transitions of pyridine and pyrimidine

Cited by 4 publications

References 17 publications

Fundamental SERS Investigation of Pyridine and Its Derivates as a Function of Functional Groups, Their Substitution Position, and Their Interaction with Silver Nanoparticles

Fundamental SERS Investigation of Pyridine and Its Derivates as a Function of Functional Groups, Their Substitution Position, and Their Interaction with Silver Nanoparticles

A General Approach for Calculating Strongly Anharmonic Vibronic Spectra with a High Density of States: The X̃2B1 ← X̃1A1 Photoelectron Spectrum of Difluoromethane

Time-independent eigenstate-free calculation of vibronic spectra beyond the harmonic approximation

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A General Approach for Calculating Strongly Anharmonic Vibronic Spectra with a High Density of States: The X̃²B₁ ← X̃¹A₁ Photoelectron Spectrum of Difluoromethane